QUINOLINEAMINE ANTIDEGRADANT COMPOUNDS AND USES THEREOF

Abstract

The present disclosure provides compounds represented by Formula (I) or salts or solvates thereof, wherein R.sup.1, R.sup.2a, R.sup.2b, R.sup.2c, R.sup.3a, R.sup.3b, R.sup.3c, R.sup.3d, and (II) are as defined in the specification. The present disclosure also provides compositions, vulcanized NH elastomeric articles, lubricant compositions, combustible fuel compositions, and fuel additive compositions comprising a compound disclosed herein. The present disclosure also provides processes for preparing the compositions and vulcanized elastomeric articles described herein. The present disclosure also provides a process for retreading tires using a composition described herein. The present disclosure also provides kits comprising a composition described

##STR00001##

custom-character (II)

Claims

1. A compound having Formula (I): ##STR00147## or a salt, solvate, or stereoisomer thereof, wherein: custom-character is a single or a double bond; R.sup.1 is selected from the group consisting of optionally substituted C.sub.1-C.sub.12 alkyl, CHR.sup.1aR.sup.1b, C.sub.3-C.sub.6 cycloalkyl, 4- to 6-membered heterocyclyl, optionally substituted phenyl, and optionally substituted 5- or 6-membered heteroaryl; R.sup.1a is selected from the group consisting of optionally substituted phenyl, C.sub.3-C.sub.6 cycloalkyl, 4- to 6-membered heterocyclo, and optionally substituted 5- or 6-membered heteroaryl; R.sup.1b is selected from the group consisting of hydrogen and C.sub.1-C.sub.9 alkyl; R.sup.2a, R.sup.2b, and R.sup.2c are independently selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.9 alkyl, C.sub.1-C.sub.9 haloalkyl, C.sub.3-C.sub.8 cycloalkyl, C.sub.1-C.sub.8 alkoxy, C.sub.1-C.sub.8 alkylthio, C(O)OR.sup.4, OC(O)R.sup.4, C(O)NR.sup.4R.sup.5, NR.sup.4C(O)R.sup.5, NR.sup.4R.sup.5, OH, SH, SC(O)R.sup.4, SC(O)SR.sup.4, SC(O)NR.sup.4R.sup.5, NR.sup.4C(O)SR.sup.5, NR.sup.4C(S)SR.sup.5, 4- to 6-membered heterocyclyl, optionally substituted phenyl, and optionally substituted 5- or 6-membered heteroaryl, with the proviso that at least one of R.sup.2a, R.sup.2b, or R.sup.2c is not hydrogen; R.sup.3a is selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.9 alkyl, optionally substituted phenyl, C(O)OR.sup.4, C(O)NR.sup.4R.sup.5, C(O)SR.sup.4, CH.sub.2OR.sup.4, CH.sub.2OC(O)R.sup.4, and ##STR00148## R.sup.3b is selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.9 alkyl, and optionally substituted phenyl; or R.sup.3a and R.sup.3b taken together with the carbon atom to which they are attached form a C.sub.3-C.sub.12 cycloalkyl; R.sup.3c is selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.9 alkyl, optionally substituted phenyl, C(O)OR.sup.4, C(O)NR.sup.4R.sup.5, C(O)SR.sup.4, CH.sub.2OR.sup.4, CH.sub.2OC(O)R.sup.4, and ##STR00149## R.sup.3d is selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.9 alkyl, and optionally substituted phenyl; or R.sup.3c and R.sup.3d taken together with the two carbon atoms to which they are attached form a C.sub.3-C.sub.12cycloalkyl; Z at each occurrence is independently selected from the group consisting of O, S, and NR.sup.7; R.sup.4 at each occurrence is independently selected from the group consisting of hydrogen, C.sub.1-C.sub.9 alkyl, C.sub.3-C.sub.6 cycloalkyl, and optionally substituted phenyl; and R.sup.5 at each occurrence is independently selected from the group consisting of hydrogen, C.sub.1-C.sub.9 alkyl, C.sub.3-C.sub.6 cycloalkyl, and optionally substituted phenyl; R.sup.6a, R.sup.6b, R.sup.60, and R.sup.6d at each occurrence are independently selected from the group consisting of hydrogen, C.sub.1-C.sub.12 alkyl, and optionally substituted phenyl; and R.sup.7 at each occurrence is independently selected from the group consisting or hydrogen and C.sub.1-C.sub.6 alkyl.

2. (canceled)

3. The compound of claim 2, or a salt, solvate, or stereoisomer thereof, wherein R.sup.3a, R.sup.3b, and R.sup.3c are methyl.

4. The compound of claim 1, or a salt, solvate, or stereoisomer thereof, wherein R.sup.1 is optionally substituted phenyl.

5. The compound of claim 1, or a salt, solvate, or stereoisomer thereof, wherein R.sup.1 is CHR.sup.1aR.sup.1b, R.sup.1a is optionally substituted phenyl, and R.sup.2a is C.sub.1-C.sub.9 alkyl.

6. The compound of claim 1, or a salt, solvate, or stereoisomer thereof, having Formula (II): ##STR00150## wherein R.sup.2a is selected from the group consisting of halogen, C.sub.1-C.sub.9 alkyl, C.sub.1-C.sub.8 alkoxy, and C.sub.1-C.sub.8.

7. (canceled)

8. The compound of claim 6, or a salt, solvate, or stereoisomer thereof, wherein R.sup.2a is methyl.

9-24. (canceled)

25. The compound of claim 6, or a salt, solvate, or stereoisomer thereof, wherein custom-character is a double bond.

26. The compound of claim 6, or a salt, solvate, or stereoisomer thereof, wherein custom-character is a single bond.

27. The compound of claim 6, or a salt, solvate, or stereoisomer thereof, wherein R.sup.3a and R.sup.3c are C(O)OR.sup.4.

28. (canceled)

29. The compound of claim 27, or a salt, solvate, or stereoisomer thereof, wherein each R.sup.4 is ethyl.

30. (canceled)

31. The compound of claim 29, or a salt, solvate, or stereoisomer thereof, wherein R.sup.3b is methyl.

32. The compound of claim 1, or a salt, solvate, or stereoisomer thereof, selected from the group consisting of: ##STR00151## ##STR00152## ##STR00153## ##STR00154## ##STR00155## ##STR00156## ##STR00157## ##STR00158## ##STR00159## ##STR00160## ##STR00161## ##STR00162## ##STR00163## ##STR00164## ##STR00165##

33. A composition comprising: (i) the compound of claim 1; and (ii) one or more elastomers; or (iii) one or more fillers; or (iv) one or more rubber chemicals; or (v) one or more plasticizers; or (vi) a second antidegradant; or (vii) a combination of one or more elastomers, one or more fillers, one or more rubber chemicals, one or more plasticizers, and/or a second antidegradant.

34. The composition of claim 33, wherein the composition comprises one or more elastomers.

35-50. (canceled)

51. The composition of claim 34, wherein the composition comprises from about 0.1 phr to about 10 phr of the compound.

52-53. (canceled)

54. The composition of claim 33, wherein the composition comprises one or more fillers.

55-60. (canceled)

61. The composition of a claim 33, wherein the composition comprises one or more rubber chemicals.

62-84. (canceled)

85. The composition of claim 33, wherein the composition comprises one or more plasticizers.

86-91. (canceled)

92. The composition of claim 33, wherein the composition further comprises a second antidegradant.

93-103. (canceled)

104. A composition comprising the compound of claim 1 and one or more carriers.

105. (canceled)

106. A vulcanized elastomeric article comprising the compound of claim 1.

107. A vulcanized elastomeric article prepared using the composition of claim 33.

108-112. (canceled)

113. A process for preparing a vulcanized elastomeric article, the process comprising: (a) forming the composition of claim 34 into a formed shape; and (b) vulcanizing the formed shape to provide a vulcanized elastomeric article.

114-126. (canceled)

127. The composition of claim 33, wherein the composition comprises from about 0.1 wt/wt % to about 10 wt/wt % of the compound.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0039] FIG. 1 is a line graph depicting a .sup.1H nuclear magnetic resonance (NMR) spectrum of Intermediate Compound 1-I in d.sub.6-dimethylsulfoxide (d.sub.6-DMSO).

[0040] FIG. 2 is a line graph depicting a .sup.13C NMR spectrum of Intermediate Compound 1-I in d.sub.6-DMSO.

[0041] FIG. 3 is a line graph depicting a NMR spectrum of Compound 1 in d.sub.6-DMSO.

[0042] FIG. 4 is a line graph depicting a .sup.13C NMR spectrum of Compound 1 in d.sub.6-DMSO.

[0043] FIG. 5 is a line graph depicting a NMR spectrum of Intermediate Compound 7-I in d.sub.6-DMSO.

[0044] FIG. 6 is a line graph depicting a .sup.13C NMR spectrum of Intermediate Compound 7-I in d.sub.6-DMSO.

[0045] FIG. 7 is a line graph depicting a NMR spectrum of Compound 7 in d.sub.6-DMSO.

[0046] FIG. 8 is a line graph depicting a .sup.13C NMR spectrum of Compound 7 in d.sub.6-DMSO.

[0047] FIG. 9 is a line graph depicting a .sup.1H NMR spectrum of Compound 2 in d.sub.6-DMSO.

[0048] FIG. 10 is a line graph depicting a .sup.13C NMR spectrum of Compound 2 in d.sub.6-DMSO.

[0049] FIG. 11 is a line graph depicting a .sup.1H NMR spectrum of Intermediate Compound 119-I in d-chloroform (CDCl.sub.3).

[0050] FIG. 12 is a line graph depicting a .sup.1H NMR spectrum of Compound 119 in d.sub.6-DMSO.

[0051] FIG. 13 is a line graph depicting a .sup.13C NMR spectrum of Compound 119 in d.sub.6-DMSO.

[0052] FIG. 14 is a line graph depicting a .sup.13C NMR spectrum of Compound 120 in d.sub.6-DMSO.

[0053] FIG. 15 is a line graph showing force retention as a function of time for sidewall compounds comprising Compound 1 or no antidegradant under dynamic conditions.

[0054] FIG. 16 is a line graph showing force retention as a function of time for tread compounds comprising Compound 1 or no antidegradant under dynamic conditions.

DETAILED DESCRIPTION

[0055] In one embodiment, Compounds of the Disclosure are compounds having Formula (I):

##STR00002##

or a salt, solvate, or stereoisomer thereof, wherein: [0056] custom-character is a single or a double bond; [0057] R.sup.1 is selected from the group consisting of optionally substituted C.sub.1-C.sub.12 alkyl, CHR.sup.1aR.sup.1b, C.sub.3-C.sub.6 cycloalkyl, 4- to 6-membered heterocyclyl, optionally substituted phenyl, and optionally substituted 5- or 6-membered heteroaryl; [0058] R.sup.1a is selected from the group consisting of optionally substituted phenyl, C.sub.3-C.sub.6 cycloalkyl, 4- to 6-membered heterocyclo, and optionally substituted 5- or 6-membered heteroaryl; [0059] R.sup.1b is selected from the group consisting of hydrogen and C.sub.1-C.sub.9 alkyl; [0060] R.sup.2a, R.sup.2b, and R.sup.2c are independently selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.9 alkyl, C.sub.1-C.sub.9 haloalkyl, C.sub.3-C.sub.8 cycloalkyl, C.sub.1-C.sub.5 alkoxy, C.sub.1-C.sub.5 alkylthio, C(O)OR.sup.4, OC(O)R.sup.4, C(O)NR.sup.4R.sup.5, NR.sup.4C(O)R.sup.5, NR.sup.4R.sup.5, OH, SH, SC(O)R.sup.4, SC(O)SR.sup.4, SC(O)NR.sup.4R.sup.5, NR.sup.4C(O)SR.sup.5, NR.sup.4C(S)SR.sup.5, 4- to 6-membered heterocyclyl, optionally substituted phenyl, and optionally substituted 5- or 6-membered heteroaryl, [0061] with the proviso that at least one of R.sup.2a, R.sup.2b, or R.sup.2c is not hydrogen, i.e., at least one of R.sup.2a, R.sup.2b, or R.sup.2c is halogen, C.sub.1-C.sub.9 alkyl, C.sub.1-C.sub.9 haloalkyl, C.sub.3-C.sub.8 cycloalkyl, C.sub.1-C.sub.5 alkoxy, C.sub.1-C.sub.8 alkylthio, C(O)OR.sup.4, OC(O)R.sup.4, C(O)NR.sup.4R.sup.5, NR.sup.4C(O)R.sup.5, NR.sup.4R.sup.5, OH, SH, SC(O)R.sup.4, SC(O)SR.sup.4, SC(O)NR.sup.4R.sup.5, NR.sup.4C(O)SR.sup.5, NR.sup.4C(S)SR.sup.5, 4- to 6-membered heterocyclyl, optionally substituted phenyl, or optionally substituted 5- or 6-membered heteroaryl; [0062] R.sup.3a is selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.9 alkyl, optionally substituted phenyl, C(O)OR.sup.4, C(O)NR.sup.4R.sup.5, C(O)SR.sup.4, CH.sub.2OR.sup.4, CH.sub.2OC(O)R.sup.4, and

##STR00003##

and [0063] R.sup.3b is selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.9 alkyl, and optionally substituted phenyl; or [0064] R.sup.3a and R.sup.3b taken together with the carbon atom to which they are attached form a C.sub.3-C.sub.12 cycloalkyl; [0065] R.sup.3c is selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.9 alkyl, optionally substituted phenyl, C(O)OR.sup.4, C(O)NR.sup.4R.sup.5, C(O)SR.sup.4, CH.sub.2OR.sup.4, CH.sub.2OC(O)R.sup.4, and

##STR00004##

and [0066] R.sup.3d is selected from the group consisting of hydrogen, halogen, C.sub.1-C.sub.9 alkyl, and optionally substituted phenyl; or [0067] R.sup.3c and R.sup.3d taken together with the two carbon atoms to which they are attached form a C.sub.3-C.sub.12 cycloalkyl; [0068] Z at each occurrence is independently selected from the group consisting of O, S, and NR.sup.7; [0069] R.sup.4 at each occurrence is independently selected from the group consisting of hydrogen, C.sub.1-C.sub.9 alkyl, C.sub.3-C.sub.6 cycloalkyl, and optionally substituted phenyl; [0070] R.sup.5 at each occurrence is independently selected from the group consisting of hydrogen, C.sub.1-C.sub.9 alkyl, C.sub.3-C.sub.6 cycloalkyl, and optionally substituted phenyl; [0071] R.sup.6a, R.sup.6b, R.sup.6c, and R.sup.6d at each occurrence are independently selected from the group consisting of hydrogen, C.sub.1-C.sub.12 alkyl, and optionally substituted phenyl; and [0072] R.sup.7 at each occurrence is independently selected from the group consisting or hydrogen and C.sub.1-C.sub.6 alkyl.

[0073] In some embodiments, Compounds of the Disclosure are compounds having Formula (I), wherein R.sup.3a, R.sup.3b, and R.sup.3c are independently selected from the group consisting of methyl, ethyl, propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, and nonyl.

[0074] In some embodiments, Compounds of the Disclosure are compounds having Formula (I), wherein R.sup.3a, R.sup.3b, and R.sup.3c are methyl.

[0075] In some embodiments, Compounds of the Disclosure are compounds having Formula (I), wherein R.sup.1 is optionally substituted phenyl.

[0076] In some embodiments, Compounds of the Disclosure are compounds having Formula (I), wherein R.sup.1 is C.sub.1-C.sub.12 alkyl.

[0077] In another embodiment, Compounds of the Disclosure are compounds having Formula (II):

##STR00005##

or a salt, solvate, or stereoisomer thereof, wherein [0078] R.sup.2a is selected from the group consisting of halogen, C.sub.1-C.sub.9 alkyl, C.sub.1-C.sub.9 haloalkyl, C.sub.3-C.sub.8 cycloalkyl, C.sub.1-C.sub.8 alkoxy, C.sub.1-C.sub.8 alkylthio, C(O)OR.sup.4, OC(O)R.sup.4, C(O)NR.sup.4R.sup.5, NR.sup.4C(O)R.sup.5, NR.sup.4R.sup.5, OH, SH, SC(O)R.sup.4, SC(O)SR.sup.4, SC(O)NR.sup.4R.sup.5, NR.sup.4C(O)SR.sup.5, NHC(S)SR.sup.4, NR.sup.4C(S)SR.sup.5, 4- to 6-membered heterocyclyl, optionally substituted phenyl, and optionally substituted 5- or 6-membered heteroaryl; [0079] custom-character is a single or a double bond; and [0080] R.sup.1, R.sup.3a, R.sup.3b, R.sup.3c, R.sup.3d, R.sup.4, and R.sup.5 are as defined in connection with Formula (I).

[0081] In some embodiments, Compounds of the Disclosure are compounds having Formula (II), wherein R.sup.2a is C.sub.1-C.sub.9 alkyl.

[0082] In some embodiments, Compounds of the Disclosure are compounds having Formula (II), wherein R.sup.2a is methyl.

[0083] In another embodiment, Compounds of the Disclosure are compounds having Formula (III):

##STR00006##

or a salt, solvate, or stereoisomer thereof, wherein [0084] R.sup.2b is selected from the group consisting of halogen, C.sub.1-C.sub.9 alkyl, C.sub.1-C.sub.9 haloalkyl, C.sub.3-C.sub.8 cycloalkyl, C.sub.1-C.sub.8 alkoxy, C.sub.1-C.sub.8 alkylthio, C(O)OR.sup.4, OC(O)R.sup.4, C(O)NR.sup.4R.sup.5, NR.sup.4C(O)R.sup.5, NR.sup.4R.sup.5, OH, SH, SC(O)R.sup.4, SC(O)SR.sup.4, SC(O)NR.sup.4R.sup.5, NR.sup.4C(O)SR.sup.5, NHC(S)SR.sup.4, NR.sup.4C(S)SR.sup.5, 4- to 6-membered heterocyclyl, optionally substituted phenyl, and optionally substituted 5- or 6-membered heteroaryl; custom-character [0085] is a single or a double bond; and [0086] R.sup.1, R.sup.3a, R.sup.3b, R.sup.3c, R.sup.3d, R.sup.4, and R.sup.5 are as defined in connection with Formula (I).

[0087] In some embodiments, Compounds of the Disclosure are compounds having Formula (III), wherein R.sup.2b is C.sub.1-C.sub.9 alkyl.

[0088] In some embodiments, Compounds of the Disclosure are compounds having Formula (III), wherein R.sup.2b is methyl.

[0089] In another embodiment, Compounds of the Disclosure are compounds having Formula (IV):

##STR00007##

or a salt, solvate, or stereoisomer thereof, wherein: [0090] R.sup.2c is selected from the group consisting of halogen, C.sub.1-C.sub.9 alkyl, C.sub.1-C.sub.9 haloalkyl, C.sub.3-C.sub.8 cycloalkyl, C.sub.1-C.sub.8 alkoxy, C.sub.1-C.sub.8 alkylthio, C(O)OR.sup.4, OC(O)R.sup.4, C(O)NR.sup.4R.sup.5, NR.sup.4C(O)R.sup.5, NR.sup.4R.sup.5, OH, SH, SC(O)R.sup.4, SC(O)SR.sup.4, SC(O)NR.sup.4R.sup.5, NR.sup.4C(O)SR.sup.5, NHC(S)SR.sup.4, NR.sup.4C(S)SR.sup.5, 4- to 6-membered heterocyclyl, optionally substituted phenyl, and optionally substituted 5- or 6-membered heteroaryl; [0091] custom-character is a single or a double bond; and [0092] R.sup.1, R.sup.3a, R.sup.3b, R.sup.3c, R.sup.3d, R.sup.4, and R.sup.5 are as defined in connection with Formula (I).

[0093] In some embodiments, Compounds of the Disclosure are compounds having Formula (IV), wherein R.sup.2c is C.sub.1-C.sub.9 alkyl.

[0094] In some embodiments, Compounds of the Disclosure are compounds having Formula (IV), wherein R.sup.2c is methyl.

[0095] In another embodiment, Compounds of the Disclosure are compounds having Formula (V):

##STR00008##

or a salt, solvate, or stereoisomer thereof, wherein: [0096] R.sup.2a and R.sup.2b are independently selected from the group consisting of halogen, C.sub.1-C.sub.9 alkyl, C.sub.1-C.sub.9 haloalkyl, C.sub.3-C.sub.8 cycloalkyl, C.sub.1-C.sub.5 alkoxy, C.sub.1-C.sub.8 alkylthio, C(O)OR.sup.4, OC(O)R.sup.4, C(O)NR.sup.4R.sup.5, NR.sup.4C(O)R.sup.5, NR.sup.4R.sup.5, OH, SH, SC(O)R.sup.4, SC(O)SR.sup.4, SC(O)NR.sup.4R.sup.5, NR.sup.4C(O)SR.sup.5, NHC(S)SR.sup.4, NR.sup.4C(S)SR.sup.5, 4- to 6-membered heterocyclyl, optionally substituted phenyl, and optionally substituted 5- or 6-membered heteroaryl; [0097] custom-character is a single or a double bond; and [0098] R.sup.1, R.sup.3a, R.sup.3b, R.sup.3c, R.sup.3d, R.sup.4, and R.sup.5 are as defined in connection with Formula (I).

[0099] In some embodiments, Compounds of the Disclosure are compounds having Formula (V), wherein R.sup.2a and R.sup.2b are independently C.sub.1-C.sub.9 alkyl.

[0100] In some embodiments, Compounds of the Disclosure are compounds having Formula (V), wherein R.sup.2a and R.sup.2b are methyl.

[0101] In another embodiment, Compounds of the Disclosure are compounds having Formula (VI):

##STR00009##

or a salt, solvate, or stereoisomer thereof, wherein: [0102] R.sup.2a and R.sup.2c are independently selected from the group consisting of halogen, C.sub.1-C.sub.9 alkyl, C.sub.1-C.sub.9 haloalkyl, C.sub.3-C.sub.8 cycloalkyl, C.sub.1-C.sub.8 alkoxy, C.sub.1-C.sub.5 alkylthio, C(O)OR.sup.4, OC(O)R.sup.4, C(O)NR.sup.4R.sup.5, NR.sup.4C(O)R.sup.5, NR.sup.4R.sup.5, OH, SH, SC(O)R.sup.4, SC(O)SR.sup.4, SC(O)NR.sup.4R.sup.5, NR.sup.4C(O)SR.sup.5, NHC(S)SR.sup.4, NR.sup.4C(S)SR.sup.5, 4- to 6-membered heterocyclyl, optionally substituted phenyl, and optionally substituted 5- or 6-membered heteroaryl; [0103] custom-character is a single or a double bond; and [0104] R.sup.1, R.sup.3a, R.sup.3b, R.sup.3c, R.sup.3d, R.sup.4, and R.sup.5 are as defined in connection with Formula (I).

[0105] In some embodiments, Compounds of the Disclosure are compounds having Formula (VI), wherein R.sup.2a and R.sup.2c are independently C.sub.1-C.sub.9 alkyl.

[0106] In some embodiments, Compounds of the Disclosure are compounds having Formula (VI), wherein R.sup.2a and R.sup.2c are methyl.

[0107] In another embodiment, Compounds of the Disclosure are compounds having Formula (VII):

##STR00010##

or a salt, solvate, or stereoisomer thereof, wherein: [0108] R.sup.2b and R.sup.2c are independently selected from the group consisting of halogen, C.sub.1-C.sub.9 alkyl, C.sub.1-C.sub.9 haloalkyl, C.sub.3-C.sub.8 cycloalkyl, C.sub.1-C.sub.5 alkoxy, C.sub.1-C.sub.8 alkylthio, C(O)OR.sup.4, OC(O)R.sup.4, C(O)NR.sup.4R.sup.5, NR.sup.4C(O)R.sup.5, NR.sup.4R.sup.5, OH, SH, SC(O)R.sup.4, SC(O)SR.sup.4, SC(O)NR.sup.4R.sup.5, NR.sup.4C(O)SR.sup.5, NHC(S)SR.sup.4, NR.sup.4C(S)SR.sup.5, 4- to 6-membered heterocyclyl, optionally substituted phenyl, and optionally substituted 5- or 6-membered heteroaryl; [0109] custom-character is a single or a double bond; and [0110] R.sup.1, R.sup.3a, R.sup.3b, R.sup.3c, R.sup.3d, R.sup.4, and R.sup.5 are as defined in connection with Formula (I).

[0111] In some embodiments, Compounds of the Disclosure are compounds having Formula (VII), wherein R.sup.2b and R.sup.2C are independently C.sub.1-C.sub.9 alkyl.

[0112] In some embodiments, Compounds of the Disclosure are compounds having Formula (VII), wherein R.sup.2b and R.sup.2C are methyl.

[0113] In some embodiments, Compounds of the Disclosure are compounds having Formulae (I)-(VII), wherein R.sup.2a, R.sup.2b, and R.sup.2c are independently selected from the group consisting of halogen, C.sub.1-C.sub.9 alkyl, C.sub.1-C.sub.6 alkoxy, and C.sub.1-C.sub.6 alkylthio.

[0114] In some embodiments, Compounds of the Disclosure are compounds having any Formulae (II)-(VII), wherein R.sup.2a, R.sup.2b, and R.sup.2C are independently selected from the group consisting of methyl, ethyl, methoxy, chloro, SCH.sub.3, and SCH.sub.2CH.sub.3.

[0115] In some embodiments, Compounds of the Disclosure are compounds of any one of Formulae (I)-(VII), wherein wherein custom-character is a double bond.

[0116] In some embodiments, Compounds of the Disclosure are compounds of any one of Formulae (I)-(VII), wherein wherein custom-character is a single bond.

[0117] In some embodiments, Compounds of the Disclosure are compounds of any one of Formulae (II)-(VII), wherein R.sup.1 is optionally substituted phenyl.

[0118] In some embodiments, Compounds of the Disclosure are compounds of any one of Formulae (II)-(VII), wherein R.sup.1 is C.sub.1-C.sub.12 alkyl.

[0119] In some embodiments, Compounds of the Disclosure are compounds of any one of Formulae (II)-(VII), wherein R.sup.1 is selected from the group consisting of methyl, ethyl, propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, and nonyl.

[0120] In some embodiments, Compounds of the Disclosure are compounds of any one of Formulae (I)-(VII), wherein R.sup.1 is CHR.sup.1aR.sup.11. In some embodiments, R.sup.1a is selected from the group consisting of optionally substituted phenyl and optionally substituted 5- or 6-membered heteroaryl. In some embodiments, R.sup.1a is phenyl or 2-furyl. In some embodiments, R.sup.1b is hydrogen or methyl.

[0121] In some embodiments, Compounds of the Disclosure are compounds of any one of Formulae (II)-(VII), wherein R.sup.3a, R.sup.3b, and R.sup.3c are independently selected from the group consisting of methyl, ethyl, propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, and nonyl.

[0122] In some embodiments, Compounds of the Disclosure are compounds of any one of Formulae (II)-(VII), wherein R.sup.3a, R.sup.3b, and R.sup.3c are methyl.

[0123] In some embodiments, Compounds of the Disclosure are compounds of any one of Formulae (I)-(VII), wherein R.sup.3b is methyl; and R.sup.3a and R.sup.3c are C.sub.2-C.sub.9 alkyl.

[0124] In some embodiments, Compounds of the Disclosure are compounds of any one of Formulae (I)-(VII), wherein R.sup.3b is methyl; and R.sup.3a and R.sup.3c are ethyl.

[0125] In some embodiments, Compounds of the Disclosure are compounds of any one of Formulae (I)-(VII), wherein R.sup.3a is C(O)OR.sup.4, C(O)NR.sup.4R.sup.5, C(O)SR.sup.4, CH.sub.2OR.sup.4, CH.sub.2OC(O)R.sup.4, or

##STR00011##

[0126] In some embodiments, Compounds of the Disclosure are compounds of any one of Formulae (I)-(VII), wherein R.sup.3a is C(O)OR.sup.4. In some embodiments, R.sup.3a is C(O)OEt.

[0127] In some embodiments, Compounds of the Disclosure are compounds of any one of Formulae (I)-(VII), wherein R.sup.3a is C(O)NR.sup.4R.sup.5.

[0128] In some embodiments, Compounds of the Disclosure are compounds of any one of Formulae (I)-(VII), wherein R.sup.3a is C(O)SR.sup.4.

[0129] In some embodiments, Compounds of the Disclosure are compounds of any one of Formulae (I)-(VII), wherein R.sup.3a is CH.sub.2OR.sup.4.

[0130] In some embodiments, Compounds of the Disclosure are compounds of any one of Formulae (I)-(VII), wherein R.sup.3a is CH.sub.2OC(O)R.sup.4.

[0131] In some embodiments, Compounds of the Disclosure are compounds of any one of Formulae (I)-(VII), wherein R.sup.3a is

##STR00012##

[0132] In some embodiments, Compounds of the Disclosure are compounds of any one of Formulae (I)-(VII), wherein R.sup.3c is C(O)OR.sup.4. In some embodiments, R.sup.3 is C(O)OEt.

[0133] In some embodiments, Compounds of the Disclosure are compounds of any one of Formulae (I)-(VII), wherein R.sup.3c is C(O)NR.sup.4R.sup.5.

[0134] In some embodiments, Compounds of the Disclosure are compounds of any one of Formulae (I)-(VII), wherein R.sup.3c is C(O)SR.sup.4.

[0135] In some embodiments, Compounds of the Disclosure are compounds of any one of Formulae (I)-(VII), wherein R.sup.3c is CH.sub.2OR.sup.4.

[0136] In some embodiments, Compounds of the Disclosure are compounds of any one of Formulae (I)-(VII), wherein R.sup.3c is CH.sub.2OC(O)R.sup.4.

[0137] In some embodiments, Compounds of the Disclosure are compounds of any one of Formulae (I)-(VII), wherein R.sup.3c is

##STR00013##

[0138] In some embodiments, Compounds of the Disclosure are compounds of any one of Formulae (I)-(VII), wherein Z is O. In some embodiments, Z is S. In some embodiments, Z is NR.sup.7. In some embodiments, R.sup.7 is hydrogen. In some embodiments, R.sup.6a, R.sup.6b, R.sup.6c, and R.sup.6d are hydrogen.

[0139] In some embodiments, Compounds of the Disclosure are compounds of any one of Formulae (I)-(VII), wherein each R.sup.4 is hydrogen or C.sub.1-C.sub.9 alkyl.

[0140] In some embodiments, Compounds of the Disclosure are compounds of any one of Formulae (I)-(VII), wherein each R.sup.4 is ethyl.

[0141] In some embodiments, Compounds of the Disclosure are compounds of any one of Formulae (I)-(VII), wherein each R.sup.4 is hydrogen.

[0142] In some embodiments, Compounds of the Disclosure are compounds of any one of Formulae (I)-(VII), wherein R.sup.3b is C.sub.1-C.sub.9 alkyl.

[0143] In some embodiments, Compounds of the Disclosure are compounds of any one of Formulae (I)-(VII), wherein R.sup.3b is methyl.

[0144] In some embodiments, Compounds of the Disclosure are compounds of any one of Formulae (I)-(VII), wherein R.sup.3b is methyl; and R.sup.3a and R.sup.3c are C(O)OR.sup.4.

[0145] In some embodiments, Compounds of the Disclosure are any one or more of the compounds of Table 1, or a salt or solvate thereof.

TABLE-US-00001 TABLE 1 Compound No. Structure 1 [00014] embedded image 2 [00015] 3 [00016] 4 [00017] 5 [00018] 6 [00019] 7 [00020] 8 [00021] 9 [00022] 10 [00023] 11 [00024] 12 [00025] 13 [00026] 14 [00027] 15 [00028] 16 [00029] 17 [00030] 18 [00031] 19 [00032] 20 [00033] 21 [00034] 22 [00035] 23 [00036] 24 [00037] 25 [00038] 26 [00039] 27 [00040] 28 [00041] embedded image 29 [00042] 30 [00043] 31 [00044] 32 [00045] 33 [00046] 34 [00047] 35 [00048] 36 [00049] 37 [00050] 38 [00051] 39 [00052] 40 [00053] 41 [00054] 42 [00055] 43 [00056] 44 [00057] 45 [00058] 46 [00059] 47 [00060] 48 [00061] 49 [00062] 50 [00063] 51 [00064] 52 [00065] 53 [00066] 54 [00067] embedded image 55 [00068] 56 [00069] 57 [00070] 58 [00071] 59 [00072] 60 [00073] 61 [00074] 62 [00075] 63 [00076] 64 [00077] 65 [00078] 66 [00079] 67 [00080] 68 [00081] 69 [00082] 70 [00083] 71 [00084] 72 [00085] 73 [00086] 74 [00087] 75 [00088] 76 [00089] 77 [00090] 78 [00091] 79 [00092] 80 [00093] embedded image 81 [00094] 82 [00095] 83 [00096] 84 [00097] 85 [00098] 86 [00099] 87 [00100] 88 [00101] 89 [00102] 90 [00103] 91 [00104] 92 [00105] 93 [00106] 94 [00107] 95 [00108] 96 [00109] 97 [00110] 98 [00111] 99 [00112] 100 [00113] 101 [00114] 102 [00115] 103 [00116] 104 [00117] 105 [00118] 106 [00119] embedded image 107 [00120] 108 [00121] 109 [00122] 110 [00123] 111 [00124] 112 [00125] 113 [00126] 114 [00127] 115 [00128] 116 [00129] 117 [00130] 118 [00131] 119 [00132] 120 [00133] 121 [00134]

[0146] Compounds of the Disclosure can be useful as antidegradants, e.g., antiozonants and/or antioxidants, as additives in lubricants, and as additives in combustible fuels.

[0147] Compounds of the Disclosure can be prepared by a three-step process comprising i) reacting a secondary arylamine with sodium nitrite in acid, ii) reducing the resulting nitroso intermediate to an amine, and iii) reacting the resulting amine with a ketone, e.g., acetone, or aldehyde, as shown in Scheme 1. Reduction of the nitroso intermediate to an amine can be carried out using any methods known in the art, such as treatment with sodium borohydride (NaBH.sub.4) in ethanol.

##STR00135##

[0148] Compounds of the Disclosure can also be prepared by further reduction of compounds synthesized using Scheme 1, as shown in Scheme 2. Reduction may be carried out using any methods known in the art, such as exposure to hydrogen over a palladium on carbon (Pd/C) catalyst.

##STR00136##

Definitions

[0149] The term alkyl as used herein by itself or as part of another group refers to a straight- or branched-chain aliphatic hydrocarbon containing one to twelve carbon atoms, i.e., a C.sub.1-C.sub.12 alkyl, or the number of carbon atoms designated, e.g., C.sub.1-C.sub.3 alkyl such as methyl, ethyl, propyl, or isopropyl; a C.sub.1-C.sub.4 alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or t-butyl; and so on. In one embodiment the alkyl is a straight-chain alkyl. In another embodiment, the alkyl is a branched-chain alkyl. In one embodiment, the alkyl is a C.sub.1-C.sub.8 alkyl. In another embodiment, the alkyl is a C.sub.1-C.sub.6 alkyl. In another embodiment, the alkyl is a C.sub.1-C.sub.4 alkyl. In another embodiment, the alkyl is a C.sub.1-C.sub.3 alkyl. Non-limiting exemplary C.sub.1-C.sub.12 alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, iso-butyl, 3-pentyl, hexyl, heptyl, octyl, nonyl, and decyl.

[0150] The term optionally substituted alkyl as used herein by itself or as part of another group refers to an alkyl that is either unsubstituted or substituted with one to three substituents, wherein the substituents are each independently nitro, cyano, hydroxyl, amino, (e.g., NH.sub.2, alkylamino, or dialkylamino), alkoxy, alkylthio, alkylcarbonyl, cycloalkyl, or C(O)OR.sup.1h, wherein R.sup.1h is C.sub.1-C.sub.6 alkyl.

[0151] The term halo or halogen as used herein by itself or as part of another group refers to Cl, F, Br, or -I.

[0152] The term nitro as used herein by itself or as part of another group refers to NO.sub.2.

[0153] The term cyano as used herein by itself or as part of another group refers to CN.

[0154] The term hydroxy as herein used by itself or as part of another group refers to OH.

[0155] The term amino as used by itself or as part of another group refers to a radical of the formula NR.sup.1fR.sup.1g, wherein R.sup.1f and R.sup.1g are independently hydrogen or alkyl.

[0156] In one embodiment, the amino is NH.sub.2.

[0157] In another embodiment, the amino is an alkylamino, i.e., an amino group wherein R.sup.1f is C.sub.1-6 alkyl and R.sup.1g is hydrogen. In one embodiment, R.sup.1f is C.sub.1-C.sub.4 alkyl. Non-limiting exemplary alkylamino groups include N(H)CH.sub.3 and N(H)CH.sub.2CH.sub.3.

[0158] In another embodiment, the amino is a dialkylamino, i.e., an amino group wherein R.sup.1f and R.sup.1g are each independently C.sub.1-6 alkyl. In one embodiment, R.sup.1f and R.sup.1g are each independently C.sub.1-C.sub.4 alkyl. Non-limiting exemplary dialkylamino groups include N(CH.sub.3).sub.2 and N(CH.sub.3)CH.sub.2CH(CH.sub.3).sub.2.

[0159] The term alkylcarbonyl as used herein by itself or as part of another group refers to a carbonyl group, i.e., C(O), substituted by an alkyl group. In one embodiment, the alkyl is a C.sub.1-C.sub.4 alkyl. A non-limiting exemplary alkylcarbonyl group is COCH.sub.3.

[0160] The term haloalkyl as used herein by itself or as part of another group refers to an alkyl substituted by one or more fluorine, chlorine, bromine, and/or iodine atoms. In one embodiment, the alkyl is substituted by one, two, or three fluorine and/or chlorine atoms. In another embodiment, the alkyl is substituted by one, two, or three fluorine atoms. In another embodiment, the alkyl is a C.sub.1-C.sub.6 alkyl and the resulting haloalkyl is referred to as a C.sub.1-C.sub.6 haloalkyl. In another embodiment, the alkyl is a C.sub.1-C.sub.4 alkyl and the resulting haloalkyl is referred to as a C.sub.1-C.sub.4 haloalkyl. In another embodiment, the alkyl group is a C.sub.1 or C.sub.2 alkyl. Non-limiting exemplary haloalkyl groups include fluoromethyl, difluoromethyl, trifluoromethyl, pentafluoroethyl, 1,1-difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, and trichloromethyl groups.

[0161] The term alkoxy as used herein by itself or as part of another group refers to an alkyl attached to a terminal oxygen atom. In one embodiment, the alkyl is a C.sub.1-C.sub.6 alkyl, and the resulting alkoxy is referred to as a C.sub.1-C.sub.6 alkoxy. In another embodiment, the alkyl is a C.sub.1-C.sub.4 alkyl group and thus the resulting alkoxy is referred to as a C.sub.1-C.sub.4 alkoxy. Non-limiting exemplary alkoxy groups include methoxy, ethoxy, and tert-butoxy.

[0162] The term alkylthio as used herein by itself or as part of another group refers to an alkyl group attached to a terminal sulfur atom. In one embodiment, the alkyl is a C.sub.1-C.sub.6 alkyl, and the resulting alkylthio is referred to as a C.sub.1-C.sub.6 alkylthio. In one embodiment, the alkyl group is a C.sub.1-C.sub.4 alkyl group and the resulting alkylthio is referred to as a C.sub.1-C.sub.4 alkylthio. Non-limiting exemplary alkylthio groups include SCH.sub.3, and SCH.sub.2CH.sub.3.

[0163] The term cycloalkyl as used herein by itself or as part of another group refers to saturated and partially unsaturated, e.g., containing one or two double bonds, monocyclic, bicyclic, or tricyclic aliphatic hydrocarbons containing three to twelve carbon atoms, i.e., a C.sub.3-C.sub.12 cycloalkyl, or the number of carbons designated, e.g., a C.sub.3-C.sub.6 cycloalkyl such a cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. In one embodiment, the cycloalkyl is bicyclic, i.e., it has two rings. In another embodiment, the cycloalkyl is monocyclic, i.e., it has one ring. In another embodiment, the cycloalkyl is a C.sub.3-C.sub.8 cycloalkyl. In another embodiment, the cycloalkyl is a C.sub.3. C.sub.6 cycloalkyl. In another embodiment, the cycloalkyl is a C.sub.5 cycloalkyl, i.e., cyclopentyl. In another embodiment, the cycloalkyl is a C.sub.6 cycloalkyl, i.e., cyclohexyl. Non-limiting exemplary C.sub.3-C.sub.12 cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, decalin, adamantyl, cyclohexenyl, and spiro[3.3]heptane.

[0164] The term optionally substituted phenyl as used herein by itself or as part of another group refers to phenyl that is either unsubstituted or substituted with one to five substitutents, wherein the substituents are each independently halo, nitro, cyano, hydroxyl, amino, (e.g., NH.sub.2, alkylamino, or dialkylamino), alkoxy, alkylthio, alkylcarbonyl, alkyl, or cycloalkyl.

[0165] The term heterocyclo as used herein by itself or as part of another group refers to saturated and partially unsaturated, e.g., containing one or two double bonds, monocyclic, bicyclic, or tricyclic groups containing three to eighteen ring members, i.e., a 3- to 18-membered heterocyclo, comprising one, two, three, or four heteroatoms. Each heteroatom is independently oxygen, sulfur, or nitrogen. Each sulfur atom may be independently oxidized to give a sulfoxide, i.e., S(O), or sulfone, i.e., S(O).sub.2. The term heterocyclo includes groups wherein one or more CH.sub.2 groups is replaced with one or more C(O) groups, including cyclic ureido groups such as imidazolidinyl-2-one, cyclic amide groups such as pyrrolidin-2-one or piperidin-2-one, and cyclic carbamate groups such as oxazolidinyl-2-one. The term heterocyclo also includes groups having fused optionally substituted aryl or optionally substituted heteroaryl groups such as indoline, indolin-2-one, 2,3-dihydro-1H-pyrrolo[2,3-c]pyridine, 2,3,4,5-tetrahydro-1H-benzo[d]azepine, or 1,3,4,5-tetrahydro-2H-benzo[d]azepin-2-one. In some embodiments, heterocyclo is a 6-membered ring comprising one nitrogen atom. The heterocyclo may be fused to the rest of the molecule to form a bicyclic group, e.g., 1,2-dihydroquinoline or 1,2,3,4-tetrahydroquinoline.

[0166] The term optionally substituted heterocyclo as used herein by itself or part of another group refers to a heterocyclo group that is either unsubstituted or substituted with one to four substituents, wherein the substituents are each independently halo, nitro, cyano, hydroxyl, amino, (e.g., NH.sub.2, alkylamino, or dialkylamino), alkoxy, alkylthio, alkylcarbonyl, alkyl, or cycloalkyl.

[0167] The term heteroaryl as used herein by itself or as part of another group refers to monocyclic aromatic ring systems having five to six ring members, i.e., a 5- to 6-membered heteroaryl, comprising one, two, three, four, or five heteroatoms. Each heteroatom is independently oxygen, sulfur, or nitrogen. In one embodiment, the heteroaryl has three heteroatoms. In another embodiment, the heteroaryl has two heteroatoms. In another embodiment, the heteroaryl has one heteroatom. In another embodiment, the heteroaryl has 5 ring atoms, e.g., furyl, a 5-membered heteroaryl having four carbon atoms and one oxygen atom. In another embodiment, the heteroaryl has 6 ring atoms, e.g., pyridyl, a 6-membered heteroaryl having five carbon atoms and one nitrogen atom. Non-limiting exemplary heteroaryl groups include thienyl, furyl, pyranyl, 2H-pyrrolyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, thiazolyl, isothiazolyl, and isoxazolyl. In one embodiment, the heteroaryl is chosen from thienyl (e.g., thien-2-yl and thien-3-yl), furyl (e.g., 2-furyl and 3-furyl), pyrrolyl (e.g., 1H-pyrrol-2-yl and 1H-pyrrol-3-yl), imidazolyl (e.g., 2H-imidazol-2-yl and 2H-imidazol-4-yl), pyrazolyl (e.g., 1H-pyrazol-3-yl, 1H-pyrazol-4-yl, and 1H-pyrazol-5-yl), pyridyl (e.g., pyridin-2-yl, pyridin-3-yl, and pyridin-4-yl), pyrimidinyl (e.g., pyrimidin-2-yl, pyrimidin-4-yl, and pyrimidin-5-yl), thiazolyl (e.g., thiazol-2-yl, thiazol-4-yl, and thiazol-5-yl), isothiazolyl (e.g., isothiazol-3-yl, isothiazol-4-yl, and isothiazol-5-yl), oxazolyl (e.g., oxazol-2-yl, oxazol-4-yl, and oxazol-5-yl) and isoxazolyl (e.g., isoxazol-3-yl, isoxazol-4-yl, and isoxazol-5-yl). The term heteroaryl also includes N-oxides. A non-limiting exemplary N-oxide is pyridyl N-oxide.

[0168] The term optionally substituted heteroaryl as used herein by itself or as part of another group refers to a heteroaryl that is either unsubstituted or substituted with one to four substituents, wherein the substituents are each independently halo, nitro, cyano, hydroxyl, amino, (e.g., NH.sub.2, alkylamino, or dialkylamino), alkoxy, alkylthio, alkylcarbonyl, alkyl, or cycloalkyl.

[0169] As used herein, the term stereoisomers is a general term for all isomers of an individual molecule that differ only in the orientation of their atoms in space. It includes enantiomers and isomers of compounds with more than one chiral center that are not mirror images of one another (diastereomers).

[0170] The term chiral center or asymmetric carbon atom refers to a carbon atom to which four different groups are attached.

[0171] The terms enantiomer and enantiomeric refer to a molecule that cannot be superimposed on its mirror image and hence is optically active wherein the enantiomer rotates the plane of polarized light in one direction and its mirror image compound rotates the plane of polarized light in the opposite direction.

[0172] The term racemic refers to a mixture of equal parts of enantiomers and which mixture is optically inactive.

[0173] The term absolute configuration refers to the spatial arrangement of the atoms of a chiral molecular entity (or group) and its stereochemical description, e.g., R or S.

[0174] The stereochemical terms and conventions used in the specification are meant to be consistent with those described in Pure & AppL. Chem 68:2193 (1996), unless otherwise indicated.

[0175] The term enantiomeric excess or ee refers to a measure for how much of one enantiomer is present compared to the other. For a mixture of R and S enantiomers, the percent enantiomeric excess is defined as |RS|*100, where R and S are the respective mole or weight fractions of enantiomers in a mixture such that R+S=1. With knowledge of the optical rotation of a chiral substance, the percent enantiomeric excess is defined as ([].sub.obs/[].sub.max)*100, where [].sub.obs is the optical rotation of the mixture of enantiomers and [].sub.max is the optical rotation of the pure enantiomer. Determination of enantiomeric excess is possible using a variety of analytical techniques, including NMR spectroscopy, chiral column chromatography, or optical polarimetry.

[0176] In thin layer chromatography (TLC), the term R.sub.f stands for retention factor. R.sub.f is defined as the distance travelled by an individual component divided by the total distance travelled by the eluent. Its value is always between zero and one.

[0177] Salts and solvates, e.g., hydrates, of the Compounds of the Disclosure can also be used in the methods disclosed herein.

[0178] The present disclosure encompasses the preparation and use of salts of Compounds of the Disclosure. Salts of Compounds of the Disclosure can be prepared during the final isolation and purification of the compounds or separately by reacting the compound with an acid having a suitable cation. Salts of Compounds of the Disclosure can be acid addition salts formed with acceptable acids. Examples of acids which can be employed to form salts include inorganic acids such as nitric, boric, hydrochloric, hydrobromic, sulfuric, and phosphoric, and organic acids such as oxalic, maleic, succinic, and citric. Non-limiting examples of salts of compounds of the disclosure include, but are not limited to, the hydrochloride, hydrobromide, hydroiodide, sulfate, bisulfate, 2-hydroxyethansulfonate, phosphate, hydrogen phosphate, acetate, adipate, alginate, aspartate, benzoate, bisulfate, butyrate, camphorate, camphorsulfonate, digluconate, glycerolphosphate, hemisulfate, heptanoate, hexanoate, formate, succinate, fumarate, maleate, ascorbate, isethionate, salicylate, methanesulfonate, mesitylenesulfonate, naphthylenesulfonate, nicotinate, 2-naphthalenesulfonate, oxalate, pamoate, pectinate, persulfate, 3-phenylproprionate, picrate, pivalate, propionate, trichloroacetate, trifluoroacetate, phosphate, glutamate, bicarbonate, paratoluenesulfonate, undecanoate, lactate, citrate, tartrate, gluconate, methanesulfonate, ethanedisulfonate, benzene sulfonate, and p-toluenesulfonate salts. In addition, available amino groups present in the compounds of the disclosure can be quaternized with methyl, ethyl, propyl, and butyl chlorides, bromides, and iodides; dimethyl, diethyl, dibutyl, and diamyl sulfates; decyl, lauryl, myristyl, and steryl chlorides, bromides, and iodides; and benzyl and phenethyl bromides. In light of the foregoing, any reference to Compounds of the Disclosure appearing herein is intended to include Compounds of the Disclosure as well as salts, hydrates, or solvates thereof.

[0179] The present disclosure encompasses the preparation and use of solvates of Compounds of the Disclosure. The term solvate as used herein is a combination, physical association and/or solvation of a compound of the present disclosure with a solvent molecule such as, e.g., a disolvate, monosolvate or hemisolvate, where the ratio of solvent molecule to compound of the present disclosure is about 2:1, about 1:1 or about 1:2, respectively. This physical association involves varying degrees of ionic and covalent bonding, including hydrogen bonding. In certain instances, the solvate can be isolated, such as when one or more solvent molecules are incorporated into the crystal lattice of a crystalline solid. Thus, solvate encompasses both solution-phase and isolatable solvates. Compounds of the Disclosure can be present as solvated forms with a solvent, such as water, methanol, and ethanol, and it is intended that the disclosure includes both solvated and unsolvated forms of Compounds of the Disclosure.

[0180] One type of solvate is a hydrate. A hydrate relates to a particular subgroup of solvates where the solvent molecule is water. Preparation of solvates is known in the art. See, for example, M. Caira et al, J. Pharmaceut. Sci., 93(3):601-611 (2004), which describes the preparation of solvates of fluconazole with ethyl acetate and with water. Similar preparation of solvates, hemisolvates, hydrates, and the like are described by van Tonder et al., AAPSPharm. Sci. Tech., 5(1): Article 12 (2004), and A. L. Bingham et al., Chem. Commun. 603-604 (2001). A typical, non-limiting, process of preparing a solvate would involve dissolving a Compound of the Disclosure in a desired solvent (organic, water, or a mixture thereof) at temperatures above 20 C. to about 25 C., then cooling the solution at a rate sufficient to form crystals, and isolating the crystals by known methods, e.g., filtration. Analytical techniques such as infrared spectroscopy can be used to confirm the presence of the solvent in a crystal of the solvate.

[0181] The use of the terms a, an, the, and similar referents in the context of describing the disclosure (especially in the context of the claims) are to be construed to cover both the singular and the plural, unless otherwise indicated. Recitation of ranges of values herein merely are intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. The use of any and all examples, or exemplary language (e.g., such as) provided herein, is intended to better illustrate the disclosure and is not a limitation on the scope of the disclosure unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the disclosure.

[0182] The term wt/wt % as used herein refers to the mass of one component in a composition or blend, e.g., a composition comprising a Compound of the Disclosure and one or more elastomers; or a Composition of the Disclosure and one or more fillers; or a blend comprising two or more elastomers, etc., divided by the combined mass of all components in the composition or blend, times 100. For example, the wt/wt % of a Compound of the Disclosure in a composition comprising 1 kg of the compound, 1 kg natural rubber, and 2 kg of synthetic rubber, is 25 wt/wt % (1 kg/4 kg=0.25100=25 wt/wt %). The wt/wt % of a Compound of the Disclosure in a composition comprising 1 kg of the compound and 1 kg of carbon black is 50 wt/wt % (1 kg/2 kg=0.20100=50 wt/wt %). The wt/wt % of a Compound of the Disclosure in a composition comprising 1 kg of the compound, 1 kg natural rubber, 2 kg of synthetic rubber, and 1 kg of carbon black is 20 wt/wt % (1 kg/5 kg=0.20100=20 wt/wt %). The wt/wt % of natural rubber in a blend of one or more elastomers comprising 20 kg natural rubber and 30 kg synthetic rubber is 40 wt/wt % (20 kg/50 kg=0.40100=40 wt/wt %).

Compositions and Methods of Use

[0183] In another embodiment, the disclosure provides compositions comprising: [0184] (i) a Compound of the Disclosure; and [0185] (ii) one or more elastomers; or [0186] (iii) one or more fillers; or [0187] (iv) one or more rubber chemicals; or [0188] (v) one or more plasticizers; or [0189] (vi) a second antidegradant; or [0190] (vii) a combination of one or more elastomers, one or more fillers, one or more rubber chemicals, one or more plasticizers, and/or a second antidegradant.

[0191] In some embodiments, a Composition of the Disclosure comprises from about 15 wt/wt % to about 85 wt/wt % of a Compound of the Disclosure. In some embodiments, the composition comprises from about 1 wt/wt % to about 5 wt/wt %, from about 1 wt/wt % to about 15 wt/wt % from about 1 wt/wt % to about 25 wt/wt % from about 1 wt/wt % to about 35 wt/wt % from about 1 wt/wt % to about 45 wt/wt % from about 1 wt/wt % to about 55 wt/wt % from about 1 wt/wt % to about 65 wt/wt % from about 1 wt/wt % to about 75 wt/wt % from about 1 wt/wt % to about 85 wt/wt % from about 1 wt/wt % to about 95 wt/wt % from about 5 wt/wt % to about 15 wt/wt % from about 5 wt/wt % to about 25 wt/wt % from about 5 wt/wt % to about 35 wt/wt % from about 5 wt/wt % to about 45 wt/wt % from about 5 wt/wt % to about 55 wt/wt % from about 5 wt/wt % to about 65 wt/wt % from about 5 wt/wt % to about 75 wt/wt % from about 5 wt/wt % to about 85 wt/wt % from about 5 wt/wt % to about 95 wt/wt % from about 15 wt/wt % to about 25 wt/wt % from about 15 wt/wt % to about 35 wt/wt % from about 15 wt/wt % to about 45 wt/wt % from about 15 wt/wt % to about 55 wt/wt % from about 15 wt/wt % to about 65 wt/wt % from about 15 wt/wt % to about 75 wt/wt % from about 15 wt/wt % to about 95 wt/wt %, from about 25 wt/wt % to about 35 wt/wt %, from about 25 wt/wt % to about 45 wt/wt %, from about 25 wt/wt % to about 55 wt/wt %, from about 25 wt/wt % to about 65 wt/wt % from about 25 wt/wt % to about 75 wt/wt % from about 25 wt/wt % to about 85 wt/wt % from about 25 wt/wt % to about 95 wt/wt % from about 35 wt/wt % to about 45 wt/wt % from about 35 wt/wt % to about 55 wt/wt % from about 35 wt/wt % to about 65 wt/wt % from about 35 wt/wt % to about 75 wt/wt % from about 35 wt/wt % to about 85 wt/wt % from about 35 wt/wt % to about 95 wt/wt % from about 45 wt/wt % to about 55 wt/wt % from about 45 wt/wt % to about 65 wt/wt % from about 45 wt/wt % to about 75 wt/wt % from about 45 wt/wt % to about 85 wt/wt % from about 45 wt/wt % to about 95 wt/wt % from about 55 wt/wt % to about 65 wt/wt % from about 55 wt/wt % to about 75 wt/wt % from about 55 wt/wt % to about 85 wt/wt % from about 55 wt/wt % to about 95 wt/wt % from about 65 wt/wt % to about 75 wt/wt % from about 65 wt/wt % to about 85 wt/wt % from about 65 wt/wt % to about 95 wt/wt % from about 75 wt/wt % to about 85 wt/wt % from about 75 wt/wt % to about 95 wt/wt % or from about 85 wt/wt % to about 95 wt/wt % of a Compound of the Disclosure. In some embodiments, the composition comprises from about 0.1 wt/wt % to about 0.5 wt/wt %, from about 0.1 wt/wt % to about 1 wt/wt %, from about 0.1 wt/wt % to about 1.5 wt/wt %, from about 0.1 wt/wt % to about 2 wt/wt %, from about 0.1 wt/wt % to about 2.5 wt/wt %, from about 0.1 wt/wt % to about 3 wt/wt %, from about 0.1 wt/wt % to about 3.5 wt/wt %, from about 0.1 wt/wt % to about 4 wt/wt %, from about 0.1 wt/wt % to about 4.5 wt/wt %, from about 0.1 wt/wt % to about 5 wt/wt %, from about 0.1 wt/wt % to about 6 wt/wt %, from about 0.1 wt/wt % to about 7 wt/wt %, from about 0.1 wt/wt % to about 8 wt/wt %, from about 0.1 wt/wt % to about 9 wt/wt %, from about 0.1 wt/wt % to about 10 wt/wt %, from about 0.5 wt/wt % to about 1 wt/wt %, from about 0.5 wt/wt % to about 1.5 wt/wt %, from about 0.5 wt/wt % to about 2 wt/wt %, from about 0.5 wt/wt % to about 2.5 wt/wt %, from about 0.5 wt/wt % to about 3 wt/wt %, from about 0.5 wt/wt % to about 3.5 wt/wt %, from about 0.5 wt/wt % to about 4 wt/wt %, from about 0.5 wt/wt % to about 4.5 wt/wt %, from about 0.5 wt/wt % to about 5 wt/wt %, from about 0.5 wt/wt % to about 6 wt/wt %, from about 0.5 wt/wt % to about 7 wt/wt %, from about 0.5 wt/wt % to about 8 wt/wt %, from about 0.5 wt/wt % to about 9 wt/wt %, from about 0.5 wt/wt % to about 10 wt/wt %, from about 1 wt/wt % to about 2 wt/wt %, from about 1 wt/wt % to about 2.5 wt/wt %, from about 1 wt/wt % to about 3 wt/wt %, from about 1 wt/wt % to about 3.5 wt/wt %, from about 1 wt/wt % to about 4 wt/wt %, from about 1 wt/wt % to about 4.5 wt/wt %, from about 1 wt/wt % to about 5 wt/wt %, from about 1 wt/wt % to about 6 wt/wt %, from about 1 wt/wt % to about 7 wt/wt %, from about 1 wt/wt % to about 8 wt/wt %, from about 1 wt/wt % to about 9 wt/wt %, from about 1 wt/wt % to about 10 wt/wt %, from about 1.5 wt/wt % to about 2 wt/wt %, from about 1.5 wt/wt % to about 2.5 wt/wt %, from about 1.5 wt/wt % to about 3 wt/wt %, from about 1.5 wt/wt % to about 3.5 wt/wt %, from about 1.5 wt/wt % to about 4 wt/wt %, from about 1.5 wt/wt % to about 4.5 wt/wt %, from about 1.5 wt/wt % to about 5 wt/wt %, from about 1.5 wt/wt % to about 6 wt/wt %, from about 1.5 wt/wt % to about 7 wt/wt %, from about 1.5 wt/wt % to about 8 wt/wt %, from about 1.5 wt/wt % to about 9 wt/wt %, from about 1.5 wt/wt % to about 10 wt/wt %, from about 2 wt/wt % to about 2.5 wt/wt %, from about 2 wt/wt % to about 3 wt/wt %, from about 2 wt/wt % to about 3.5 wt/wt %, from about 2 wt/wt % to about 4 wt/wt %, from about 2 wt/wt % to about 4.5 wt/wt %, from about 2 wt/wt % to about 5 wt/wt %, from about 2 wt/wt % to about 6 wt/wt %, from about 2 wt/wt % to about 7 wt/wt %, from about 2 wt/wt % to about 8 wt/wt %, from about 2 wt/wt % to about 9 wt/wt %, from about 2 wt/wt % to about 10 wt/wt %, from about 2.5 wt/wt % to about 3 wt/wt %, from about 2.5 wt/wt % to about 3.5 wt/wt %, from about 2.5 wt/wt % to about 4 wt/wt %, from about 2.5 wt/wt % to about 4.5 wt/wt %, from about 2.5 wt/wt % to about 5 wt/wt %, from about 2.5 wt/wt % to about 6 wt/wt %, from about 2.5 wt/wt % to about 7 wt/wt %, from about 2.5 wt/wt % to about 8 wt/wt %, from about 2.5 wt/wt % to about 9 wt/wt %, from about 2.5 wt/wt % to about 10 wt/wt %, from about 3 wt/wt % to about 4 wt/wt %, from about 3 wt/wt % to about 4.5 wt/wt %, from about 3 wt/wt % to about 5 wt/wt %, from about 3 wt/wt % to about 6 wt/wt %, from about 3 wt/wt % to about 7 wt/wt %, from about 3 wt/wt % to about 8 wt/wt %, from about 3 wt/wt % to about 9 wt/wt %, from about 3 wt/wt % to about 10 wt/wt %, from about 3.5 wt/wt % to about 4 wt/wt %, from about 3.5 wt/wt % to about 4.5 wt/wt %, from about 3.5 wt/wt % to about 5 wt/wt %, from about 3.5 wt/wt % to about 6 wt/wt %, from about 3.5 wt/wt % to about 7 wt/wt %, from about 3.5 wt/wt % to about 8 wt/wt %, from about 3.5 wt/wt % to about 9 wt/wt %, from about 3.5 wt/wt % to about 10 wt/wt %, from about 4 wt/wt % to about 4.5 wt/wt %, from about 4 wt/wt % to about 5 wt/wt %, from about 4 wt/wt % to about 6 wt/wt %, from about 4 wt/wt % to about 7 wt/wt %, from about 4 wt/wt % to about 8 wt/wt %, from about 4 wt/wt % to about 9 wt/wt %, from about 4 wt/wt % to about 10 wt/wt %, from about 4.5 wt/wt % to about 5 wt/wt %, from about 4.5 wt/wt % to about 6 wt/wt %, from about 4.5 wt/wt % to about 7 wt/wt %, from about 4.5 wt/wt % to about 8 wt/wt %, from about 4.5 wt/wt % to about 9 wt/wt %, from about 4.5 wt/wt % to about 10 wt/wt %, from about 5 wt/wt % to about 6 wt/wt %, from about 5 wt/wt % to about 7 wt/wt %, from about 5 wt/wt % to about 8 wt/wt %, from about 5 wt/wt % to about 9 wt/wt %, from about 5 wt/wt % to about 10 wt/wt %, from about 6 wt/wt % to about 7 wt/wt %, from about 6 wt/wt % to about 8 wt/wt %, from about 6 wt/wt % to about 9 wt/wt %, from about 6 wt/wt % to about 10 wt/wt %, from about 7 wt/wt % to about 8 wt/wt %, from about 7 wt/wt % to about 9 wt/wt %, from about 8 wt/wt % to about 10 wt/wt %, from about 8 wt/wt % to about 9 wt/wt %, from about 8 wt/wt % to about 10 wt/wt %, or from about 9 wt/wt % to about 10 wt/wt % of a Compound of the Disclosure.

[0192] In some embodiments, a Composition of the Disclosure comprises about 50 wt/wt % of a Compound of the Disclosure. In some embodiments, the composition comprises about 1 wt/wt %, about 5 wt/wt %, about 10 wt/wt %, about 15 wt/wt %, about 20 wt/wt %, about 25 wt/wt %, about 30 wt/wt %, about 35 wt/wt %, about 40 wt/wt %, about 45 wt/wt %, about 55 wt/wt %, about 60 wt/wt %, about 65 wt/wt %, about 70 wt/wt %, about 75 wt/wt %, about 80 wt/wt %, about 85 wt/wt %, about 90 wt/wt %, or about 95 wt/wt % of a Compound of the Disclosure. In some embodiments, the composition comprises about 0.1 wt/wt %, about 0.5 wt/wt %, about 1 wt/wt %, about 1.5 wt/wt %, about 2 wt/wt %, about 2.5 wt/wt %, about 3 wt/wt %, about 3.5 wt/wt %, about 4 wt/wt %, about 4.5 wt/wt %, about 5 wt/wt %, about 5.5 wt/wt %, about 6 wt/wt %, about 6.5 wt/wt %, about 7 wt/wt %, about 7.5 wt/wt %, about 8 wt/wt %, about 8.5 wt/wt %, about 9 wt/wt %, or about 10 wt/wt % of a Compound of the Disclosure.

[0193] In another embodiment, a Composition of the Disclosure comprises a Compound of the Disclosure and one or more elastomers.

[0194] The term elastomer as used herein is a polymer with viscoelasticity (i.e., having both viscosity and elasticity) that typically has low intermolecular forces, low Young's modulus, and high failure strain. Elastomers can typically be cross-linked by heating in the presence of one or more cross-linking agents, a process called curing or vulcanization. Rubber is one type of elastomer. Non-limiting types of rubber include natural rubber (NR), synthetic rubber, and blends thereof. The term natural rubber as used herein refers to a naturally occurring elastomer that can be obtained from Hevea rubber trees. Non-limiting types of synthetic rubbers include unsaturated rubbers, saturated rubbers, rubbers with fluoro and fluoralkyl or fluoralkoxy substituent groups on the polymer chain (FKM), silicone rubbers (Q), and blends thereof. Non-limiting examples of unsaturated rubbers include polyisoprene rubber (IR), butyl rubber (IIR), polybutadiene rubber (BR), styrene-isoprene-butadiene rubber (SIBR), styrene butadiene rubber (SBR), nitrile butadiene rubber (NBR), chloroprene rubber (CR), ethylene propylene diene rubber (EPDM), and blends thereof. These unsaturated rubbers undergo cyclization and crosslinking reactions that lead to hardening of the aged part. As oxidation occurs, these vulcanizates harden and eventually become brittle products. Partial oxidation of vulcanizates leads to losses in performance when used in applications such as vehicle tire sidewalls. Saturated rubbers are rubbers that do not contain CC unsaturation and include, but are not limited to, acrylic rubber (ACM), chlorinated polyethylene (CM), chlorosulfonated polyethylene (CSM), polychloromethyloxiran (CO), ethylene-ethyl acrylate copolymer (EAM), epichlorohydrin rubber (ECO), ethylene propylene rubber (EPM), ethylenevinylacetate copolymer (EVM), rubbers with fluoro and fluoralkyl or fluoralkoxy substituent groups on the polymer chain (FKM), silicone rubber (Q), and blends thereof.

[0195] In some embodiments, the natural rubber comprises rubber derived from an alternative rubber plant. The term natural rubber comprises rubber derived from an alternative rubber plant as used herein refers to a naturally occurring elastomer that can be obtained from non-Hevea sources. In some embodiments, the alternative rubber plant is Parthenium argentatum (guayule) or Taraxacum kok-saghyz (Russian dandelion).

[0196] In some embodiments, the one or more elastomers further comprises recycled rubber. The term recycled rubber as used herein refers to an elastomer that has been reclaimed from scrap materials such as used tires.

[0197] In some embodiments, a Composition of the Disclosure comprises from about 15 wt/wt % to about 85 wt/wt % of one or more elastomers. In some embodiments, the composition comprises from about 1 wt/wt % to about 5 wt/wt %, from about 1 wt/wt % to about 15 wt/wt %, from about 1 wt/wt % to about 25 wt/wt %, from about 1 wt/wt % to about 35 wt/wt % from about 1 wt/wt % to about 45 wt/wt % from about 1 wt/wt % to about 55 wt/wt % from about 1 wt/wt % to about 65 wt/wt % from about 1 wt/wt % to about 75 wt/wt % from about 1 wt/wt % to about 85 wt/wt % from about 1 wt/wt % to about 95 wt/wt % from about 5 wt/wt % to about 15 wt/wt % from about 5 wt/wt % to about 25 wt/wt % from about 5 wt/wt % to about 35 wt/wt % from about 5 wt/wt % to about 45 wt/wt % from about 5 wt/wt % to about 55 wt/wt % from about 5 wt/wt % to about 65 wt/wt % from about 5 wt/wt % to about 75 wt/wt % from about 5 wt/wt % to about 85 wt/wt %, from about 5 wt/wt % to about 95 wt/wt %, from about 15 wt/wt % to about 25 wt/wt %, from about 15 wt/wt % to about 35 wt/wt %, from about 15 wt/wt % to about 45 wt/wt %, from about 15 wt/wt % to about 55 wt/wt %, from about 15 wt/wt % to about 65 wt/wt %, from about 15 wt/wt % to about 75 wt/wt %, from about 15 wt/wt % to about 95 wt/wt % from about 25 wt/wt % to about 35 wt/wt % from about 25 wt/wt % to about 45 wt/wt % from about 25 wt/wt % to about 55 wt/wt % from about 25 wt/wt % to about 65 wt/wt % from about 25 wt/wt % to about 75 wt/wt % from about 25 wt/wt % to about 85 wt/wt % from about 25 wt/wt % to about 95 wt/wt % from about 35 wt/wt % to about 45 wt/wt % from about 35 wt/wt % to about 55 wt/wt % from about 35 wt/wt % to about 65 wt/wt % from about 35 wt/wt % to about 75 wt/wt % from about 35 wt/wt % to about 85 wt/wt % from about 35 wt/wt % to about 95 wt/wt % from about 45 wt/wt % to about 55 wt/wt % from about 45 wt/wt % to about 65 wt/wt % from about 45 wt/wt % to about 75 wt/wt % from about 45 wt/wt % to about 85 wt/wt % from about 45 wt/wt % to about 95 wt/wt % from about 55 wt/wt % to about 65 wt/wt % from about 55 wt/wt % to about 75 wt/wt % from about 55 wt/wt % to about 85 wt/wt % from about 55 wt/wt % to about 95 wt/wt % from about 65 wt/wt % to about 75 wt/wt % from about 65 wt/wt % to about 85 wt/wt % from about 65 wt/wt % to about 95 wt/wt % from about 75 wt/wt % to about 85 wt/wt % from about 75 wt/wt % to about 95 wt/wt % or from about 85 wt/wt % to about 95 wt/wt % of one or more elastomers.

[0198] In some embodiments, a Composition of the Disclosure comprises about 50 wt/wt % of one or more elastomers. In some embodiments, the composition comprises about 1 wt/wt %, about 5 wt/wt %, about 10 wt/wt %, about 15 wt/wt %, about 20 wt/wt %, about 25 wt/wt %, about 30 wt/wt %, about 35 wt/wt %, about 40 wt/wt %, about 45 wt/wt %, about 55 wt/wt %, about 60 wt/wt %, about 65 wt/wt %, about 70 wt/wt %, about 75 wt/wt %, about 80 wt/wt %, about 85 wt/wt %, about 90 wt/wt %, or about 95 wt/wt % of one or more elastomers.

[0199] The term phr as used herein refers to parts per hundred parts of rubber by weight. The parts by weight of individual components are based on 100 parts by weight of the total mass of the one or more elastomers present in the composition.

[0200] In some embodiments, a Composition of the Disclosure comprises from about 1 phr to about 5 phr of a Compound of the Disclosure. In some embodiments, the composition comprises from about 0.01 phr to about 0.1 phr, from about 0.01 phr to about 0.5 phr, from about 0.01 phr to about 1 phr, from about 0.01 phr to about 2 phr, from about 0.01 phr to about 3 phr, from about 0.01 phr to about 4 phr, from about 0.01 phr to about 5 phr, from about 0.01 phr to about 7.5 phr, from about 0.01 phr to about 10 phr, from about 0.01 phr to about 20 phr, from about 0.1 phr to about 0.5 phr, from about 0.1 phr to about 1 phr, from about 0.1 phr to about 2 phr, from about 0.1 phr to about 3 phr, from about 0.1 phr to about 4 phr, from about 0.1 phr to about 5 phr, from about 0.1 phr to about 7.5 phr, from about 0.1 phr to about 10 phr, from about 0.1 phr to about 20 phr, from about 1 phr to about 2 phr, from about 1 phr to about 3 phr, from about 1 phr to about 4 phr, from about 1 phr to about 7.5 phr, from about 1 phr to about 10 phr, from about 1 phr to about 20 phr, from about 2 phr to about 3 phr, from about 2 phr to about 4 phr, from about 2 phr to about 5 phr, from about 2 phr to about 7.5 phr, from about 2 phr to about 10 phr, from about 2 phr to about 20 phr, from about 3 phr to about 4 phr, from about 3 phr to about 5 phr, from about 3 phr to about 7.5 phr, from about 3 phr to about 10 phr, from about 3 phr to about 20 phr, from about 4 phr to about 5 phr, from about 4 phr to about 7.5 phr, from about 4 phr to about 10 phr, from about 4 phr to about 20 phr, from about 5 phr to about 7.5 phr, from about 5 phr to about 10 phr, from about 5 phr to about 20 phr, from about 7.5 phr to about 10 phr, from about 7.5 phr to about 20 phr, or from about 10 phr to about 20 phr of a Compound of the Disclosure.

[0201] In some embodiments, a Composition of the Disclosure comprises about 3 phr of a Compound of the Disclosure. In some embodiments, the composition comprises about 0.01 phr, about 0.1 phr, about 0.5 phr, about 1 phr, about 2 phr, about 3 phr, about 4 phr, about 5 phr, about 7.5 phr, about 10 phr, or about 20 phr of a Compound of the Disclosure.

[0202] In some embodiments, a Composition of the Disclosure comprises a Compound of the Disclosure and one or more fillers.

[0203] The term filler as used herein is a substance that reinforces an elastomeric composition or gives an elastomeric composition other properties, including but not limited to expanding the volume of the composition. Non-limiting examples of fillers include carbon black, silica, kaolin, calcium silicate, talc, carbon nanotubes (CNT), carbon fibers (HCF), graphite, graphenes, aluminosilicates, starch, and fibers, and combinations thereof.

[0204] In some embodiments, the filler is derived from natural sources. For example, silica may be derived from rice husks.

[0205] In some embodiments, a Composition of the Disclosure comprises from about 15 wt/wt % to about 85 wt/wt % of one or more fillers. In some embodiments, the composition comprises from about 1 wt/wt % to about 5 wt/wt %, from about 1 wt/wt % to about 15 wt/wt %, from about 1 wt/wt % to about 25 wt/wt %, from about 1 wt/wt % to about 35 wt/wt % from about 1 wt/wt % to about 45 wt/wt % from about 1 wt/wt % to about 55 wt/wt % from about 1 wt/wt % to about 65 wt/wt % from about 1 wt/wt % to about 75 wt/wt % from about 1 wt/wt % to about 85 wt/wt % from about 1 wt/wt % to about 95 wt/wt % from about 5 wt/wt % to about 15 wt/wt % from about 5 wt/wt % to about 25 wt/wt % from about 5 wt/wt % to about 35 wt/wt % from about 5 wt/wt % to about 45 wt/wt % from about 5 wt/wt % to about 55 wt/wt % from about 5 wt/wt % to about 65 wt/wt % from about 5 wt/wt % to about 75 wt/wt % from about 5 wt/wt % to about 85 wt/wt % from about 5 wt/wt % to about 95 wt/wt % from about 15 wt/wt % to about 25 wt/wt % from about 15 wt/wt % to about 35 wt/wt % from about 15 wt/wt % to about 45 wt/wt % from about 15 wt/wt % to about 55 wt/wt % from about 15 wt/wt % to about 65 wt/wt % from about 15 wt/wt % to about 75 wt/wt % from about 15 wt/wt % to about 95 wt/wt % from about 25 wt/wt % to about 35 wt/wt % from about 25 wt/wt % to about 45 wt/wt % from about 25 wt/wt % to about 55 wt/wt % from about 25 wt/wt % to about 65 wt/wt % from about 25 wt/wt % to about 75 wt/wt % from about 25 wt/wt % to about 85 wt/wt % from about 25 wt/wt % to about 95 wt/wt % from about 35 wt/wt % to about 45 wt/wt % from about 35 wt/wt % to about 55 wt/wt % from about 35 wt/wt % to about 65 wt/wt % from about 35 wt/wt % to about 75 wt/wt % from about 35 wt/wt % to about 85 wt/wt % from about 35 wt/wt % to about 95 wt/wt % from about 45 wt/wt % to about 55 wt/wt % from about 45 wt/wt % to about 65 wt/wt % from about 45 wt/wt % to about 75 wt/wt % from about 45 wt/wt % to about 85 wt/wt % from about 45 wt/wt % to about 95 wt/wt % from about 55 wt/wt % to about 65 wt/wt % from about 55 wt/wt % to about 75 wt/wt % from about 55 wt/wt % to about 85 wt/wt % from about 55 wt/wt % to about 95 wt/wt % from about 65 wt/wt % to about 75 wt/wt % from about 65 wt/wt % to about 85 wt/wt % from about 65 wt/wt % to about 95 wt/wt % from about 75 wt/wt % to about 85 wt/wt % from about 75 wt/wt % to about 95 wt/wt % or from about 85 wt/wt % to about 95 wt/wt % of one or more fillers.

[0206] In some embodiments, a Composition of the Disclosure comprises about 50 wt/wt % of one or more fillers. In some embodiments, the composition comprises about 1 wt/wt %. about 5 wt/wt %. about 10 wt/wt %. about 15 wt/wt %. about 20 wt/wt %. about 25 wt/wt %, about 30 wt/wt %, about 35 wt/wt %, about 40 wt/wt %, about 45 wt/wt %, about 55 wt/wt %, about 60 wt/wt %, about 65 wt/wt %, about 70 wt/wt %, about 75 wt/wt %, about 80 wt/wt %, about 85 wt/wt %, about 90 wt/wt %, or about 95 wt/wt % of one or more fillers.

[0207] In some embodiments, a Composition of the Disclosure comprises from about 30 phr to about 500 phr of one or more fillers. In some embodiments, the composition comprises from about 30 phr to about 50 phr, from about 30 phr to about 100 phr, from about 30 phr to about 150 phr, from about 30 phr to about 200 phr, from about 30 phr to about 250 phr, from about 30 phr to about 300 phr, from about 30 phr to about 350 phr, from about 30 phr to about 400 phr, from about 30 phr to about 450 phr, from about 30 phr to about 500 phr, from about 50 phr to about 100 phr, from about 50 phr to about 150 phr, from about 50 phr to about 200 phr, from about 50 phr to about 250 phr, from about 50 phr to about 300 phr, from about 50 phr to about 350 phr, from about 50 phr to about 400 phr, from about 50 phr to about 450 phr, from about 50 phr to about 500 phr, from about 100 phr to about 150 phr, from about 100 phr to about 200 phr, from about 100 phr to about 250 phr, from about 100 phr to about 300 phr, from about 100 phr to about 350 phr, from about 100 phr to about 400 phr, from about 100 phr to about 450 phr, from about 100 phr to about 500 phr, from about 150 phr to about 200 phr, from about 150 phr to about 250 phr, from about 150 phr to about 300 phr, from about 150 phr to about 350 phr, from about 150 phr to about 400 phr, from about 150 phr to about 450 phr, from about 150 phr to about 500 phr, from about 200 phr to about 250 phr, from about 200 phr to about 300 phr, from about 200 phr to about 350 phr, from about 200 phr to about 400 phr, from about 200 phr to about 450 phr, from about 200 phr to about 500 phr, from about 250 phr to about 300 phr, from about 250 phr to about 350 phr, from about 250 phr to about 400 phr, from about 250 phr to about 450 phr, from about 250 phr to about 500 phr, from about 300 phr to about 350 phr, from about 300 phr to about 400 phr, from about 300 phr to about 450 phr, from about 300 phr to about 500 phr, from about 350 phr to about 400 phr, from about 350 phr to about 450 phr, from about 350 phr to about 500 phr, from about 400 phr to about 450 phr, from about 400 phr to about 500 phr, or from about 450 phr to about 500 phr of one or more fillers.

[0208] In some embodiments, a Composition of the Disclosure comprises about 300 phr of one or more fillers. In some embodiments, the composition comprises about 30 phr, about 50 phr, about 100 phr, about 150 phr, about 200 phr, about 250 phr, about 350 phr, about 400 phr, about 450 phr, or about 500 phr of one or more fillers.

[0209] In some embodiments, a Composition of the Disclosure comprises a Compound of the Disclosure and one or more rubber chemicals. The term rubber chemicals as used herein refers to a compound or substance used to facilitate the vulcanization of rubber. Rubber chemicals include, but are not limited to, vulcanizing agents, accelerators, activators, and pre-vulcanization inhibitors.

[0210] The term vulcanization as used herein refers to a process wherein cross-links are formed between elastomers to effect changes in the material properties of elastomers. In particular, vulcanization typically increases the rigidity and durability of elastomers. Vulcanization is carried out at room temperature or at elevated temperatures, depending on the nature of the elastomer(s), filler(s), and rubber chemical(s) being used. The term curing is also used in the art to describe this process.

[0211] The term vulcanizing agent as used herein refers to any substance that enables cross-linking between elastomers. Vulcanizing agents can enable cross-linking between separate polymer chains of an elastomer by various mechanisms, including, but not limited to, by formation of covalent bonds between the vulcanizing agent and two or more separate polymer chains or by generating radical species on separate polymer chains that can combine to form covalent bonds between the two polymer chains. Non-limiting examples of vulcanizing agents include sulfur, peroxides, vulcanized vegetable oil, factices and resins. Non-limiting examples of sulfur include octasulfur (S.sub.8), cyclododecasulfur (S.sub.12), and polymeric sulfur. Non-limiting examples of peroxides include benzoyl peroxide, dicumyl peroxide (DC), 2,5-dimethyl-2,5-di-(tert-butylperoxy)-3-hexyne (2,5 Tri), 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane (DDPH), di-(2-tert-butylperoxyisopropyl)benzene (VC), butyl-4,4-di-(tert-butylperoxy)valerate (VAL), and 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane (TMC). Nonlimiting examples of resins include bonding resins. The term bonding resin as used herein refers to a chemical such as resorcinol formaldehyde resins and phenolic resins that reacts with methylene donors (such as hexamethylenetetramine (HMTA) or hexamethoxymethyl melamine (HMMM)) to promote adhesion.

[0212] The term accelerator as used herein refers to any substance that increases the kinetics of vulcanization. In some embodiments, accelerators enable vulcanization to be performed at lower temperatures and/or to use the vulcanization agent, e.g., sulfur, more efficiently. Non-limiting examples of accelerators include guanidines, thiazoles, sulfenamides, thiurams, dithiocarbamates, xanthates, and thiophosphates. Non-limiting examples of guanidines include diphenylguanidine (DPG). Non-limiting examples of thiazoles include 2-mercaptobenzothiazole (MBT), zinc 2-mercaptobenzothiazole (ZMBT), mercaptobenzothiazole disulfide (MBTS), and N-tert-butyl-2-benzothiazole sulfenimide (TBSI). Non-limiting examples of sulfenamides include N-tert-butyl-2-benzothiazylsulfenamide (TBBS), N-cyclohexylbenzothiazol-2-sulfenamide (CBS), dicyclohexyl-2-benzothiazolesulfenamide (DCBS), N-oxydiethylene benzothiazole sulfenamide (OBTS), N-oxydiethylenethiocarbamyl-N-oxydiethylene sulfenamide (OTOS), and thiocarbamyl sulfenamide. Non-limiting examples of thiurams include dimethylcarbamothioic dithioperoxyanhydride (thiram), dipentamethylene thiuram tetrasulfide (DPIT), tetrabenzyl thiuram disulfide (TBzTD), tetraethylthiuram disulfide (TETD), tetramethylthiuram disulfide (TMTD), and tetramethylthiuram monosulfide (TMTM). Non-limiting examples of dithiocarbamates include zinc dimethyldithiocarbamate (ZDMC), zinc diethyldithiocarbamate (ZDEC), zinc dibutyldithiocarbamate (ZDBC), nickel dibutyldithiocarbamate (NDBC), sodium dibenzyldithiocarbamate (SBEC), sodium diethyldithiocarbamate (SDEC), tellurium diethyldithiocarbamate (TDEC), and zinc dibenzyldithiocarbamate (ZEBC).

[0213] The term activator as used herein refers to any substance that activates a vulcanizing agent and enables it to cross-link elastomers as described above. Activators may act via various mechanisms, including, but not limited to, by forming chemical complexes with accelerators or by coordinating to sulfur (when sulfur is used as a vulcanizing agent). Non-limiting examples of activators include metal oxides, acids, and metal complexex. Non-limiting examples of metal oxides include zinc oxide, magnesium oxide, and lead oxide. Non-limiting examples of acids include stearic acid and lauric acid. Non limiting examples of metal complexes include zinc ethylhexanoate.

[0214] The term pre-vulcanization inhibitor as used herein refers to compounds that delay the onset and/or the rate of vulcanization. These compounds are also referred to as retarders. Non-limiting examples of pre-vulcanization inhibitors include N-(cyclohexylthio)phthalimide (CTP), benzoic anhydride, salicylic anhydride, and phthalic anhydride.

[0215] In some embodiments, a Composition of the Disclosure comprises from about 15 wt/wt % to about 85 wt/wt % of one or more rubber chemicals. In some embodiments, the composition comprises from about 1 wt/wt % to about 5 wt/wt %, from about 1 wt/wt % to about 15 wt/wt %, from about 1 wt/wt % to about 25 wt/wt %, from about 1 wt/wt % to about 35 wt/wt %, from about 1 wt/wt % to about 45 wt/wt %, from about 1 wt/wt % to about 55 wt/wt % from about 1 wt/wt % to about 65 wt/wt % from about 1 wt/wt % to about 75 wt/wt % from about 1 wt/wt % to about 85 wt/wt % from about 1 wt/wt % to about 95 wt/wt % from about 5 wt/wt % to about 15 wt/wt % from about 5 wt/wt % to about 25 wt/wt % from about 5 wt/wt % to about 35 wt/wt % from about 5 wt/wt % to about 45 wt/wt % from about 5 wt/wt % to about 55 wt/wt % from about 5 wt/wt % to about 65 wt/wt % from about 5 wt/wt % to about 75 wt/wt % from about 5 wt/wt % to about 85 wt/wt % from about 5 wt/wt % to about 95 wt/wt % from about 15 wt/wt % to about 25 wt/wt % from about 15 wt/wt % to about 35 wt/wt % from about 15 wt/wt % to about 45 wt/wt % from about 15 wt/wt % to about 55 wt/wt % from about 15 wt/wt % to about 65 wt/wt % from about 15 wt/wt % to about 75 wt/wt % from about 15 wt/wt % to about 95 wt/wt % from about 25 wt/wt % to about 35 wt/wt % from about 25 wt/wt % to about 45 wt/wt % from about 25 wt/wt % to about 55 wt/wt % from about 25 wt/wt % to about 65 wt/wt % from about 25 wt/wt % to about 75 wt/wt % from about 25 wt/wt % to about 85 wt/wt % from about 25 wt/wt % to about 95 wt/wt % from about 35 wt/wt % to about 45 wt/wt % from about 35 wt/wt % to about 55 wt/wt % from about 35 wt/wt % to about 65 wt/wt % from about 35 wt/wt % to about 75 wt/wt % from about 35 wt/wt % to about 85 wt/wt % from about 35 wt/wt % to about 95 wt/wt % from about 45 wt/wt % to about 55 wt/wt % from about 45 wt/wt % to about 65 wt/wt % from about 45 wt/wt % to about 75 wt/wt % from about 45 wt/wt % to about 85 wt/wt % from about 45 wt/wt % to about 95 wt/wt % from about 55 wt/wt % to about 65 wt/wt % from about 55 wt/wt % to about 75 wt/wt % from about 55 wt/wt % to about 85 wt/wt % from about 55 wt/wt % to about 95 wt/wt % from about 65 wt/wt % to about 75 wt/wt % from about 65 wt/wt % to about 85 wt/wt % from about 65 wt/wt % to about 95 wt/wt % from about 75 wt/wt % to about 85 wt/wt % from about 75 wt/wt % to about 95 wt/wt % or from about 85 wt/wt % to about 95 wt/wt % of one or more rubber chemicals.

[0216] In some embodiments, a Composition of the Disclosure comprises about 15 wt/wt % of one or more rubber chemicals. In some embodiments, the composition comprises about 1 wt/wt %, about 5 wt/wt %, about 10 wt/wt %, about 20 wt/wt %, about 25 wt/wt %, about 30 wt/wt %, about 35 wt/wt %, about 40 wt/wt %, about 45 wt/wt %, about 50 wt/wt %, about 55 wt/wt %, about 60 wt/wt %, about 65 wt/wt %, about 70 wt/wt %, about 75 wt/wt %, about 80 wt/wt %, about 85 wt/wt %, about 90 wt/wt %, or about 95 wt/wt % of one or more rubber chemicals.

[0217] In some embodiments, a Composition of the Disclosure comprises from about 1 phr to about 20 phr of one or more rubber chemicals. In some embodiments, the composition comprises from about 0.1 phr to about 1 phr, from about 0.1 phr to about 5 phr, from about 0.1 phr to about 10 phr, from about 0.1 phr to about 15 phr, from about 0.1 phr to about 20 phr, from about 0.1 phr to about 25 phr, from about 0.1 phr to about 30 phr, from about 0.1 phr to about 35 phr, from about 0.1 phr to about 40 phr, from about 1 phr to about 5 phr, from about 1 phr to about 10 phr, from about 1 phr to about 15 phr, from about 1 phr to about 25 phr, from about 1 phr to about 30 phr, from about 1 phr to about 35 phr, from about 1 phr to about 40 phr, from about 5 phr to about 10 phr, from about 5 phr to about 15 phr, from about 5 phr to about 20 phr, from about 5 phr to about 25 phr, from about 5 phr to about 30 phr, from about 5 phr to about 35 phr, from about 5 phr to about 40 phr, from about 10 phr to about 15 phr, from about 10 phr to about 20 phr, from about 10 phr to about 25 phr, from about 10 phr to about 30 phr, from about 10 phr to about 35 phr, from about 10 phr to about 40 phr, from about 15 phr to about 20 phr, from about 15 phr to about 25 phr, from about 15 phr to about 30 phr, from about 15 phr to about 35 phr, from about 15 phr to about 40 phr, from about 20 phr to about 25 phr, from about 20 phr to about 30 phr, from about 20 phr to about 35 phr, from about 20 phr to about 40 phr, from about 25 phr to about 30 phr, from about 25 phr to about 35 phr, from about 25 phr to about 40 phr, from about 30 phr to about 35 phr, from about 30 phr to about 40 phr, or from about 35 phr to about 40 phr of one or more rubber chemicals.

[0218] In some embodiments, a Composition of the Disclosure comprises about 10 phr of one or more rubber chemicals. In some embodiments, the composition comprises about 0.1 phr, about 1 phr, about 5 phr, about 15 phr, about 20 phr, about 25 phr, about 30 phr, about 35 phr, or about 40 phr of one or more rubber chemicals.

[0219] The term plasticizer as used herein refers to a processing aid used to reduce the viscosity, increase the plasticity, and/or extend the volume of a composition. Plasticizers facilitate the process of mixing and forming a composition comprising an elastomer before the composition is vulcanized. Non-limiting examples of plasticizers include mineral oils (paraffinic, aromatic, or naphthenic), organic esters, resins, waxes, ester plasticizers, and naturally derived oils, such as soybean oil, vegetable oil, or orange oil.

[0220] In some embodiments, a Composition of the Disclosure comprises from about 15 wt/wt % to about 85 wt/wt % of one or more plasticizers. In some embodiments, the composition comprises from about 1 wt/wt % to about 5 wt/wt %, from about 1 wt/wt % to about 15 wt/wt %, from about 1 wt/wt % to about 25 wt/wt %, from about 1 wt/wt % to about 35 wt/wt % from about 1 wt/wt % to about 45 wt/wt % from about 1 wt/wt % to about 55 wt/wt % from about 1 wt/wt % to about 65 wt/wt % from about 1 wt/wt % to about 75 wt/wt % from about 1 wt/wt % to about 85 wt/wt % from about 1 wt/wt % to about 95 wt/wt % from about 5 wt/wt % to about 15 wt/wt % from about 5 wt/wt % to about 25 wt/wt % from about 5 wt/wt % to about 35 wt/wt % from about 5 wt/wt % to about 45 wt/wt % from about 5 wt/wt % to about 55 wt/wt % from about 5 wt/wt % to about 65 wt/wt % from about 5 wt/wt % to about 75 wt/wt % from about 5 wt/wt % to about 85 wt/wt % from about 5 wt/wt % to about 95 wt/wt % from about 15 wt/wt % to about 25 wt/wt % from about 15 wt/wt % to about 35 wt/wt % from about 15 wt/wt % to about 45 wt/wt % from about 15 wt/wt % to about 55 wt/wt % from about 15 wt/wt % to about 65 wt/wt % from about 15 wt/wt % to about 75 wt/wt % from about 15 wt/wt % to about 95 wt/wt % from about 25 wt/wt % to about 35 wt/wt % from about 25 wt/wt % to about 45 wt/wt % from about 25 wt/wt % to about 55 wt/wt % from about 25 wt/wt % to about 65 wt/wt % from about 25 wt/wt % to about 75 wt/wt % from about 25 wt/wt % to about 85 wt/wt % from about 25 wt/wt % to about 95 wt/wt % from about 35 wt/wt % to about 45 wt/wt % from about 35 wt/wt % to about 55 wt/wt % from about 35 wt/wt % to about 65 wt/wt % from about 35 wt/wt % to about 75 wt/wt % from about 35 wt/wt % to about 85 wt/wt % from about 35 wt/wt % to about 95 wt/wt % from about 45 wt/wt % to about 55 wt/wt % from about 45 wt/wt % to about 65 wt/wt % from about 45 wt/wt % to about 75 wt/wt % from about 45 wt/wt % to about 85 wt/wt % from about 45 wt/wt % to about 95 wt/wt % from about 55 wt/wt % to about 65 wt/wt % from about 55 wt/wt % to about 75 wt/wt % from about 55 wt/wt % to about 85 wt/wt % from about 55 wt/wt % to about 95 wt/wt % from about 65 wt/wt % to about 75 wt/wt % from about 65 wt/wt % to about 85 wt/wt % from about 65 wt/wt % to about 95 wt/wt % from about 75 wt/wt % to about 85 wt/wt % from about 75 wt/wt % to about 95 wt/wt % or from about 85 wt/wt % to about 95 wt/wt % of one or more plasticizers.

[0221] In some embodiments, a Composition of the Disclosure comprises about 15 wt/wt % of one or more plasticizers. In some embodiments, the composition comprises about 1 wt/wt %. about 5 wt/wt %. about 10 wt/wt %. about 20 wt/wt %. about 25 wt/wt %. about 30 wt/wt %, about 35 wt/wt %, about 40 wt/wt %, about 45 wt/wt %, about 50 wt/wt %, about 55 wt/wt %, about 60 wt/wt %, about 65 wt/wt %, about 70 wt/wt %, about 75 wt/wt %, about 80 wt/wt %, about 85 wt/wt %, about 90 wt/wt %, or about 95 wt/wt % of one or more plasticizers.

[0222] In some embodiments, a Composition of the Disclosure comprises from about 1 phr to about 20 phr of one or more plasticizers. In some embodiments, the composition comprises from about 0.1 phr to about 1 phr, from about 0.1 phr to about 5 phr, from about 0.1 phr to about 10 phr, from about 0.1 phr to about 15 phr, from about 0.1 phr to about 20 phr, from about 0.1 phr to about 25 phr, from about 0.1 phr to about 30 phr, from about 0.1 phr to about 35 phr, from about 0.1 phr to about 40 phr, from about 1 phr to about 5 phr, from about 1 phr to about 10 phr, from about 1 phr to about 15 phr, from about 1 phr to about 25 phr, from about 1 phr to about 30 phr, from about 1 phr to about 35 phr, from about 1 phr to about 40 phr, from about 5 phr to about 10 phr, from about 5 phr to about 15 phr, from about 5 phr to about 20 phr, from about 5 phr to about 25 phr, from about 5 phr to about 30 phr, from about 5 phr to about 35 phr, from about 5 phr to about 40 phr, from about 10 phr to about 15 phr, from about 10 phr to about 20 phr, from about 10 phr to about 25 phr, from about 10 phr to about 30 phr, from about 10 phr to about 35 phr, from about 10 phr to about 40 phr, from about 15 phr to about 20 phr, from about 15 phr to about 25 phr, from about 15 phr to about 30 phr, from about 15 phr to about 35 phr, from about 15 phr to about 40 phr, from about 20 phr to about 25 phr, from about 20 phr to about 30 phr, from about 20 phr to about 35 phr, from about 20 phr to about 40 phr, from about 25 phr to about 30 phr, from about 25 phr to about 35 phr, from about 25 phr to about 40 phr, from about 30 phr to about 35 phr, from about 30 phr to about 40 phr, or from about 35 phr to about 40 phr of one or more plasticizers.

[0223] In some embodiments, a Composition of the Disclosure comprises about 10 phr of one or more plasticizers. In some embodiments, the composition comprises about 0.1 phr, about 1 phr, about 5 phr, about 15 phr, about 20 phr, about 25 phr, about 30 phr, about 35 phr, or about 40 phr of one or more plasticizers.

[0224] In some embodiments, a Composition of the Disclosure further comprises a second antidegradant that is not a Compound of the Disclosure. In some embodiments, the second antidegradant is an antioxidant. In some embodiments, the second antidegradant is an antiozonant. Non-limiting examples of antidegradants include paraphenylenediamines (PPDs), trimethyl-dihydroquinolines (TMQs), phenolics, alkylated diphenylamines (DPAs), diphenylamine-ketone condensates, and natural antidegradants. Non-limiting examples of PPDs include N.sup.1-(4-methylpentan-2-yl)-N.sup.4-phenylbenzene-1,4-diamine (6PPD), N-(1,4-dimethylpentyl)-N-phenyl-p-phenylenediamine (7PPD), N.sup.1-phenyl-N.sup.4-(propan-2-yl)benzene-1,4-diamine (IPPD), N,N-di-sec-butyl-p-phenylenediamine (44PD), N,N-bis(1,3-dimethylbutyl)-p-phenylenediamine (66PD), N,N-bis(1,4-dimethylpentyl)-p-phenylenediamine (77PD), and N-N-dioctyl-p-phenylenediamine (88PD). Non-limiting examples of TMQs include 2,2,4-trimethyl-1,2-dihydroquinoline and oligomers or polymers thereof.

[0225] In some embodiments, a Composition of the Disclosure comprises from about 15 wt/wt % to about 85 wt/wt % of a second antidegradant. In some embodiments, the composition comprises from about 1 wt/wt % to about 5 wt/wt %, from about 1 wt/wt % to about 15 wt/wt %, from about 1 wt/wt % to about 25 wt/wt %, from about 1 wt/wt % to about 35 wt/wt % from about 1 wt/wt % to about 45 wt/wt % from about 1 wt/wt % to about 55 wt/wt % from about 1 wt/wt % to about 65 wt/wt % from about 1 wt/wt % to about 75 wt/wt % from about 1 wt/wt % to about 85 wt/wt % from about 1 wt/wt % to about 95 wt/wt % from about 5 wt/wt % to about 15 wt/wt % from about 5 wt/wt % to about 25 wt/wt % from about 5 wt/wt % to about 35 wt/wt % from about 5 wt/wt % to about 45 wt/wt % from about 5 wt/wt % to about 55 wt/wt % from about 5 wt/wt % to about 65 wt/wt % from about 5 wt/wt % to about 75 wt/wt % from about 5 wt/wt % to about 85 wt/wt % from about 5 wt/wt % to about 95 wt/wt % from about 15 wt/wt % to about 25 wt/wt % from about 15 wt/wt % to about 35 wt/wt % from about 15 wt/wt % to about 45 wt/wt % from about 15 wt/wt % to about 55 wt/wt % from about 15 wt/wt % to about 65 wt/wt % from about 15 wt/wt % to about 75 wt/wt % from about 15 wt/wt % to about 95 wt/wt % from about 25 wt/wt % to about 35 wt/wt % from about 25 wt/wt % to about 45 wt/wt % from about 25 wt/wt % to about 55 wt/wt % from about 25 wt/wt % to about 65 wt/wt % from about 25 wt/wt % to about 75 wt/wt % from about 25 wt/wt % to about 85 wt/wt % from about 25 wt/wt % to about 95 wt/wt % from about 35 wt/wt % to about 45 wt/wt % from about 35 wt/wt % to about 55 wt/wt %, from about 35 wt/wt % to about 65 wt/wt % from about 35 wt/wt % to about 75 wt/wt % from about 35 wt/wt % to about 85 wt/wt % from about 35 wt/wt % to about 95 wt/wt % from about 45 wt/wt % to about 55 wt/wt % from about 45 wt/wt % to about 65 wt/wt % from about 45 wt/wt % to about 75 wt/wt % from about 45 wt/wt % to about 85 wt/wt % from about 45 wt/wt % to about 95 wt/wt % from about 55 wt/wt % to about 65 wt/wt % from about 55 wt/wt % to about 75 wt/wt %, from about 55 wt/wt % to about 85 wt/wt %, from about 55 wt/wt % to about 95 wt/wt % from about 65 wt/wt % to about 75 wt/wt % from about 65 wt/wt % to about 85 wt/wt % from about 65 wt/wt % to about 95 wt/wt % from about 75 wt/wt % to about 85 wt/wt % from about 75 wt/wt % to about 95 wt/wt % or from about 85 wt/wt % to about 95 wt/wt % of a second antidegradant.

[0226] In some embodiments, a Composition of the Disclosure comprises about 15 wt/wt % of a second antidegradant. In some embodiments, the composition comprises about 1 wt/wt %, about 5 wt/wt %, about 10 wt/wt %, about 20 wt/wt %, about 25 wt/wt %, about 30 wt/wt %, about 35 wt/wt %, about 40 wt/wt %, about 45 wt/wt %, about 50 wt/wt %, about 55 wt/wt %, about 60 wt/wt %, about 65 wt/wt %, about 70 wt/wt %, about 75 wt/wt %, about 80 wt/wt %, about 85 wt/wt %, about 90 wt/wt %, or about 95 wt/wt % of a second antidegradant.

[0227] In some embodiments, a Composition of the Disclosure comprises from about 1 to about 5 phr of a second antidegradant. In some embodiments, the composition comprises from about 0.001 phr to about 0.01 phr, from about 0.001 phr to about 0.1 phr, from about 0.001 phr to about 1 phr, from about 0.001 phr to about 5 phr, from about 0.001 phr to about 7.5 phr, from about 0.001 phr to about 10 phr, from about 0.01 phr to about 0.1 phr, from about 0.01 phr to about 1 phr, from about 0.01 phr to about 5 phr, from about 0.01 phr to about 7.5 phr, from about 0.01 phr to about 10 phr, from about 0.1 phr to about 1 phr, from about 0.1 phr to about 5 phr, from about 0.1 phr to about 7.5 phr, from about 0.1 phr to about 10 phr, from about 1 phr to about 7.5 phr, from about 1 phr to about 10 phr, from about 5 phr to about 7.5 phr, from about 5 phr to about 10 phr, or from about 7.5 phr to about 10 phr.

[0228] In some embodiments, a Composition of the Disclosure comprises about 3 phr of a second antidegradant. In some embodiments, the composition comprises about 0.001 phr, about 0.01 phr, about 0.1 phr, about 1 phr, about 2 phr, about 4 phr, about 5 phr, about 7.5 phr, or about 10 phr of a second antidegradant.

[0229] In some embodiments, the disclosure provides a composition comprising a Compound of the Disclosure and one or more carriers. The term carrier as used herein refers to a solid that can adsorb a liquid while retaining the general properties of a solid at room temperature. In some embodiments, the carrier is an inert material. In some embodiments, the carrier has a high surface area. In some embodiments, the carrier comprises particles with diameters of less than 500 microns.

[0230] In some embodiments, the composition comprises from about 15 wt/wt % to about 85 wt/wt % of one or more carriers. In some embodiments, the composition comprises from about 1 wt/wt % to about 5 wt/wt %, from about 1 wt/wt % to about 15 wt/wt %, from about 1 wt/wt % to about 25 wt/wt %, from about 1 wt/wt % to about 35 wt/wt 0 from about 1 wt/wt % to about 45 wt/wt %, from about 1 wt/wt % to about 55 wt/wt 0 from about 1 wt/wt % to about 65 wt/wt %, from about 1 wt/wt % to about 75 wt/wt 0 from about 1 wt/wt % to about 85 wt/wt %, from about 1 wt/wt % to about 95 wt/wt 0 from about 5 wt/wt % to about 15 wt/wt %, from about 5 wt/wt % to about 25 wt/wt 0 from about 5 wt/wt % to about 35 wt/wt %, from about 5 wt/wt % to about 45 wt/wt from about 5 wt/wt % to about 55 wt/wt %, from about 5 wt/wt % to about 65 wt/wt 0 from about 5 wt/wt % to about 75 wt/wt %, from about 5 wt/wt % to about 85 wt/wt from about 5 wt/wt % to about 95 wt/wt %, from about 15 wt/wt % to about 25 wt/wt 0 from about 15 wt/wt % to about 35 wt/wt %, from about 15 wt/wt % to about 45 wt/wt 00 from about 15 wt/wt % to about 55 wt/wt %, from about 15 wt/wt % to about 65 wt/wt 00 from about 15 wt/wt % to about 75 wt/wt %, from about 15 wt/wt % to about 95 wt/wt 00 from about 25 wt/wt % to about 35 wt/wt %, from about 25 wt/wt % to about 45 wt/wt 0 from about 25 wt/wt % to about 55 wt/wt %, from about 25 wt/wt % to about 65 wt/wt from about 25 wt/wt % to about 75 wt/wt %, from about 25 wt/wt % to about 85 wt/wt from about 25 wt/wt % to about 95 wt/wt %, from about 35 wt/wt % to about 45 wt/wt from about 35 wt/wt % to about 55 wt/wt %, from about 35 wt/wt % to about 65 wt/wt 0 from about 35 wt/wt % to about 75 wt/wt %, from about 35 wt/wt % to about 85 wt/wt 0 from about 35 wt/wt % to about 95 wt/wt %, from about 45 wt/wt % to about 55 wt/wt 0 from about 45 wt/wt % to about 65 wt/wt %, from about 45 wt/wt % to about 75 wt/wt from about 45 wt/wt % to about 85 wt/wt %, from about 45 wt/wt % to about 95 wt/wt from about 55 wt/wt % to about 65 wt/wt %, from about 55 wt/wt % to about 75 wt/wt 00 from about 55 wt/wt % to about 85 wt/wt %, from about 55 wt/wt % to about 95 wt/wt 00 from about 65 wt/wt % to about 75 wt/wt %, from about 65 wt/wt % to about 85 wt/wt from about 65 wt/wt % to about 95 wt/wt %, from about 75 wt/wt % to about 85 wt/wt 00 from about 75 wt/wt % to about 95 wt/wt %, or from about 85 wt/wt % to about 95 wt/wt % of one or more carriers.

[0231] In some embodiments, the composition comprises about 15 wt/wt % of one or more carriers. In some embodiments, the composition comprises about 1 wt/wt %, about 5 wt/wt %, about 10 wt/wt %, about 20 wt/wt %, about 25 wt/wt %, about 30 wt/wt %, about 35 wt/wt %, about 40 wt/wt %, about 45 wt/wt %, about 50 wt/wt %, about 55 wt/wt %, about 60 wt/wt %, about 65 wt/wt %, about 70 wt/wt %, about 75 wt/wt %, about 80 wt/wt %, about 85 wt/wt %, about 90 wt/wt %, or about 95 wt/wt % of one or more carriers.

[0232] The present disclosure also provides processes for preparing a composition comprising a Compound of the Disclosure and one or more carriers, the process comprising admixing the compound and the one or more carriers.

[0233] The present disclosure also provides lubricant compositions comprising a Compound of the Disclosure and a lubricant. Non-limiting examples of lubricants include mineral oil, higher molecular weight petroleum distillates such as aromatic, naphthenic, and paraffinic distillates, synthetic oils such as polyalpha-olefin (PAO), synthetic esters, polyalkylene glycols (PAG), phosphate esters, perfluoropolyether (PFPE), alkylated naphthlalenes (AN), silicate esters, ionic fluids, and multiply alkylated cyclopentanes (MAC), solid lubricants such as polytetrafluoroethylene (PTFE), graphite, hexagonal boron nitride, molybdenum disulfide, tungsten disulfide, aqueous lubricants such as hydrated brush polymers, and biolubricants such as triglyceride esters, high oleic canola oil, castor oil, palm oil, sunflower seed oil, and rapeseed oil.

[0234] The present disclosure also provides combustible fuel compositions comprising a combustible fuel and a Compound of the Disclosure. Non-limiting examples of combustible fuel include gasoline, diesel, kerosene, liquefied petroleum gas, synthetic fuel, and biodisesel.

[0235] The present disclosure also provides fuel additive compositions comprising a fuel additive and a Compound of the Disclosure. Non-limiting examples of fuel additives include oxygenates such as alcohols and ethers, antioxidants, stabilizers, detergents, antiknock agents, lead scavengers, fuel dyes, viscosity modifiers, and butyl rubber. In some embodiments, the butyl rubber is in the form of polyisobutylene succinimide. In some embodiments, the butyl rubber is added as a detergent to prevent fouling of diesel fuel injectors.

Vulcanized Elastomeric Articles

[0236] The present disclosure also provides vulcanized elastomeric articles comprising a Compound of the Disclosure. The term vulcanized elastomeric article refers to an article that is made by forming a composition comprising an elastomer into a specific shape and vulcanizing the composition to provide the article.

[0237] The present disclosure also provides vulcanized elastomeric articles prepared using a composition described herein.

[0238] In some embodiments, the vulcanized elastomeric article is a tire. In some embodiments, the tire is a passenger vehicle tire, a light truck tire, a heavy truck or bus tire, a motorcycle tire, an agriculture tire, an earthmover tire, an airplane tire, or a racing tire.

[0239] In some embodiments, the vulcanized elastomeric article is a component of a tire. In some embodiments, the component is a bead, a belt, a body ply, an inner liner, a sidewall, an undertread, or a tread.

[0240] In some embodiments, the vulcanized elastomeric article is a rubber overshoe, a sealing strip, an acoustic panel, an air spring, a bellow, a membrane, a tactile sensor, a crash pad, a hose, a conveyor belt, or a flooring.

Processes

[0241] The present disclosure also provides processes for preparing a vulcanized elastomeric article, the process comprising: [0242] (a) forming a composition described herein into a formed shape; and [0243] (b) vulcanizing the formed shape, to provide a vulcanized elastomeric article.

[0244] In some embodiments, the vulcanizing is performed at an average temperature of from about 140 C. to about 160 C. In some embodiments, the vulcanizing is performed at an average temperature of from about 80 C. to about 100 C., from about 80 C. to about 120 C., from about 80 C. to about 140 C., from about 80 C. to about 160 C., from about 80 C. to about 180 C., from about 80 C. to about 200 C., from about 100 C. to about 120 C., from about 100 C. to about 140 C., from about 100 C. to about 160 C., from about 100 C. to about 180 C., from about 100 C. to about 200 C., from about 120 C. to about 140 C., from about 120 C. to about 160 C., from about 120 C. to about 180 C., from about 120 C. to about 200 C., from about 140 C. to about 180 C., from about 140 C. to about 200 C., from about 160 C. to about 180 C., from about 160 C. to about 200 C., or from about 180 C. to about 200 C.

[0245] In some embodiments, the vulcanizing is performed at an average temperature of about 150 C. In some embodiments, the vulcanizing is performed at an average temperature of about 80 C., about 100 C., about 120 C., about 140 C., about 160 C., about 180 C., or about 200 C.

[0246] The present disclosure also provides processes for retreading tires, the process comprising: [0247] (a) applying a composition described herein to a tire; [0248] (b) disposing a pre-vulcanized tread around the tire; [0249] (c) disposing a curing envelope around the tire; and [0250] (d) vulcanizing the tire.

Kits

[0251] The present disclosure also provides kits comprising a composition described herein, packaged in a manner, e.g., in a container, that facilitates use of the composition to practice the processes and/or methods of the present disclosure. In some embodiments, the kit comprises a composition described herein and instructions for using the composition in a vulcanizable elastomeric composition. In some embodiments, the kit comprises a composition described herein and instructions for using the composition to prepare a vulcanized elastomeric article. The composition may be packaged in any suitable container, such as a sealed bottle or vessel, with a label affixed to the container or included in the kit that describes the composition and proper use thereof.

EXAMPLES

Example 1

Synthesis of 2,2,4,8-tetramethyl-N-phenyl-1,2-dihydroquinolin-6-amine (Compound 1)

Step 1

##STR00137##

[0252] A 250-mL round bottom flask fitted with a stir-bar and a thermometer was purged with N.sub.2, then protected with N.sub.2 blanket (the outlet was connected to a base trap containing about 250 mL of 1 mol/L NaOH). Glacial acetic acid (18.0 mL) was loaded to the flask, then stirred was started. 3-Methyldiphenylamine (4.8 mL; 27.9 mmol) was added (no exotherm was observed). Once 3-methyldiphenylamine was fully dissolved, aq. 37% HCl (2.9 mL; 35.0 mmol HCl) was added over 40 seconds. The temperature rose to 26 C. The flask was chilled with ice-water bath. Once the temperature reached 5 C., a solution of sodium nitrite (1.93 g; 27.9 mmol) in DI water (5.6 mL) was drop-wise added such that the temperature was kept below 8 C., over a period of 9.5-10.0 minutes. A dense liquid phase separated. The ice-water bath was removed. The reaction mixture was stirred at 7-20 C. for 35 min to complete formation of the nitrosamine intermediate. The flask was chilled with an ice-water bath. Once the temperature reached 10 C., aq. 37% HCl (5.8 mL; 70.0 mmol) was added over 2.5-3.0 min (no exotherm was observed). The ice-water bath was removed. The reaction mixture was stirred at 10-25 C. to complete formation of the desired product. A red solid separated after approx. 30 min. After 120 min (total reaction time), the mixture was diluted with DI water (76 mL), whereupon a slurry formed. The solid was collected by vacuum filtration (Buchner-filter paper) and washed with DI water. An aliquot of the damp solid analyzed by LC-MS/UV (260 nm) indicated the presence of 87% desired product. The damp solid was triturated with EtOH (45 mL). The slurry was filtered under suction. The obtained solid was dried under vacuum at 40 C. for a couple of hours. Yield=5.1 g (86% of the theoretical yield with respect to 3-methyldiphenylamine) as a brick red powder. The crude material was involved in the next step without further purification.

Step 2

##STR00138##

[0253] To a 250-mL flask fitted with a stir-bar and a thermometer were loaded 3-methyl-4-nitroso-N-phenylaniline (see Step 1; 5.0 g; 23.6 mmol) and EtOH (100 mL). The mixture was stirred under N.sub.2 protection (most of the solid dissolved; a brown solution was obtained). Ammonium sulfate (3.11 g; 23.6 mmol) was added in one portion (no exotherm was observed). The mixture was stirred for approx. 1 hour at room temperature. The flask was chilled with a cold tap water bath. Sodium borohydride (1.80 g; 47.6 mmol) was portion-wise added over approximately 2 minutes. The reaction mixture was stirred with the water bath for 10 min (the temperature rose to 32 C.). The water batch was removed. the temperature rose to 35 C. About one hour later, additional NaBH.sub.4 (0.48 g; 12.7 mmol) was added. The reaction mixture was stirred for additional 1.5 hours. Additional NaBH.sub.4 (0.89 g; 23.5 mmol) and ammonium sulfate (3.49 g; 26.4 mmol) were added (at 2.5 hours reaction time). The reaction mixture was stirred for additional time. The total reaction time was 3 hours. DI water (66 mL) was slowly added. The mixture was diluted with ethyl acetate (200 mL). The organic phase was washed with aq. 1M NaOH (3100 mL), with brine (100 mL), dried over MgSO.sub.4, filtered, and stripped of volatiles under reduced pressure (rotary evaporator; water bath=50 C.). The resulting black oil was dried on a rotary evaporator (55 C.; <5 mbar) for 15-20 minutes. Yield=3.2 g (68% based on 3-methyl-4-nitroso-N-phenylaniline) as a black gooey material (Intermediate Compound 1-I). An aliquot of Intermediate Compound 1-I was characterized by LC-MS/UV (260 nm) as well as .sup.1H and APT .sup.13C NMR spectroscopy, as shown in FIGS. 1 and 2, respectively. Intermediate Compound 1-I (83.4% pure according to LC-MS/UV (260 nm)) was used in the next step without further purification.

Step 3

##STR00139##

[0254] To a 250-mL flask fitted with a stir-bar and a reflux condenser were loaded crude 3-methyl-N.sup.1-phenylbenzene-1,4-diamine (Intermediate Compound 1-I; 83.4% pure; 3.1 g; <15.6 mmol), and acetone (6.5 mL; 87.9 mol). The mixture was stirred under N.sub.2 protection. Zinc(II) triflate (679 mg; 1.87 mmol) was loaded in one portion. The reaction mixture was heated (oil bath=62 C.). After 16.5 hours, additional acetone (3 mL; 40.6 mmol) was added. The total reaction time at 62 C. was 25 hours. The reaction mixture was stirred at room temperature for about 48 hours. The obtained black liquid was diluted with a mixture of hexanes and ethyl acetate (5 mL). The obtained solution was loaded into a 41 mm diameter chromatography column previously prepared with silica gel 60 (approx. 23 cm height) and eluent (10% ethyl acetate in hexanes). The column was eluted with 10% ethyl acetate in hexanes. Several fractions (approx. 30 mL each) were collected and characterized by silica gel TLC (10% ethyl acetate in hexanes). The portions containing the dots at Rf=0.35 (desired product) were collected, combined, and stripped of volatiles under reduced pressure (rotary evaporator; water bath=50 C.). Note that mesityl oxide shows as a dot at Rf=0.40 and was not separated from the product at that stage. The resulting yellow liquid was dried on a rotary evaporator (65 C.; <5 mbars) for 10 min. Yield=0.34 g as a yellow viscous material (Compound 1). An aliquot of Compound 1 was characterized by LC-MS/UV (260 nm) as well as by .sup.1H and APT .sup.13C NMR spectroscopy, as shown in FIGS. 3 and 4, respectively.

Example 2

Synthesis of 8-methoxy-2,2,4-trimethyl-N-phenyl-1,2-dihydroquinolin-6-amine (Compound 7)

Step 1

##STR00140##

[0255] To a 250-mL round bottom flask fitted with a stir-bar and a thermometer was loaded 3-methoxydiphenylamine (11.8 g; 59.2 mmol) and glacial acetic acid (36 mL). The mixture was stirred under N.sub.2 protection (the outlet was connected to a base trap containing about 250 mL of 1 M NaOH). Aq. 37% HCl (18 mL; 217 mmol HCl) was added by portions over a couple of minutes. 3-methoxydiphenylamine dissolved during the addition of aq. HCl. No exotherm was observed. A light-yellow solution was obtained. The flask was chilled with ice-water bath. Once the temperature reached 4-5 C., a solution of sodium nitrite (4.169 g; 60.4 mmol) in distilled water (12 mL) was gradually added over a period of 17-18 min such that the temperature was kept under 10 C. The resulting dark-red mixture was stirred between 2 C. and 9 C. for 30 min, then the chilling bath was removed. The reaction mixture was stirred without external cooling or heating (2-22 C.) for 2 h 40 min, whereupon a dark red solid separated. Distilled water (80 mL) was added and the slurry was stirred for a few minutes. The solid was collected by filtration under suction, then rinsed quickly with distilled water and EtOH (50 mL). Drying under vacuum at 40 C. for about 2 h, then at room temperature overnight, yielded 7.8 g (57% of the theoretical with respect to 3-methoxydiphenylamine) of a dark red powder. An aliquot of this material was characterized by LC-MS/UV (260 nm). The crude material was involved in the next step without further purification.

Step 2

##STR00141##

[0256] To a 500-mL flask fitted with a stir-bar and a thermometer were loaded 3-methoxy-4-nitroso-N-phenylaniline (See Step 1; 7.8 g; 34.2 mmol) and EtOH (210 mL). The mixture was stirred under N.sub.2 protection (some solid remained insoluble; a red slurry was obtained). Ammonium sulfate (9.05 g; 68.5 mmol) was added in one portion (no exotherm was observed) and the mixture was stirred for approximately 1 h at room temperature. The flask was chilled with a cold tap water bath. Sodium borohydride (3.31 g; 87.5 mmol) was portion-wise added over a period of 16 min such that the temperature was kept under 28 C. (frothing occurred). The reaction mixture was stirred with the water bath for 110 min, during which the reaction mixture turned black. The water bath was removed. Approximately 10 min later, distilled water (150 mL) was slowly added and the mixture was stirred for a few minutes. The mixture was diluted with ethyl acetate (450 mL) in a separatory funnel containing distilled water (100 mL) and aq. 1 M NaOH (100 mL). After shaking and decanting, the aqueous layer was discarded. The organic layer was washed with aqueous 1 M NaOH (100 mL) and brine (100 mL), dried over MgSO.sub.4, filtered, and stripped of volatiles under reduced pressure (rotary evaporator; water bath=55 C.). The resulting black oil was dried on a rotary evaporator (55 C.; <12 mbar) for 1 h. Crude yield=6.2 g as a black gooey material. The crude material was dissolved in toluene (10 mL). The obtained black solution was loaded into a 71 mm diameter chromatography column previously prepared with silica gel 60 (8 height) and eluent (50% ethyl acetate in hexanes). The flask was rinsed with 50% ethyl acetate in hexanes (5-10 mL). The column was eluted with 50% ethyl acetate in hexanes. The portions (100 mL each) containing the desired product (TLC 50% ethyl acetate in hexanes; dots at Rf=0.7) were collected, combined, and stripped of volatiles under reduced pressure (rotary evaporator; water bath=50 C.). The resulting black/purple viscous liquid was dried on a rotary evaporator (55 C.; <2 mbar) for 15-30 min. Yield=4.3 g (58% based on 3-methoxy-4-nitroso-N-phenylaniline) as a dark viscous material (Intermediate Compound 7-I). An aliquot of Intermediate Compound 7-I was characterized by .sup.1H and APT .sup.13C NMR spectroscopy, as shown in FIGS. 5 and 6, respectively.

Step 3

##STR00142##

[0257] To a 250-mL flask fitted with a stir-bar and a reflux condenser were loaded 3-methoxy-N.sup.1-phenylbenzene-1,4-diamine (Intermediate Compound 7-I, see Step 2; 4.3 g; 20.1 mmol), acetone (8.9 mL; 120 mol), and zinc(II) triflate (0.727 g; 2.00 mmol). The mixture was stirred under N.sub.2 protection and heated (oil bath=62 C.) for 40.5 h. The substrate took about 2 h to initially dissolve, then a dark homogenous solution was obtained. Upon cooling to room temperature, the obtained black liquid was loaded into a 41 mm diameter chromatography column previously prepared with silica gel 60 (30 cm height) and eluent (20% ethyl acetate in hexanes). The flask was rinsed with additional acetone (3-4 mL). The column was eluted with 20% ethyl acetate in hexanes. Several fractions (approx. 30 mL each) were collected and characterized by silica gel TLC (20% ethyl acetate in hexanes). The fractions containing the dot at Rf=0.6 (desired product) were collected, combined, and stripped of volatiles under reduced pressure (rotary evaporator; water bath=50 C.). The resulting powder was dried on a rotary evaporator (55 C.; <3 mbars) for 20 min. Yield=2.5 g (42% of the theoretical with respect to 3-methoxy-N.sup.1-phenylbenzene-1,4-diamine) as an almost-white crystalline powder (Compound 7). An aliquot of Compound 7 was characterized by LC-MS/UV (260 nm) as well as by .sup.1H and APT .sup.13C NMR spectroscopy, as shown in FIGS. 7 and 8, respectively.

Example 3

Synthesis of 2,2,4,8-tetramethyl-N-phenyl-1,2,3,4-tetrahydroquinolin-6-amine (Compound 2)

##STR00143##

[0258] To a 20-mL vial was loaded a stir-bar, 2,2,4,8-tetramethyl-N-phenyl-1,2-dihydroquinolin-6-amine (Compound 1; 1.07 g; 3.84 mmol), and MeOH (12 mL). The mixture was stirred. Once Compound 1 was fully dissolved, aqueous 37% HCl (0.32 mL; 3.9 mmol) was added. A deep purple solution was obtained, which was added to a 300-mL Parr autoclave with MeOH (130 mL) and 10% Pd on C (Sigma, 0.25 g). The reaction mixture was maintained at 21 C. (water circulator). The autoclave was charged with H.sub.2 until 52 PSIG was attained. A modest exotherm ensued (up to 24 C.), which subsided after 10 minutes. The total reaction time was 75 minutes (the pressure decreased from 52 to 45 PSIG over the first 10 minutes, then plateaued at 44 PSIG the rest of the reaction time). The mixture was filtered through Celite S and the cake was rinsed with methanol. The combined filtrates (dark blue solution) were kept under N.sub.2 protection overnight. The volatiles were stripped under reduced pressure (rotary evaporator; water bath=50 C.). The resulting dark solid was taken up in a mixture of ethyl acetate (50 mL) and aqueous 1 mol/L NaOH (40 mL). The 2-phase system was magnetically stirred until complete dissolution of the solids over a period of 10-15 minutes. The 2-phase system was transferred to a separatory funnel. After shaking and decanting, the aqueous phase was discarded. The organic phase (brownish solution) was washed with aqueous saturated NaCl solution (40 mL), dried over anhydrous MgSO.sub.4, filtered, and stripped of volatiles under reduced pressure (rotary evaporator; water bath=50 C.). The resulting dark oil (0.95 grams) was dissolved in 10% ethyl acetate in hexanes (approx. 4 mL). The obtained solution was loaded into a 1 inner diameter column previously prepared with silica gel 60 (70-230 mesh) and 20% ethyl acetate in hexanes. The height of wet silica gel in the column was approx. 6.5. The column was eluted with 20% ethyl acetate in hexanes. The fractions containing the dot at R.sub.f=0.6 (silica gel TLC; 20% ethyl acetate in hexanes) were collected, combined, and stripped of volatiles under reduced pressure (rotary evaporator; water bath=50 C.). The obtained oil was dried on the rotary evaporator (water bath=55 C.; <3 mbars) for 1 h 40 min to yield 0.81 grams (75% with respect to Compound 1) of 2,2,4,8-tetramethyl-N-phenyl-1,2,3,4-tetrahydroquinolin-6-amine (Compound 2) as a light-brown oil. Compound 2 was characterized by .sup.1H and .sup.13C APT NMR spectroscopy, as shown in FIGS. 9 and 10, respectively. LC-UV analysis indicated 98.1% purity at 260 nm detection.

Example 4

Synthesis of 2,2,8-trimethyl-N-(1-phenylethyl)-1,2,3,4-tetrahydroquinolin-6-amine (Compound 119)

Step 1

##STR00144##

[0259] To a 250-mL round bottom flask fitted with a stir-bar, a thermometer, and a reflux condenser was loaded 2-methyl-4-nitroaniline (5.0 g; 32.9 mmol), anhydrous grade toluene (38 mL), and 2-methylbut-3-yn-2-ol (4.8 mL; 49.5 mmol). The mixture was stirred. Dry N.sub.2 was bubbled through the solution for a couple of minutes, then the system was protected with N.sub.2 blanket. Copper(II) chloride (450 mg; 3.35 mmol) and copper(I) chloride (330 mg; 3.33 mmol) were sequentially added to the flask. The reaction mixture was heated to reflux for 44 hours. Upon cooling to room temperature, the mixture was vacuum filtered through Celite S (disposable 0.2-micron polyethylene frit) and the flask/cake was rinsed with copious amounts of toluene. The filtrate was stripped of volatiles under reduced pressure (rotary evaporator; water bath=65 C.). To the residue was added 10% isopropanol in hexanes (20 mL) and the obtained slurry was magnetically stirred overnight. The yellow solid was collected by vacuum filtration (disposable 0.2-micron polyethylene frit) and rinsed with hexanes (20 mL). LC indicated about 75.1% purity at that stage. The solid was washed with 50% isopropanol in hexanes (20 mL). LC indicated about 82.3% purity at that stage. The solid was washed with 25% MeOH in hexanes containing a few drops of isopropanol (20 mL). LC indicated about 88.0% purity at that stage. Finally, the solid was washed with 50% MeOH in hexanes containing a few drops of isopropanol (20 mL) and dried under vacuum at 45 C. for about two hours to yield 1.9 grams (26.5% with respect to 2-methyl-4-nitroaniline) 2,2,8-trimethyl-6-nitro-1,2-dihydroquinoline (Intermediate Compound 119-I) as a yellow solid. Intermediate Compound 119-I was characterized by .sup.1H NMR spectroscopy, as shown in FIG. 11. LC-UV analysis indicated 98.1% purity at 260 nm detection.

Step 2

##STR00145##

[0260] To a 300-mL Parr autoclave was loaded 2,2,8-trimethyl-6-nitro-1,2-dihydroquinoline (Intermediate Compound 119-I; 0.949 g; 4.35 mmol), toluene (130 mL), acetophenone (1.00 mL; 8.57 mmol), and sulfided 3% Pt/C frm (Johnson Matthey; 0.134 g wet). The reaction mixture was heated to 120 C. Once the temperature was reached, the autoclave was continuously fed with H.sub.2 (set pressure=300 PSIG) for 2 hours. The reaction mixture was allowed to stand at room temperature under N.sub.2 protection overnight. LC-UV/MS analysis indicated incomplete conversion at that stage. The reaction mixture was heated to 150 C. under 300 PSIG of H.sub.2 for approx. 3 hours. LC-UV/MS analysis indicated better conversion at that stage. Finally, the reaction mixture was heated to 170 C. under 350 PSIG of H.sub.2 for 3 hours. LC-UV/MS analysis indicated almost complete conversion at that stage. The mixture post reaction was filtered under suction through Celite S. The cake was rinsed with minute amounts of isopropanol. The volatiles were stripped under reduced pressure (rotary evaporator; water bath=65 C.). The resulting light-brown liquid was diluted with hexanes (1 mL). The solution was loaded into a 1 inner diameter column previously prepared with silica gel 60 (70-230 mesh) and 10% ethyl acetate in hexanes. The height of wet silica gel in the column was approx. 22 cm. The column was eluted with 10% ethyl acetate in hexanes, then 20% ethyl acetate in hexanes. The fractions containing the dot at R.sub.f=0.2 (silica gel TLC; 10% ethyl acetate in hexanes) were collected, combined, and stripped of volatiles under reduced pressure (rotary evaporator; water bath=50 C.). The obtained oil was dried on the rotary evaporator (water bath=55 C.; <5 mbars) for 2.5 hours to yield 0.78 grams (61% with respect to Intermediate Compound 119-I) of 2,2,8-trimethyl-N-(1-phenylethyl)-1,2,3,4-tetrahydroquinolin-6-amine (Compound 119) as a clear light-brown oil. Compound 119 was characterized by .sup.1H and .sup.13C APT NMR spectroscopy, as shown in FIGS. 12 and 13, respectively. LC-UV analysis indicated 98.9% purity at 260 nm detection.

Example 5

Synthesis of diethyl 2,8-dimethyl-6-(phenylamino)-1,2-dihydroquinoline-2,4-dicarboxylate (Compound 120)

##STR00146##

[0261] To a 250-mL round bottom flask fitted with a stir-bar and a reflux condenser was loaded 3-methyl-N.sup.1-phenylbenzene-1,4-diamine (1.8 g; 9.08 mmol) and acetonitrile (15 mL). The mixture was stirred under N.sub.2 protection. Ethyl pyruvate (2.1 mL; 18.9 mmol) and iodine (0.070 g; 0.276 mmol) were sequentially added to the flask. The reaction mixture was heated (oil bath temperature set to 60 C.). The temperature was maintained for 90 minutes. Upon cooling to room temperature, sodium sulfite (0.26 g; 2.06 mmol) was added and the mixture was stirred for 30 minutes. The volatiles were stripped under reduced pressure (rotary evaporator; water bath=50 C.). The crude material was diluted with 50% ethyl acetate in hexanes (10 mL). The obtained slurry was loaded to a 41 mm inner diameter column chromatography prepared with silica gel 60 and eluent (50% ethyl acetate in hexanes). The height of wet silica gel in the column was approx. 11. The column was eluted with the same eluent. The fractions coming out (50 mL each) were analyzed by silica gel TLC (50% ethyl acetate in hexanes). The fractions containing Compound 120 were collected, combined, and stripped of their volatiles under reduced pressure (rotary evaporator; water bath=50 C.). Further drying on the rotary evaporator (50 C.; <5 mbars) for approx. 2 hours afforded 2.7 g of diethyl 2,8-dimethyl-6-(phenylamino)-1,2-dihydroquinoline-2,4-dicarboxylate (Compound 120) as a dark oil. Compound 120 was characterized by .sup.13C APT NMR spectroscopy, as shown in FIG. 14. LC-UV analysis indicated 97.5% purity at 260 nm detection.

Example 6

Oxidative Induction Time (OIT) Performance of Compounds of the Disclosure

[0262] The oxidative induction time (OIT) of selected Compounds of the Disclosure was evaluated. OIT is measured according to a procedure carried out in a differential scanning calorimeter (DSC; TA Instruments, Q200). In this procedure, a sample is held in a cell and heated under a nitrogen atmosphere to a preselected temperature. Oxygen (O.sub.2) is then introduced to the cell and the length of time before the onset of degradation, as observed by the initiation of an endothermic process in the DSC trace, is measured.

[0263] 0.5 wt % of a Compound of the Disclosure, N.sup.1-(4-methylpentan-2-yl)-N.sup.4-phenylbenzene-1,4-diamine (6PPD), or no antidegradant (blank) was mixed with polyisoprene and heated isothermally at 150 C. or 160 C. in O.sub.2. The OIT in minutes is shown in Table 2. As indicated by the data in Table 2, Compounds of the Disclosure demonstrate antioxidant activity compared to the blank control.

TABLE-US-00002 TABLE 2 OIT at 150 C. OIT at 160 C. Material (minutes) (minutes) Blank 2.1 1.9 6PPD 47.7 22.0 Compound 1 33.9 15.2 Compound 2 37.0 17.8 Compound 7 59.5 31.0 Compound 119 36.7 21.9 Compound 120 24.1 11.5

Example 7 Use of Compounds of the Disclosure in Sidewall Formulations

Rubber sidewall compounds were prepared using Compound 1 in sidewall formulations. As shown in Table 3, the rubber sidewall compounds are a 50/50 blend of natural rubber and butadiene rubber with a carbon black of the N500 series. Example #1 is a sidewall compound comprising Compound 1. A control sidewall compound comprising no antidegradant was also prepared. According to American Society for Testing Materials (ASTM) test method D5289, vulcanization properties of all the compounds were characterized by a moving die rheometer (Alpha Technologies MDR 2000), also known as MDR, at a temperature of 160 C. for 60 minutes. The oscillation strain and frequency were set to 0.5 C. and 1.667 Hz, respectively. The MDR test results are summarized in Table 4.

TABLE-US-00003 TABLE 3 Material Example #1 TSR-10 (SIR-10) 50 BR (CB24) 50 N-550 Carbon Black 50 Stearic Acid 2 Calsol 8240 (Naphthenic oil) 6.25 Zinc oxide 4 Sulfur (RMS) 1.5 TBBS 0.6 Compound 1 2.07

TABLE-US-00004 TABLE 4 Parameter Example #1 ML (dNM) .sup.1 2.3 MH (dNM) .sup.2 15.3 tMH (min) .sup.3 12.5 ts1 (min) .sup.4 3.2 ts2 (min) .sup.5 3.6 t10 (min) .sup.6 3.4 t25 (min) .sup.7 4.0 t50 (min) .sup.8 4.8 t90 (min) .sup.9 7.9 .sup.1 ML is the minimum torque, which is a measure of rigidity and viscosity of the non-vulcanized compound. .sup.2 MH is the maximum torque, which is a measure of the cross-linking density of the fully vulcanized compound. .sup.3 tMH is the time taken to reach maximum torque. .sup.4 ts1 is the time for viscosity to increase 1 unit (dNm) above ML. .sup.5 ts2 is the time for viscosity to increase 2 units (dNm) above ML. .sup.6 t10 is the moment when 10% cross-linking has been reached. .sup.7 t25 is the moment when 25% cross-linking has been reached. .sup.8 t50 is the moment when 50% cross-linking has been reached. .sup.9 t90 is the moment when 90% cross-linking has been reached.

Example 8

Antiozonant Performance of Compounds of the Disclosure in Sidewall Compounds

[0264] The rubber sidewall compounds prepared in Example 7 were cured at 160 C. to a state equivalent to its T90+2 min time. The ozone test specimens were died out from vulcanized tensile sheets by using a die followed the American Society for Testing and Materials (ASTM) D1329 standard. The ozone test specimens were stored in an ambient environment for more than 24 hours prior to antiozonant performance testing in an ozone chamber, which was maintained at an ozone concentration of 10+2 parts per hundred million (pphm) and 40+2 C. The ozone test specimens were simultaneously relaxed and extended within ozone chamber under dynamic conditions. The ozone test specimens were alternately relaxed and extended to 25% strain at a rate of 90 cycles per minute during dynamic exposure. Exposure was in increments of 24 hours followed by at least one hour of relaxation after removal from the ozone chamber and prior to measurement of force at a strain of 100%.

[0265] Antiozonant performance of antidegradant formulated compounds were evaluated by percentage of force retention. The percentage of force retention is defined by equation 1.

Percentage of force retention=F/F.sub.0*100%:Equation 1:

wherein F.sub.0 is the force at a strain of 100% prior to ozone testing and F is the force at a strain of 100% after samples are aged in ozone chamber for 16-hour cycle at dynamic exposure. Higher percentage of force retention is an indication of better antiozonant performance of an antidegradant compound incorporated in the vulcanized rubber compound.

[0266] The force of aged and unaged ozone test specimens was measured by using a tensometer (Alpha Technologies, 2000) at a strain of 100%. The percentage of force retention for the sidewall compounds were calculated and plotted as a function of ozone aging time in FIG. 15.

Example 9

Use of Compounds of the Disclosure in Tread Formulations

[0267] Rubber tread compounds were prepared using Compound 1 as an antidegradant in tread formulations. As shown in Table 5, these rubber tread compounds are a 70/30 blend of styrene-butadiene rubber and butadiene rubber with silica and carbon black. Example #la is a tread compound comprising Compound 1. A control tread compound comprising no antidegradant was also prepared. According to American Society for Testing Materials (ASTM) test method D5289, vulcanization properties of all the compounds were characterized by a moving die rheometer (Alpha Technologies MDR 2000), also known as MIDR, at a temperature of 160 C. for 60 minutes. The oscillation strain and frequency were set to 0.5 C. and 1.667 Hz, respectively. The MVDR test results were summarized in Table 6.

TABLE-US-00005 TABLE 5 Material Example #1a Duradene 738 (SBR) 70 Firestone 140ND (BR) 30 Ultrasil 7000GR 80 Si69 Silane 8 N330 Carbon black 10 TDAE Oil 17 Stearic Acid 1 Zinc Oxide 3 Sulfur (RMS) 1.5 CBS 1.5 DPG 2 TDAE oil 3 Compound 1 2.07

TABLE-US-00006 TABLE 6 Parameter Example #1a ML (dNM) .sup.1 2.8 MH (dNM) .sup.2 19.9 tMH (min) .sup.3 59.8 ts1 (min) .sup.4 0.7 ts2 (min) .sup.5 1.0 t10 (min) .sup.6 0.9 t25 (min) .sup.7 1.6 t50 (min) .sup.8 3.2 t90 (min) .sup.9 15.9 .sup.1 ML is the minimum torque, which is a measure of rigidity and viscosity of the non-vulcanized compound. .sup.2 MH is the maximum torque, which is a measure of the cross-linking density of the fully vulcanized compound. .sup.3 tMH is the time taken to reach maximum torque. .sup.4 ts1 is the time for viscosity to increase 1 unit (dNm) above ML. .sup.5 ts2 is the time for viscosity to increase 2 units (dNm) above ML. .sup.6 t10 is the moment when 10% cross-linking has been reached. .sup.7 t25 is the moment when 25% cross-linking has been reached. .sup.8 t50 is the moment when 50% cross-linking has been reached. .sup.9 t90 is the moment when 90% cross-linking has been reached.

Example 10

Antiozonant Performance of Compounds of the Disclosure in Tread Compounds

[0268] Each of the rubber tread compounds prepared in Example 9 were cured at 160 C. to a state equivalent to its T90+2 min time. The ozone test specimens were died out from vulcanized tensile sheets by using a die followed the American Society for Testing and Materials. (ASTM) D1329 standard. The ozone test specimens were stored in an ambient environment for more than 24 hours prior to antiozonant performance testing in an ozone chamber, which was maintained at an ozone concentration of 10+2 parts per hundred million (pphm) and 40+2 C. The ozone test specimens were simultaneously relaxed and extended within ozone chamber under dynamic conditions. The ozone test specimens extended to 25% strain at a rate of 90 cycles per minute during dynamic exposure. Exposure was in increments of 24 hours followed by at least one hour of relaxation after removal from the ozone chamber and prior to measurement of force at a strain of 100%.

[0269] Antiozonant performance of antidegradant formulated compounds were evaluated by percentage of force retention, which is defined in Example 8.

[0270] The percentage of force retention for the tread compounds were calculated and plotted as a function of ozone aging time in FIG. 16.

[0271] Having now fully described the methods, compounds, and compositions herein, it will be understood by those of skill in the art that the same can be performed within a wide and equivalent range of conditions, formulations, and other parameters without affecting the scope of the methods, compounds, and compositions provided herein or any embodiment thereof. All patents, patent applications, and publications cited herein are fully incorporated by reference herein in their entirety.

QUINOLINEAMINE ANTIDEGRADANT COMPOUNDS AND USES THEREOF

Inventors

Cpc classification

Classification Explorer

C07D405/12

CHEMISTRY; METALLURGY

Classification Explorer

C07D215/50

CHEMISTRY; METALLURGY

Classification Explorer

C07D221/20

CHEMISTRY; METALLURGY

Classification Explorer

C09K15/30

CHEMISTRY; METALLURGY

International classification

Classification Explorer

C07D215/50

CHEMISTRY; METALLURGY

Classification Explorer

C07D405/12

CHEMISTRY; METALLURGY

Classification Explorer

C07D221/20

CHEMISTRY; METALLURGY

Classification Explorer

C09K15/30

CHEMISTRY; METALLURGY

Abstract

Claims

Description