Aromatic enol ethers

Abstract

Disclosed are novel aromatic enol ethers. The aromatic enol ethers exhibit low volatile organic content and are reactive film-hardening compounds. The aromatic enol ethers are useful in a variety of chemical applications. The aromatic enol ethers can be used in applications as plasticizers, diluents, wetting agents, coalescing aids and as intermediates in chemical processes. The aromatic enol ethers also have utility as film-hardening additives for coating formulations.

Claims

1. A compound according to Formula I: ##STR00046## wherein: ##STR00047## wherein ** indicates the point of attachment; and ##STR00048## each R.sup.2 is (C.sub.4-10)aryl each R.sup.3 is (C.sub.1-10)alkyl or (C.sub.4-10)aryl; R.sup.4 is hydrogen, (C.sub.1-12)alkyl, (C.sub.2-12)alkenyl, or C(O)R.sup.5; R.sup.5 is (C.sub.1-12) alkyl unsubstituted or substituted by R.sup.6, (C.sub.2-12) alkenyl unsubstituted or substituted by R.sup.6, (C.sub.3-8)cycloalkyl, or 5- to 9-membered aryl; R.sup.6 is (C.sub.1-4)alkoxy, or oxo; and n is an integer from 1 to 15.

2. The compound of claim 1 wherein R.sup.2 is phenyl, substituted phenyl, naphthyl, substituted napththyl, furanyl, or substituted furanyl.

3. The compound of claim 1 wherein R.sup.3 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, substituted phenyl, naphthyl, substituted napththyl, furanyl, or substituted furanyl.

4. The compound of claim 1 wherein n is an integer from 1 to 4.

5. The compound of claim 1 wherein R.sup.2 is phenyl or substituted phenyl; R.sup.3 is methyl, ethyl, phenyl, or substituted phenyl and n is an integer from 1 to 3.

6. A compound according to Formula II: ##STR00049## wherein: each A is independently ##STR00050## and wherein ** indicates the point of attachment; ##STR00051## each R.sup.2 is (C.sub.4-10)aryl; each R.sup.3 is (C.sub.1-10)alkyl or (C.sub.4-10)aryl; and n is an integer from 1 to 15.

7. The compound of claim 6 wherein each R.sup.2 is phenyl, substituted phenyl, naphthyl, substituted napththyl, furanyl, or substituted furanyl.

8. The compound of claim 6 wherein R.sup.3 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, substituted phenyl, naphthyl, substituted napththyl, furanyl, or substituted furanyl.

9. The compound of claim 6 wherein R.sup.2 is phenyl or substituted phenyl, R.sup.3 is methyl, ethyl, phenyl, or substituted phenyl and n is an integer from 1 to 3.

10. An enol ether compound selected from the group consisting of compounds 1-3, 4(a), 4(b), 5(a), 5(b), 6-24, 25(a), 25(b), 26(a) and 26(b): ##STR00052## ##STR00053## ##STR00054## ##STR00055## ##STR00056## and isomers thereof.

Description

DETAILED DESCRIPTION

Definitions

(1) In this specification and in the claims that follow, reference will be made to a number of terms, which shall be defined to have the following meanings.

(2) Alkyl means an aliphatic hydrocarbon. The alkyl can specify the number of carbon atoms, for example (C.sub.1-5)alkyl. Unless otherwise specified, the alkyl group can be unbranched or branched. In some embodiments, the alkyl group is branched. In some embodiments, the alkyl group is unbranched. Non-limiting examples of alkanes include methane, ethane, propane, isopropyl (i.e., branched propyl), butyl, and the like.

(3) Alkenyl means an aliphatic hydrocarbon with one or more unsaturated carbon-carbon bonds. The alkenyl can specify the number of carbon atoms, for example (C.sub.2-12)alkenyl. Unless otherwise specified, the alkyl group can be unbranched or branched. In some embodiments, the alkyl group is branched. In some embodiments, the alkyl group is unbranched. Non-limiting examples of alkanes include ethenyl, propenyl, butenyl, hexa-3,5-dienyl, and the like.

(4) Alcohol means a chemical containing one or more hydroxyl groups.

(5) Aldehyde means a chemical containing one or moreC(O)H groups.

(6) Cycloalkyl means a cyclic hydrocarbon compound. The cycloalkyl can specify the number of carbon atoms in ring system, for example (C.sub.3-8)cycloalkyl. Non-limiting examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclohexyl, and cyclooctyl.

(7) Aryl means a ring system made up carbon atoms that has at least one ring that is aromatic. The carbon units making up the aryl ring may be specified, for example 5- to 9-membered aryl. Non-limiting examples of aryl include phenyl, naphthyl, 2,3-dihydro-1H-indene, and 1,2,3,4-tetrahydronaphthalene.

(8) Values may be expressed as about or approximately a given number. Similarly, ranges may be expressed herein as from about one particular value and/or to about or another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent about, it will be understood that the particular value forms another aspect.

(9) As used herein, the terms a, an, and the mean one or more.

(10) As used herein, the term and/or, when used in a list of two or more items, means that any one of the listed items can be employed by itself or any combination of two or more of the listed items can be employed. For example, if a composition is described as containing components A, B, and/or C, the composition can contain A alone; B alone; C alone; A and B in combination; A and C in combination, B and C in combination; or A, B, and C in combination.

(11) As used herein, the terms comprising, comprises, and comprise are open-ended transition terms used to transition from a subject recited before the term to one or more elements recited after the term, where the element or elements listed after the transition term are not necessarily the only elements that make up the subject.

(12) As used herein, the terms having, has, and have have the same open-ended meaning as comprising, comprises, and comprise provided above.

(13) As used herein, the terms including, includes, and include have the same open-ended meaning as comprising, comprises, and comprise provided above.

(14) Chosen from as used herein can be used with or or and. For example, Y is chosen from A, B, and C means Y can be individually A, B, or C. Alternatively, Y is chosen from A, B, or C means Y can be individually A, B, or C; or a combination of A and B, A and C, B and C, or A, B, and C.

(15) Presented herein are novel enol ethers which can be used in applications such as (but not limited to) plasticizers, diluents, wetting agents, coalescing aids and paint additives.

(16) In some embodiments the invention is a compound according to Formula I:

(17) ##STR00007##

(18) wherein:

(19) ##STR00008##

(20) wherein ** indicates the point of attachment,

(21) ##STR00009##

(22) R.sup.2 is (C.sub.5-10)aryl; R.sup.3 is (C.sub.1-10)alkyl or (C.sub.5-10)aryl; R.sup.4 is hydrogen, (C.sub.1-12)alkyl, (C.sub.2-12)alkenyl, or C(O)R.sup.5; R.sup.5 is (C.sub.1-12)alkyl unsubstituted or substituted by R.sup.6, (C.sub.2-12)alkenyl unsubstituted or substituted by R.sup.6, (C.sub.3-8)cycloalkyl, or 5- to 9-membered aryl; each R.sup.6 is (C.sub.1-4)alkoxy, or oxo; and n is an integer from 1 to 15.

(23) In another embodiment,

(24) ##STR00010##

(25) wherein ** indicates the point of attachment.

(26) In some embodiments, R.sup.2 is phenyl, substituted phenyl, naphthyl, substituted napththyl, furanyl, or substituted furanyl. In some embodiments, R.sup.3 is methyl, ethyl, propyl, butyl, pentyl, heptyl, hexyl, heptyl, octyl, nonyl, or decyl. In some embodiments, R.sup.3 is phenyl, substituted phenyl, naphthyl, substituted napththyl, furanyl, or substituted furanyl. In some embodiments n is an integer from 1 to 4.

(27) In some embodiments, R.sup.2 is phenyl or substituted phenyl; and R.sup.3 is methyl, ethyl, phenyl, or substituted phenyl. In some embodiments n can be an integer from 1 to 4.

(28) In some embodiments, R.sup.4 is C(O)R.sup.5. In some embodiments, R.sup.5 can be (C.sub.1-12)alkyl unsubstituted or substituted by R.sup.6. In some embodiments, R.sup.5 can be (C.sub.2-12)alkenyl unsubstituted or substituted by R.sup.6. In some embodiments, R.sup.5 can be (C.sub.3-8)cycloalkyl. In some embodiments, R.sup.5 can be 5- to 9-membered aryl.

(29) In some embodiments, R.sup.4 is hydrogen. In some embodiments, R.sup.4 is (C.sub.1-12)alkyl.

(30) In some embodiments, R.sup.4 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or nonyl. In some embodiments, R.sup.4 is ethyl, propyl, or butyl. In some embodiments, R.sup.4 is ethyl or butyl. In some embodiments, R.sup.4 is (C.sub.2-12)alkenyl.

(31) In some embodiments, R.sup.4 is C(O)R.sup.5. In some embodiments, R.sup.5 is (C.sub.1-12)alkyl unsubstituted or substituted by R.sup.6. In some embodiments, R.sup.5 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or nonyl. In some embodiments, R.sup.5 is methyl. In some embodiments, R.sup.5 is (C.sub.2-12)alkenyl unsubstituted or substituted by R.sup.6.

(32) In some embodiments, R.sup.5 is (C.sub.3-8)cycloalkyl. In some embodiments, R.sup.5 is cyclobutyl, cyclopenyl, cyclohexyl, cycloheptyl, or cyclooctyl. In some embodiments, R.sup.5 is cyclohexyl.

(33) In some embodiments, R.sup.5 is a 5- to 9-membered aryl. In some embodiments, R.sup.5 is phenyl or naphthyl. In some embodiments, R.sup.5 is phenyl.

(34) In some embodiments, n is an integer from 1 to 2. In some embodiments, n is an integer from 1 to 3. In some embodiments, n is an integer from 1 to 4. In some embodiments, n is an integer from 1 to 5. In some embodiments, n is an integer from 1 to 6. In some embodiments, n is an integer from 1 to 7. In some embodiments, n is an integer from 1 to 8. In some embodiments, n is an integer from 1 to 9. In some embodiments, n is an integer from 1 to 10. In some embodiments, n is an integer from 1 to 11. In some embodiments, n is an integer from 1 to 12. In some embodiments, n is an integer from 1 to 13. In some embodiments, n is an integer from 1 to 14. In some embodiments, n is an integer from 1 to 15.

(35) In some embodiments, the compounds of Formula I have a volatile organic content of less than 50 wt % according to ASTM D6886. In some embodiments, the volatile organic content is less than 30 wt %. In embodiments, the volatile organic content is less than 10 wt %. In some embodiments, the volatile organic content is less than 5 wt %. In some embodiments, the volatile organic content is less than 3 wt %. In some embodiments, the volatile organic content is less than 2 wt %. In some embodiments, the volatile organic content is less than 1 wt %. In some embodiments, the volatile organic content is less than 0.8 wt %.

(36) Another embodiment of the invention is an enol ether compound according to Formula II:

(37) ##STR00011##

(38) wherein:

(39) each A is independently

(40) ##STR00012##

(41) wherein ** indicates the point of attachment, or R.sup.1c is

(42) ##STR00013##

(43) each R.sup.2 is independently (C.sub.5-10)aryl; each R.sup.3 is independently (C.sub.1-10)alkyl or (C.sub.5-10)aryl; and n is an integer from 1 to 15.

(44) In some embodiments, each

(45) ##STR00014##

(46) wherein ** indicates the point of attachment. In some embodiments of this invention, n is an integer 1 to 3.

(47) In some embodiments, R.sup.2 is phenyl, substituted phenyl, naphthyl, substituted napththyl, furanyl, or substituted furanyl. In some embodiments, R.sup.3 is methyl, ethyl, propyl, butyl, pentyl, heptyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, substituted phenyl, naphthyl, substituted napththyl, furanyl, or substituted furanyl. In some embodiments, n is an integer from 1 to 3.

(48) In some embodiments, R.sup.2 is phenyl or substituted phenyl; and R.sup.3 is methyl, ethyl, phenyl, or substituted phenyl. In some embodiments, n is an integer from 1 to 3.

(49) In some embodiments, R.sup.2 is butyl; and R.sup.3 is ethyl. In some embodiments, n is an integer from 1 to 3.

(50) In some embodiments, n is an integer from 1 to 2. In some embodiments, n is an integer from 1 to 3. In some embodiments, n is an integer from 1 to 4. In some embodiments, n is an integer from 1 to 5. In some embodiments, n is an integer from 1 to 6. In some embodiments, n is an integer from 1 to 7. In some embodiments, n is an integer from 1 to 8. In some embodiments, n is an integer from 1 to 9. In some embodiments, n is an integer from 1 to 10. In some embodiments, n is an integer from 1 to 11. In some embodiments, n is an integer from 1 to 12. In some embodiments, n is an integer from 1 to 13. In some embodiments, n is an integer from 1 to 14. In some embodiments, n is an integer from 1 to 15.

(51) In some embodiments, the compound of Formula II has a volatile organic content of less than 50 wt % according to ASTM D6886. In one class of this embodiment, the volatile organic content is less than 30 wt %. In one class of this embodiment, the volatile organic content is less than 10 wt %. In one class of this embodiment, the volatile organic content is less than 5 wt %. In one class of this embodiment, the volatile organic content is less than 3 wt %. In one class of this embodiment, the volatile organic content is less than 2 wt %. In one class of this embodiment, the volatile organic content is less than 1 wt %. In one class of this embodiment, the volatile organic content is less than 0.8 wt %.

(52) Compositions

(53) The enol ether compounds disclosed in the present application exhibit a low volatile organic content (less than 50 wt %, but as low as 0.7 wt % according to ASTM D6886). The enol ethers can be used as reactive film-hardening compounds. Reactive film-hardening compounds react with components in coating compositions to form crosslinks in the films providing improved film properties. When we say that the enol ether compounds of this invention can be used as reactive film-hardening additives, we mean when added to a coating composition, that a harder film is obtained upon curing the composition than is obtained in the absence of the invention enol ether additives, or that the coating composition exhibits a higher gel fraction than in the absence of the enol ether additive, or that both coating composition hardness and increased gel fraction properties are improved by the addition of the enol ether reactive film-hardening additives.

(54) Not wishing to be bound by any theory, the increase in hardness observed in a coating that contains the enol ether additives described herein may be the result of a chemical reaction, so that the additives described herein may be described as reactive enol ether film-hardening additives.

(55) The enol ether materials described herein can also facilitate the individual latex particles coming together to form a continuous film at a given temperature by reducing the minimum film-forming temperature (MFFT) of the latex polymer.

(56) In some embodiments, the composition comprises the compound represented by Formula I. In some embodiments, the composition comprises the compound represented Formula II.

(57) In some embodiments, the compounds of Formula I or II are enol ethers represented by the Formulas 1-26 (a,b):

(58) ##STR00015## ##STR00016## ##STR00017## ##STR00018## ##STR00019##

(59) and isomers thereof.

(60) The enol ethers depicted by Formulas 1-26(a,b) are representative of the enol ethers claimed herein. Isomers of the enol ethers depicted by Formulas 1-26(a,b) are expected to be produced during synthesis of the enol ethers depicted by Formulas 1-26(a,b). All isomers of the enol ethers depicted by Formulas 1-26(a,b) and are within the scope of the claims set forth herein.

(61) The compounds depicted by Formula I and II include those having a weight percent volatile content of less than 50%, as measured according to ASTM Method D6886. This test may be conducted generally by heating the sample in a forced air oven at 110 C. for 60 minutes. The weight loss after the test is deemed to result from a loss of volatiles originally present in the sample; the percent volatile present in the original sample may then be calculated. Although the cited test can be conducted on coating compositions containing other components such as latex polymers, the values cited herein may be obtained from a sample of the additive itself. The weight percent volatile of a film-hardening aid may be used herein as a yardstick to measure the amount of VOC the additive would contribute to the VOC in a particular end use such as a component of a coating composition.

EXAMPLES

(62) This invention can be further illustrated by the following examples thereof, although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention unless otherwise specifically indicated.

(63) Abbreviations:

(64) mL is milliliter; wt % is weight percent; eq is equivalent(s); hrs or h is hour(s); mm is millimeter; m is meter; GC is gas chromatography; C. is degree Celsius; min is minute; t.sub.R is retention time; VOC is volatile organic compound; MeP is methyl palmitate; w/v is weight/volume; L is microliter. RFHA is reactive film-hardening additive.

Example 1: Preparation of (E/Z)-(1-(2-(2-butoxyethoxy)ethoxy)prop-1-en-2-yl)benzene [1]

(65) ##STR00020##
Method 1:

(66) 2-phenylpropionaldehyde (100 g) was added to a nitrogen-swept, 1 L 4-necked round-bottom flask fitted with overhead-stirrer, thermocouple, and Dean-Stark. Diethyleneglycol monobutyl ether (260 g) was added all at once, followed by the addition of 250 g of toluene. Sodium methanesulfonate (2.20 g) was added to the flask, followed by the addition of methanesulfonic acid (1.21 mL). The reaction was heated to reflux and held at that temperature for 15 hrs. During that time, ca. 13.5 mL of water collected. The toluene was removed under reduced pressure using a rotary evaporator. Then 50% caustic (0.902 mL) was added all at once. The mixture was fractionally distilled under reduced pressure. The product distilled at a vapor temperature of 188 C. at 3 torr. The product was isolated as a mixture of E/Z isomers and was a near colorless oil (164 g, 79% yield). GC-MS (Instrument A) t.sub.R: 9.41 min, 9.58 min (Exact mass: 278.1882, found: 278.1882 m/z).

(67) The remaining examples were prepared according to Method 1.

Example 2: Preparation of (E/Z)-13-phenyl-2,5,8,11-tetraoxatetradec-12-ene [2]

(68) ##STR00021##

(69) GC-MS (Instrument A) t.sub.R: 9.54 min, 9.72 min (Exact mass: 280.1675 m/z, found 280.1675 m/z).

Example 3: Preparation of (E/Z)-2-phenyl-4,7,10,13-tetraoxaheptadec-2-ene [3]

(70) ##STR00022##

(71) The product enol ether was isolated as a mixture of E/Z isomers and was isolated as a near colorless liquid. GC-MS (Instrument A) t.sub.R: 10.49 min, 10.52 min (Exact mass: 322.2144 m/z, found 322.4500 m/z).

Example 4: Preparation of a mixture of (2E/Z, 14E/Z) 2,15-diphenyl-4,7,10,13-tetraoxahexadeca-2,14-diene [4a] and (E/Z)-2-(2-(2-((2-phenyl prop-1-en-1-yl)oxy)ethoxy)ethoxy)ethan-1-ol [4b]

(72) ##STR00023##

(73) GC-MS (Instrument A) t.sub.R: 9.60 min, 9.80 min (Exact mass: 266.1518 m/z, found: 266.1518 m/z), 12.42 min, 12.62 min, 12.84 min (Exact mass: 382.2144 m/z, found: 382.2144 m/z).

Example 5: Preparation of an isomeric mixture of (EIZ)-2,2,4-trimethyl-3-((2-phenylprop-1-en-1-yl)oxy)pentyl isobutyrate [5a] and (E/Z)-2,2,4-trimethyl-1-((2-phenylprop-1-en-1-yl)oxy)pentan-3-yl isobutyrate [5b]

(74) ##STR00024##

(75) GC-MS (Instrument B) t.sub.R: 17.28 min, 17.46 min, 17.69 min, 18.06 min (Exact mass: 332.24 m/z, found: 332.3 m/z).

Example 6: Preparation of (E/Z)-1-(1-(2-(2-ethoxyethoxy)ethoxy)prop-1-en-2-yl)-4-methoxybenzene [6]

(76) ##STR00025##

(77) GC-MS (Instrument B) t.sub.R: 17.41 min, 17.71 min (Exact mass: 280.17 m/z, found: 280.1 m/z).

Example 7: Preparation of (E/Z)-1-(1-(2-(2-butoxyethoxy)ethoxy)prop-1-en-2-yl)-4-methoxybenzene [7]

(78) ##STR00026##

(79) GC-MS (Instrument B) t.sub.R: 18.52 min, 18.91 min (Exact mass: 308.20 m/z, found: 308.3 m/z).

Example 8: Preparation of (E/Z)-1-methoxy-4-(1-((1-((1-methoxypropan-2-yl)oxy)propan-2-yl)oxy)prop-1-en-2-yl)benzene [8]

(80) ##STR00027##

(81) GC-MS (Instrument B) t.sub.R: 17.09 min, 17.21 min, 17.43 min, 17.55 min (Exact mass: 294.18 m/z, found: 294.1 m/z).

Example 9: Preparation of (E/Z)-4-(1-(2-(2-butoxyethoxy)ethoxy)prop-1-en-2-yl)benzonitrile [9]

(82) ##STR00028##

(83) GC-MS (Instrument B) t.sub.R: 19.31 min, 19.75 min (Exact mass: 303.18 m/z, found: 303.1 m/z).

Example 10: Preparation of (E/Z)-4-(1-(2-(2-butoxyethoxy)ethoxy)prop-1-en-2-yl)-1,2-dimethoxybenzene [10]

(84) ##STR00029##

(85) GC-MS (Instrument B) t.sub.R: 19.64 min, 20.22 min (Exact mass: 338.21 m/z, found: 338.3 m/z).

Example 11: Preparation of (2-((1-methoxypropan-2-yl)oxy)ethene-1,1-diyl)dibenzene [11]

(86) ##STR00030##

(87) GC-MS (Instrument A) t.sub.R: 9.41 min (Exact mass: 268.1463, found: m/z=268.1463).

Example 12: Preparation of (2-(2-butoxyethoxy)ethene-1,1-diyl)dibenzene [12]

(88) ##STR00031##

(89) GC-MS (Instrument A) t.sub.R: 10.34 min (Exact mass: 296.1776 m/z, found: 296.1776 m/z).

Example 13: Preparation of (2-(2-(2-methoxyethoxy)ethoxy)ethene-1,1-diyl)dibenzene [13]

(90) ##STR00032##

(91) GC-MS (Instrument A) t.sub.R: 10.48 min (Exact mass: 298.1569 m/z, found: 298.1569 m/z).

Example 14: Preparation of (2-(2-(2-ethoxyethoxy)ethoxy)ethene-1,1-diyl)dibenzene [14]

(92) ##STR00033##

(93) GC-MS (Instrument A) t.sub.R: 10.67 min (Exact mass: 312.1725 m/z, found: 312.1725 m/z).

Example 15: Preparation of (2-(2-(2-butoxyethoxy)ethoxy)ethene-1,1-diyl) dibenzene [15]

(94) ##STR00034##

(95) GC-MS (Instrument A) t.sub.R: 11.29 min (Exact mass: 340.2038 m/z, found: 340.2038 m/z).

Example 16: Preparation of 1,1-diphenyl-3,6,9,12-tetraoxahexadec-1-ene [16]

(96) ##STR00035##

(97) GC-MS (Instrument A) t.sub.R: 12.18 min (Exact mass: 384.2301 m/z, found: 384.2301 m/z).

Example 17: Preparation of 2-(2-((2,2-diphenylvinyl)oxy)ethoxy)ethyl acetate [17]

(98) ##STR00036##

(99) GC-MS (Instrument B) t.sub.R: 18.69 min, 18.74 min, 18.90 min (Exact mass: 326.19 m/z, found: 326.2 m/z).

Example 18: Preparation of (2-((1-((1-methoxypropan-2-yl)oxy)propan-2-yl)oxy)ethene-1,1-diyl)dibenzene [18]

(100) ##STR00037##

(101) GC-MS (Instrument B) t.sub.R: 18.69 min, 18.74 min, 18.90 min (Exact mass: 326.19 m/z, found: 326.2 m/z).

Example 19: Preparation of (E/Z)-1-(2-(2-(2-ethoxyethoxy)ethoxy)-1-phenylvinyl)-4-methylbenzene [19]

(102) ##STR00038##

(103) GC-MS (Instrument B) t.sub.R: 19.94 min, 20.06 min (Exact mass: 326.19 m/z, found 326.3 m/z).

Example 20: Preparation of 4,4-(2-(2-(2-ethoxyethoxy)ethoxy)ethene-1,1-diyl)bis(methylbenzene) [20]

(104) ##STR00039##

(105) GC-MS (Instrument B) t.sub.R: 20.95 min (Exact mass: 340.20 m/z, found: 340.3 m/z).

Example 21: Preparation of (E/Z)-1-methoxy-4-(2-((1-methoxypropan-2-yl)oxy)-1-phenylvinyl)benzene [21]

(106) ##STR00040##

(107) GC-MS (Instrument B) t.sub.R: 18.58 min, 18.65 min (Exact mass: 298.16, found: 298.1 m/z).

Example 22: Preparation of (E/Z)-1-(2-(2-(2-ethoxyethoxy)ethoxy)-1-phenylvinyl)-4-methoxybenzene [22]

(108) ##STR00041##

(109) GC-MS (Instrument B) t.sub.R: 21.17 min, 21.35 min (Exact mass: 342.18 m/z, found: 342.2 m/z).

Example 23: Preparation of (E/Z)-1-methoxy-4-(1-phenyl-2-(2-(2-propoxyethoxy)ethoxy)vinyl)benzene [23]

(110) ##STR00042##

(111) GC-MS (Instrument B) t.sub.R: 22.51 min, 22.70 min (Exact mass: 356.20 m/z, found: 356.2 m/z).

Example 24: Preparation of (E/Z)-1-(2-(2-(2-butoxyethoxy)ethoxy)-1-phenylvinyl)-4-methoxybenzene [24]

(112) ##STR00043##

(113) GC-MS (Instrument B) t.sub.R: 23.91 min, 24.16 min (Exact mass: 370.21 m/z, found: 370.3 m/z).

Example 25a and 25b: a mixture of 1,1,14,14-tetraphenyl-3,6,9,12-tetraoxatetradeca-1,13-diene [25a] and 2-(2-(2-((2,2-diphenylvinyl)oxy)ethoxy)ethoxy)ethan-1-ol [25b]

(114) ##STR00044##

(115) GC-MS (Instrument B) t.sub.R: 21.68 min (Exact mass 25b: 328.17 m/z, found: 238.2 m/z), 58.24 min (Exact mass 25a: 506.25 m/z, found: 506.3 m/z).

Example 26a and 26b: Preparation of Example 26, a Mixture of (E/Z, E/Z) 2,15-bis(4-methoxyphenyl)-4,7,10,13-tetraoxahexadeca-2,14-diene [26a] and (E/Z)-2-(2-(2-((2-(4-methoxyphenyl)prop-1-en-1-yl)oxy)ethoxy)ethoxy)ethan-1-ol [26b]

(116) ##STR00045##

(117) GC-MS (Instrument B) t.sub.R: 19.88 min (26bExact mass: 296.2 m/z, found: 296.1 m/z), 42.99 min, 47.28 min, 52.19 min (26aExact mass: 442.2 m/z, found: 442.3 m/z),

(118) Unless noted otherwise, all examples described above are defined as non-VOC by ASTM D6886. This method uses MeP as a standardif compound t.sub.R>MeP t.sub.R, compound is defined as non-VOC.

(119) Instrument ParametersThermo ISQ GCMS (Instrument A)

(120) Sample Prep: 100 L sample diluted to 1 mL with toluene; Column: DB-5 30 m0.25 mm0.25 m; Oven Ramp: 0-3 mins at 100 C.; Ramp 25 C/min to 280 C, Hold 15 mins; Injector: Temperature300 C.; Split Flow60; Carrier Flow Rate1.4 mL/min; Volume0.5 L; MS: Transfer Line280 C.; Ion Source Temp250 C.; Mass Range16-750 amu. Methyl palmitate t.sub.R=8.67 min using the above method.

(121) Instrument ParametersAgilent 6890N GC with Agilent 5975B VL MSD (Instrument B)

(122) Sample Prep: 100 L sample diluted to 1 mL with toluene; Column: DB-5 30 m0.25 mm0.25 m; Oven Ramp: 0-4.5 mins at 40 C.; Ramp 20 C/min to 280 C, Hold 53.5 mins; Injector: Temperature250 C.; Split Flow65 mL/min; Carrier Flow Rate1.3 mL/min; Volume1.0 L; MS: Transfer Line280 C.; Ion Source Temp230 C.; Mass Range34-700 amu. Methyl palmitate t.sub.R=16.6 min using the above method.

(123) The invention has been described in detail with reference to the embodiments disclosed herein, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.