HEAT-SENSITIVE RECORDING MATERIAL
20210331508 · 2021-10-28
Inventors
Cpc classification
B41M5/323
PERFORMING OPERATIONS; TRANSPORTING
C07C311/60
CHEMISTRY; METALLURGY
International classification
B41M5/333
PERFORMING OPERATIONS; TRANSPORTING
B41M5/323
PERFORMING OPERATIONS; TRANSPORTING
Abstract
The invention relates to a color developer of the formula (I), wherein m and n independently of one another are ≥1, Ar.sup.1 is an unsubstinited or substituted (hetero) aromatic radical, Ar.sup.2 is an unsubstituted or substituted phenyl radical, and Y is at least one (m+n)-times substituted benzene or naphthalene group, and to a heat-sensitive recording material, comprising a supporting substrate and a heat-sensitive color-forming layer containing at least one color former and at least one phenol-free color developer, wherein the at least one color developer is the compound of the formula (I). The invention further relates to a method for producing said heat-sensitive recording material.
##STR00001##
Claims
1. Compound of the formula (I), ##STR00011## wherein m and n independently of one another are I, Art is an unsubstituted or substituted (hetero) aromatic radical, Ar2 is an unsubstituted or substituted phenyl radical, and Y is at least one (m+n)-times substituted benzene or naphthalene group.
2. Compound according to claim 1, wherein m is 1 or 2.
3. Compound according to claim 1, wherein n is 1 or 2.
4. Compound according to claim 1, wherein Arl is an unsubstituted phenyl radical, an unsubstituted 1-napthyl radical, an unsubstituted 2-naphtyl radical, a monosubstituted phenyl radical, in particular a 4-alkoxycarbonylphenyl radical, a monosubstituted 1-naphtyl radical or a monosubstituted 2-naphtyl radical.
5. Compound according to claim 4, wherein Ar1 is an unsubstituted phenyl radical or a monosubstituted phenyl radical.
6. Compound according to claim 5, wherein the monosubstituted phenyl radical is substituted with a Cl-05-alkyl radical, an alkenyl radical, an aklinyl radical, a benzyl radical, an RO radical, a halogen radical, an ROC radical, an RO2C radical, a CN radical, an NO2 radical, an R-S020 radical, an RO-S02 radical, an R—NH—S02 radical, an R—SO2NH radical, an R—NH—CO—NH radical, an R—S02—NH—CO—NH radical, an R—NH—CO—NH—S02 radical or an R—CO—NH radical, wherein R is a C1-05-alkyl radical, an alkenyl radical, an alkinyl radical, a phenyl radical, a tolyl radical or a benzyl radical.
7. Compound according to claim 1, wherein Ar2 is an unsubstituted phenyl radical or a monosubstituted phenyl radical, or a phenyl radical substituted with a C1-C4-alkyl radical.
8. Compound according to claim 1, wherein Y is an (m+n)-times substituted benzene or naphthalene group.
9. Compound according to claim 1, wherein Ar1 is an unsubstituted phenyl radical or a monosubstituted phenyl radical, Ar2 is an unsubstituted phenyl radical or a monosubstituted phenyl radical and Y is an (m+n)-times substituted benzene group.
10. Heat-sensitive recording material comprising a supporting substrate as well as a heat-sensitive color-forming layer containing at least one color former and at least one phenol-free color developer, wherein the at least one color developer is the compound of the formula (I) according to claim 1.
11. Heat-sensitive recording material according to claim 10, wherein the at least one color former is a dye of the triphenyl methane type, of the fluoran type, of the azaphthalide type and/or of the fluoren type.
12. Heat-sensitive recording material according to claim 10, wherein in addition to the compound of the formula (I) one or more additional non-phenolic color developers are present.
13. Heat-sensitive recording material according to claim 10, wherein the compound of the formula (I) is present in a quantity of approximately 3 to approximately 35 weight percent, referring to the total solid content of the heat-sensitive layer.
14. Heat-sensitive recording material according to claim 10, wherein the heat-sensitive color-forming layer contains a urea-urethane compound of the general formula (II) ##STR00012##
15. Method for producing a heat-sensitive recording material according to of claim 10, wherein on the supporting substrate is applied an aqueous suspension containing the raw materials of the heat-sensitive colorforming layer and this is dried, wherein the aqueous application suspension has a solid content of approximately 20 to approximately 75 weight percent, and is applied with the curtain-coating method at a coater operating speed of at least approximately 400 m/min, and then is dried.
16. Heat-sensitive recording material obtainable according to the method according to claim 15.
17. Compound according to claim 5, wherein the monosubstituted phenyl radical is a phenyl or p-toyl radical.
18. Compound according to claim 1, wherein Y is a benzene group.
19. Heat-sensitive recording material according to claim 10, wherein that at least one color former is a fluoran type dye.
20. Method of claim 15, wherein the aqueous application suspension has a sold content of approximately 30 to approximately 50 weight percent and is applied with the curtain-coating method at a coater operating speed of at least approximately 1500 m/min.
Description
EXAMPLES
[0101] Production of the compounds of the formula (I) according to the invention.
[0102] The compounds I-XXXII (Table 2) were produced as follows:
[0103] Step A—Production of the Nitro Arylsulfonanilide
[0104] To a mixture of 55 mmol aromatic amine and 50 mmol pyridine is added 50 mmol of the nitro arylsulfonylchloride in portions while stirring. The mixture is heated to 95-100° C. for a short time (5-10 min), cooled and brayed with 100-150 ml of hydrochloric acid (2 mol/l). After collection, it is neutrally washed with water and dried. The nitro arylsulfonanilides were used without previous filtration in Step B.
[0105] Step B—Reduction of the Nitro Group to a Primary Amine 40 mmol of the product from Step A are dissolved in 140 ml of ethyl acetate, mixed with 140 mmol SnCl.sub.2.2H.sub.2O while stirring and heated during the return flow. The course of the reaction is followed on TLC (eluent: cyclohexane/ethyl acetate 1:1). After ending the reaction (approx. 2-3 h), it is thinned with 140 ml ethyl acetate, mixed with a 10% aqueous K.sub.2CO.sub.3 solution and stirred at room temperature for 30 min. The Sn compounds are filtered out and the aqueous separated from the organic phase in the filtrate. The organic phase is extracted twice with 100 ml each time of a saturated sodium chloride solution and subsequently dried over MgSO.sub.4. After rotating off the solvent, the amino arylsulfanilide is left in a solid state. Filtration takes place through recrystallization from aqueous methanol.
[0106] Step C—Production of the Sulfonylurea Compounds
[0107] 15 mmol of the product from Step B are dissolved in methylene dichloride (60-100 ml) and added in portions to 15 mmol sulfonyl isocyanate while stirring at room temperature. The course of the reaction is followed on TLC (eluent: n-hexane/CHCl.sub.3/CH.sub.3OH 4:2:1). After ending the reaction, the precipitated product is filtered out, washed with methylene dichloride and dried at <70° C.
[0108] Compounds XXXIII-XXXIV (Table 2) were converted, starting with the corresponding bis-amine sulfonylchlorides (schema 2, G. Barnikow, K. Krüger, G. Hilgetag, Z. Chem., 6,(7), 262 (1966)), following the general provision of Step A, into bis-amino benzene bis-sulfonanilides and these were converted, following the provision of Step C, into the final products.
[0109] The production of the starting compound is known and these are commercially available.
TABLE-US-00002 TABLE 2 Compilation of chosen compounds of the formula (I) Y Ar.sup.1 Ar.sup.2 m n I 1,2-phenylene C.sub.6H.sub.5 C.sub.6H.sub.5 1 1 II 1,2-phenylene 2-CH.sub.3—C.sub.6H.sub.4 C.sub.6H.sub.5 1 1 III 1,2-phenylene 4-CH.sub.3—C.sub.6H.sub.4 C.sub.6H.sub.5 1 1 IV 1,2-phenylene 4-OCH.sub.3—C.sub.6H.sub.4 C.sub.6H.sub.5 1 1 V 1,2-phenylene 2-(CO.sub.2C.sub.2H.sub.5)—C.sub.6H.sub.4 C.sub.6H.sub.5 1 1 VI 1,2-phenylene 4-(CO.sub.2CH.sub.3)—C.sub.6H.sub.4 C.sub.6H.sub.5 1 1 VII 1,2-phenylene 3-Cl—C.sub.6H.sub.4 C.sub.6H.sub.5 1 1 VIII 1,2-phenylene 2-(NH—CO—NH—C.sub.6H.sub.5)—C.sub.6H.sub.4 C.sub.6H.sub.5 1 1 IX 1,2-phenylene C.sub.6H.sub.5 4-CH.sub.3—C.sub.6H.sub.4 1 1 X 1,2-phenylene 2-CH.sub.3—C.sub.6H.sub.4 4-CH.sub.3—C.sub.6H.sub.4 1 1 XI 1,2-phenylene 4-CH.sub.3—C.sub.6H.sub.4 4-CH.sub.3—C.sub.6H.sub.4 1 1 XII 1,2-phenylene 3-CH.sub.3—C.sub.6H.sub.4 4-CH.sub.3—C.sub.6H.sub.4 1 1 XIII 1,2-phenylene 4-OCH.sub.3—C.sub.6H.sub.4 4-CH.sub.3—C.sub.6H.sub.4 1 1 XIV 1,2-phenylene 2-(CO.sub.2C.sub.2H.sub.5)—C.sub.6H.sub.4 4-CH.sub.3—C.sub.6H.sub.4 1 1 XV 1,2-phenylene 4-(CO.sub.2CH.sub.3)—C.sub.6H.sub.4 4-CH.sub.3—C.sub.6H.sub.4 1 1 XVI 1,2-phenylene 2-Cl—C.sub.6H.sub.4 4-CH.sub.3—C.sub.6H.sub.4 1 1 XVII 1,2-phenylene 3-Cl—C.sub.6H.sub.4 4-CH.sub.3—C.sub.6H.sub.4 1 1 XVIII 1,2-phenylene 4-Cl—C.sub.6H.sub.4 4-CH.sub.3—C.sub.6H.sub.4 1 1 XIX 1,2-phenylene 4-OC.sub.2H.sub.5—C.sub.6H.sub.4 4-CH.sub.3—C.sub.6H.sub.4 1 1 XX 1,2-phenylene 2-OCH.sub.3—C.sub.6H.sub.4 4-CH.sub.3—C.sub.6H.sub.4 1 1 XXI 1,2-phenylene 3-(O—SO.sub.2—C.sub.6H.sub.4-4-CH.sub.3)—C.sub.6H.sub.4 4-CH.sub.3—C.sub.6H.sub.4 1 1 XXII 1,2-phenylene 2-(NH—CO—NH—C.sub.6H.sub.5)—C.sub.6H.sub.4 4-CH.sub.3—C.sub.6H.sub.4 1 1 XXIII 1,2-phenylene 4-(CO.sub.2C.sub.2H.sub.5)—C.sub.6H.sub.4 4-CH.sub.3—C.sub.6H.sub.4 1 1 XXIV 1,3-phenylene C.sub.6H.sub.5 4-CH.sub.3—C.sub.6H.sub.4 1 1 XXV 1,3-phenylene 2-(NH—CO—NH—C.sub.6H.sub.5)—C.sub.6H.sub.4 4-CH.sub.3—C.sub.6H.sub.4 1 1 XXVI 1,4-phenylene C.sub.6H.sub.5 4-CH.sub.3—C.sub.6H.sub.4 1 1 XXVII 1,4-phenylene 3—CH.sub.3—C.sub.6H.sub.4 4-CH.sub.3—C.sub.6H.sub.4 1 1 XXVIII 1,4-phenylene 4-(CO.sub.2C.sub.2H.sub.5)—C.sub.6H.sub.4 4-CH.sub.3—C.sub.6H.sub.4 1 1 XXIX 1,4-phenylene 4-Cl—C.sub.6H.sub.4 4-CH.sub.3—C.sub.6H.sub.4 1 1 XXX 1,4-phenylene 2-(NH—CO—NH—C.sub.6H.sub.5)—C.sub.6H.sub.4 4-CH.sub.3—C.sub.6H.sub.4 1 1 XXXI 1,4-phenylene 4-(CO.sub.2C.sub.2H.sub.5)—C.sub.6H.sub.4 4-CH.sub.3—C.sub.6H.sub.4 1 1 XXXII Benzene-1,2,4-triyl C.sub.6H.sub.5 4-CH.sub.3—C.sub.6H.sub.4 1 2 XXXIII Benzene-1,3,4,6-tetryl C.sub.6H.sub.5 C.sub.6H.sub.5 2 2 XXXIV Benzene-1,3,4,6-tetryl C.sub.6H.sub.5 4-CH.sub.3—C.sub.6H.sub.4 2 2 XXXV Benzene-1,3,4,6-tetryl 4-(CO.sub.2C.sub.2H.sub.5)—C.sub.6H.sub.4 4-CH.sub.3—C.sub.6H.sub.4 2 2
[0110] Analytical data:
[0111] Analytical data:
[0112] I, C.sub.19H.sub.17N.sub.3O.sub.5S.sub.2, M=431.5, N-phenyl-2-(3-(phenylsulfonyl)ureide)benzene sulfonamide
[0113] MS (ESI):m/z (%)=430.0 (13) [M—H].sup.−, 273.0 (100) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 247.0 (6) [M-H—Ar.sup.2SO.sub.2NCO].sup.−.
[0114] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=11.71 (1H, s), 10.37 (1H, s), 8.72 (1H, s), 8.04-7.97 (2H, m,), 7.77 (1H, dd, J=8.3=1.2 Hz), 7.73 (1H, dd, J=8.1, 1.7 Hz) 7.71 (1H, tt, J=7.4, 1.5 Hz), 7.67-7.62 (2H, m), 7.49 (1H, ddd, J=8.3, 7.4, 1.6 Hz), 7.21-7.13 (3H, m), 7.02-6.97 (3H, m).
[0115] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=149.06 (NHC(O)NH), 139.71, 136.65, 135.21, 133.62, 133.40, 131.67, 129.09, 129.04, 128.96, 128.82, 127.34, 125.52, 124.59, 120.54.
[0116] II, C.sub.20H.sub.19N.sub.3O.sub.5S.sub.2, M=445.5, N-(2-tolyl)-2-(3-(phenylsulfonyl)ureide)benzene sulfonamide
[0117] MS (ESI):m/z (%)=444.0 (20) [M-H].sup.−, 287.0 (100), [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 261.1(10) [M-H—Ar.sup.2SO.sub.2NCO].sup.−.
[0118] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=11.73 (1H, s), 9.73 (1H, s), 8.74 (1H, s), 8.00-7.98 (2H, m), 7.83 (1H, dd, J=8.5, 1.1 Hz), 7.70 (1H, tt, J=7.4, 1.6 Hz), 7.66-7.60 (3H, m), 7.51 (1H, ddd, J=8.3, 7.6, 1.7 Hz), 7.13 (1H, ddd, J=7.6, 1.1 Hz),7.05 (1H, ddd, J=8.1, 6.5, 2.2 Hz), 7.03-6.97 (3H, m), 1.95 (3H, s).
[0119] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=148.96 (NHC(O)NH), 139.78, 135.17, 134.24, 133.72, 133.57, 133.35, 130.68, 129.01, 128.90, 128.43, 127.31, 126.81, 126.56, 126.29, 123.41, 122.77, 17.24 (CH.sub.3).
[0120] III, C.sub.20H.sub.19N.sub.3O.sub.5S.sub.2, M=445.5, N-(4-tolyl)-2-(3-(phenylsulfonyl)ureide)benzene sulfonamide
[0121] MS (ESI):m/z (%)=287.0 (100) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 261.1(5) [M-H—Ar.sup.2SO.sub.2NCO].sup.−.
[0122] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=11.74 (1H, s), 10.23 (1H, s), 8.75 (1H, s), 8.04-7.99 (2H, m), 7.78 (1H, dd, J=8.4, 1.1 Hz), 7.71 (1H, dd, 8.0, 1.6 Hz), 7.70(1H, tt, J=7.4, 1.5 Hz), 766-7.61 (2H, m) 7.46 (1H, ddd, J=8.4, 7.4, 1.6 Hz), 7.14 (1H, ddd, J=7.8, 7.5, 1.2 Hz), 7.00-6.94 (2H, m), 6.93-6.89 (2H, m), 2.14 (3H, s).
[0123] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=149.11 (NHC(O)NH), 139.81, 135.28, 134.11, 133.96, 133.54, 133.38, 129.58, 129.06, 129.01, 127.88, 127.35, 123.66, 123.32, 121.14, 20.25, (CH.sub.3).
[0124] IV, C.sub.20H.sub.19N.sub.3O.sub.6S.sub.2, M=461.5, N-(4-methoxyphenyl)-2-(3-(phenylsulfonyl)ureide)benzene sulfonamide
[0125] MS (ESI):m/z (%)=460.0 (25) [M-H].sup.−, 303.0 (100) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 278.0(4) [M-H—Ar.sup.2SO.sub.2NCO].sup.−.
[0126] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=11.75 (1H, s), 10.06 (1H, s), 8.76 (1H, s), 8.02-7.99 (2H, m), 7.78 (1H, dd, J=8.4, 1.2 Hz), 7.70 (1H, tt, J=7.4, 1.6 Hz), 7.67-7.61 (3H, m) 7.47 (1H, ddd, J=8.4, 7.4, 1.6 Hz), 7.14 (1H, ddd, J=7.9, 7.4, 1.2 Hz), 6.94-6.90 (2H, m), 6.77-6.72 (2H, m), 3.65 (3H, s).
[0127] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=156.95 (C—OCH.sub.3), 149.14 (NHC(O)NH), 139.82, 135.27, 133.50, 133.37, 129.06, 129.04, 128.93, 127.78, 127.31, 124.02, 123.60, 123.22, 114.32, 55.09 (OCH.sub.3).
[0128] V, C.sub.22H.sub.21N.sub.3O.sub.7S.sub.2, M=503.5, ethyl 2-2-(3-(phenylsulfonyl)ureide)phenyl sulfonamide) benzoate
[0129] MS (ESI):m/z (%)=501.9 (4) [M-H].sup.−, 345.1(100) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 319.0(15) [M-H—Ar.sup.2SO.sub.2NCO].sup.−.
[0130] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=11.93 (1H, s), 10.73 (1H, s), 8.66 (1H, s), 8.00-7.96 (2H, m), 7.81 (1H, dd, J=8.0, 1.6 Hz), 7.77 (2H, 2xdd, J=8.2, 1.4 Hz), 7.69 (1H, tt, J=7.4, 1.6 Hz), 766-7.61 (2H, m) 7.46 (1H, ddd, J=8.4, 7.4, 1.6 Hz), 7.14 (1H, ddd, J=7.8, 7.5, 1.2 Hz), 7.64-7.59 (2H, m), 7.58-7.46 (3H, m), 7.53 (1H, ddd, J=8.3, 7.4, 1.6), 7.49 (1H, ddd, J=8.3, 7.4, 1.6 Hz), 7.18 (1H, ddd, J=7.7, 7.8, 1.2 Hz), 7.12 (1H, ddd, J=7.9, 7.4, 1.2 Hz), 4.18 (2H, q, J=7.1 Hz), 1.23 (3H, t,J=7.1 Hz).
[0131] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=166.80 (CO.sub.2R), 149.07 (NHC(O)NH), 139.74, 138.05, 135.04, 134.32, 134.25, 133.38, 130.87, 129.37, 129.02, 127.24, 127.10, 125.52, 124.24, 123.89, 120.15, 117.87, 61.47 (OCH.sub.2CH.sub.3), 13.71(OCH.sub.2CH.sub.3).
[0132] VI, C.sub.21H.sub.19N.sub.3O.sub.7S.sub.2, M=489.5, methyl 4-(2-(3-(phenylsulfonyl)ureide)phenyl sulfonamide) benzoate
[0133] MS (ESI):m/z (%)=488.0 (26) [M-H].sup.−, 331.0 (100) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 305.0 (50) [M-H—Ar.sup.2SO.sub.2NCO].sup.−.
[0134] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=11.68 (1H, s), 10.97 (1H, s), 8.71 (1H, s), 8.0-7.99 (2H, m), 7.80 (1H, dd, J=8.1, 1.6 Hz), 7.79-7.74 (3H, m), 7.71 (1H,tt, J=7.4, 1.3 Hz), 7.67-7.62 (2H, m), 7.51 (1H, ddd, J=8.3, 7.4, 1.6 Hz), 7.20 (1H, ddd, J=7.7, 1.2 Hz), 7.16-7.12 (2H, m), 3.78 (3H, s), 3.35 (1H, q, J=7.0 Hz), 1.07 (2H, t, J=7.0 Hz).
[0135] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=165.47 (CO.sub.2R), 149.13 (NHC(O)NH), 141.49, 139.70, 135.17, 133.95, 133.40, 130.52, 129.05, 129.00, 127.99, 127.34, 125.54, 124.87, 124.05, 118.43, 51.84 (OCH.sub.3).
[0136] VII, C.sub.19H.sub.16CIN.sub.3O.sub.5S.sub.2, M=465.9, N-(3-chlorophenyl)-2-(3-(phenylsulfonyl)ureide) benzene sulfonamide
[0137] MS (ESI):m/z (%)=307.0 (100) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 281.0 (26) [M-H—Ar.sup.2SO.sub.2NCO].sup.−.
[0138] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=11.70 (1H, s), 10.67 (1H, s), 8.71 (1H, s), 8.02-7.99 (2H, m), 7.77 (1H, dd, J=8.4, 1.2 Hz), 7.76 (2H, dd, J=8.0, 1.6 Hz) 7.70 (1H,tt, J=7.4, 1.3 Hz), 7.66-7.61 (2H, m), 7.52 (1H, ddd, J=8.4 7.3, 1.6 Hz), 7.22 (1H, ddd, J=9.1,7.9, 1.7 Hz), 7.18 (1H, dd, J=8.1 Hz), 7.08 (1H, dd, J=2.1 Hz), 7.03 (1H, ddd, J=8.0, 2.1, 0.9 Hz)), 6.97 (1H, ddd, J=8.2, 2.1, 0.9 Hz). .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=149.10 (NHC(O)NH), 139.71, 138.33, 135.26, 133.90, 133.43, 133.39, 130.76, 129.04, 128.88, 127.80, 127.31, 124.30, 123.97, 123.83, 119.76, 118.5.
[0139] VIII, C.sub.26H.sub.23N.sub.5O.sub.6S.sub.2, M=565.6, 2-(3-(phenylsulfonyl)ureide)-N-(2-(3-phenylureido)phenyl)benzene sulfonamide
[0140] MS (ESI):m/z (%)=564.1(100) [M-H].sup.−, 407.0 (80) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 381.2 (12) [M-H—Ar.sup.2SO.sub.2NCO].sup.−.
[0141] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=11.74 (1H, s), 9.78 (1H, s), 9.47 (1H, s), 8.72 (1H, s), 8.00 (1H, dd, J=8.3, 1.4 Hz), 8.00-7.97 (2H, m), 7.84 (1H, dd, J=8.3, 1.2 Hz), 7.70 (1H, tt, J=7.5, 1.6 Hz), 7.66 (1H, dd, J=8.0, 1.6 Hz), 7.65-7.62 (2H, m), 7.58-7.54 (1H, m)7.54-7.51 (2H, m), 7.34-7.29 (2H, m), 7.17 (1H, ddd, J=8.0, 7.2, 0.9 Hz), 7.05 (1H, ddd, J=8.3, 7.4, 1.6 Hz), 7.00 (1H, tt, J=7.4, 1.1Hz), 6.67 (1H, ddd, J=7.8, 6.4, 1.5 Hz), 6.42 (1H, dd, J=8.0, 1.5 Hz).
[0142] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=152.67(NHC(O)NH), 149.17(NHC(O)NH), 139.80, 139.67, 136.96, 135.56, 133.39, 131.70, 129.06, 128.85, 128.78, 128.74, 127.54, 127.33, 125.55, 124.14, 123.03, 122.18, 121.96, 121.15, 118.33, 118.31.
[0143] IX, C.sub.20H.sub.19N.sub.3O.sub.5S.sub.2, M=445.5, N-phenyl-2-(3-tosylureide)benzene sulfonamide
[0144] MS (ESI):m/z (%)=444.0 (22) [M-H].sup.−, 273.0 (100) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 247.0 (9) [M-H—Ar.sup.2SO.sub.2NCO].sup.−.
[0145] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=11.65 (1H, s), 10.38 (1H, s), 8.72 (1H, s), 7.92-7.87 (2H, m), 7.79 (1H, dd, J=8.4, 1.1 Hz), 7.74 (1H, dd, J=8.0, 1.6 Hz), 7.48 (1H, ddd, J=8.4, 7.3, 1.6 Hz), 7.44-7.40 (2H, m), 7.26-7.12 (3H, m), 7.05-7.01 (2H, m), 6.99 (1H, tt, J=7.4, 1.4 Hz), 2.38 (3H, s).
[0146] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=149.11 (NHC(O)NH), 143.93, 136.91, 136.70, 135.31, 133.61, 129.46, 129.10, 128.97, 127.88, 127.45, 124.60, 123.69, 123.44, 120.54, 20.99 (CH.sub.3).
[0147] X, C.sub.21H.sub.21N.sub.3O.sub.5S.sub.2, M=459.5, N-(2-tolyl)-2-(3-tosylureide)benzene sulfonamide
[0148] MS (ESI):m/z (%)=457.9 (1) [M-H].sup.−, 287.1 (100) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 261.1(16) [M-H—Ar.sup.2SO.sub.2NCO].sup.−.
[0149] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=11.61 (1H, s), 9.69 (1H, s), 8.70 (1H, s), 7.87-7.80 (2H, m), 7.82 (1H, dd, J=8.3, 1.1 Hz) 7.60 (1H, dd, J=8.0, 1.6 Hz), 7.52 (1H, ddd, J=8.4, 7.3, 1.6 Hz), 7.45-7.40 (2H, m), 7.25-7.19 (1H, m), 7.14 (1H, ddd, J=8.0, 7.4, 1.1 Hz), 7.09-7.05 (1H, m), 7.03-7.00 (2H, m), 6.97-6.94 (1H, m), 2.40 (3H, s), 1.95 (3H, s)
[0150] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=149.00(NHC(O)NH), 143.85, 136.95, 135.23, 134.22, 133.74, 133.56, 130.69, 129.42, 128.90, 128.38, 127.36, 126.78, 126.48, 126.28, 123.35, 122.74, 20.98 (CH.sub.3), 17.26 (CH.sub.3).
[0151] XI, C.sub.21H.sub.21N.sub.3O.sub.5S.sub.2, M=459.5, N-(4-tolyl)-2-(3-tosylureide)benzene sulfonamide
[0152] MS (ESI):m/z (%)=287.1(100) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 261.1(8) [M-H—Ar.sup.2SO0.sub.2NCO].sup.−.
[0153] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=11.63 (1H, s), 10.20 (1H, s), 8.71 (1H, s), 7.90-7.86 (2H, m), 7.79 (1H, dd, J=8.4, 1.2 Hz), 7.70 (1H, dd, J=8.0, 1.6 Hz), 7.47 (1H, ddd, J=8.4, 7.4, 1.6 Hz), 7.44-7.41 (2H, m), 7.14 (1H, ddd, J=8.0, 7.3, 1.2 Hz), 6.97-6.94 (2H, m,), 6.91-6.88 (2H, m), 2.39 (3H, s), 2.15 (3H, s).
[0154] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=149.06 (NHC(O)NH), 143.84, 136.95, 135.33, 134.00, 133.95, 133.48, 129.52, 129.44, 128.96, 127.78, 127.41, 123.55, 123.23, 121.05, 20.95(CH.sub.3), 20.20(CH.sub.3).
[0155] XII, C.sub.21H.sub.21N.sub.3O.sub.5S.sub.2, M=459.5, N-(3-tolyl)-2-(3-tosylureide)benzene sulfonamide
[0156] MS (ESI):m/z (%)=58.0 (1) [M-H].sup.−, 287.1 (100) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 261.0(10) [M-H—Ar.sup.2SO.sub.2NCO].sup.−.
[0157] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=11.64 (1H, s), 10.29 (1H, s), 8.72 (1H, s), 7.90-7.86 (2H, m), 7.79 (1H, dd, J=8.4, 1.1 Hz), 7.74 (1H, dd, J=8.0, 1.6 Hz), 7.48 (1H, ddd, J=8.4, 7.4, 1.6 Hz), 7.42 (2H, d, J=8.1 Hz), 7.17 (1H, ddd, J=7.7, 1.2 Hz), 7.03 (1H, t, J=7.8 Hz), 6.86 (1H, t, J=1.9 Hz), 6.82-6.78 (2H, m), 2.38 (3H, s), 2.15 (3H, s).
[0158] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=149.05 (NHC(O)NH), 143.89, 138.55, 136.92, 136.60, 135.36, 133.56, 129.44, 128.89, 127.84, 127.39, 125.37, 123.63, 123.23, 121.12, 117.65, 20.97(CH.sub.3), 20.85(CH.sub.3).
[0159] XIII, C.sub.21H.sub.21N.sub.3O.sub.6S.sub.2, M=475.5, N-(4-methoxyphenyl)-2-(3-tosylureide)benzene sulfonamide
[0160] MS (ESI):m/z (%) =473.9 (2) [M-H].sup.−, 303.0 (100) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 277.0 (5) [M-H—Ar.sup.2SO.sub.2NCO].sup.−.
[0161] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=11.64 (1H, s), 10.03 (1H, s), 8.72 (1H, s), 7.89-7.85 (2H, m), 7.79 (1H, dd, J=8.4, 1.1 Hz), 7.64 (1H, dd, J=8.0, 1.6 Hz), 7.48 (1H, ddd, J=8.4, 7.3, 1.6 Hz), 7.44-7.40 (2H, m), 7.14 (1H, ddd, J=7.9, 7.5, 1.2 Hz), 6.93-6.88 (2H, m), 6.75-6.71 (2H, m) 3.66 (3H, s), 2.39 (3H, s).
[0162] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=156.89 (C—OCH.sub.3), 149.10 (NHC(O)NH), 143.84, 136.96, 135.32, 133.45, 129.45, 129.42, 128.92, 127.68, 127.36, 123.94, 123.50, 123.13, 114.26, 55.04 (OCH.sub.3), 20.95(CH.sub.3).
[0163] XIV, C.sub.23H.sub.23N.sub.3O.sub.7S.sub.2, M=517.6, ethyl 2-(2-(3-tosylureido)phenyl sulfonamide) benzoate
[0164] MS (ESI):m/z (%)=516.0 (5) [M-H].sup.−, 345.0 (100) ([M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 319.1 (23) [M-H—Ar.sup.2SO.sub.2NCO].sup.−.
[0165] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=11.84 (1H, s), 10.73 (1H, s), 8.64 (1H, s), 7.87-7.84 (2H, m), 7.82 (1H, dd, J=8.0, 1.7 Hz), 7.78 (1H, dd, J=8.2, 1.1 Hz), 7.77 (1H, dd, J=7,9, 1.6 Hz), 7.53 (1H, ddd, J=8.3, 7.5, 1.6 Hz), 7.49 (1H, ddd, J=8.4, 7.2, 1.7 Hz), 7.41 (1H, dd, J=8.3, 1.1 Hz), 7.40-7.38 (2H, m), 7.18 (1H, ddd, J=7.8, 7.6, 1.2 Hz), 7.13 (1H, ddd, J=7.8, 7.5, 1.3 Hz), 4.19 (2H, q, J=7.1 Hz), 2.37 (3H, s), 1.24 (3H, t, J=7.1 Hz).
[0166] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=166.78 (CO.sub.2R), 149.07 (NHC(O)NH), 143.86, 138.08, 136.91, 135.09, 134.29, 134.23, 130.85, 129.39, 129.33, 127.31, 127.07, 124.17, 123.86, 123.82, 120.06, 117.81, 61.45 (OCH.sub.2CH.sub.3), 20.93(CH.sub.3), 13.70 (OCH.sub.2CH.sub.3).
[0167] XV, C.sub.22H.sub.21N.sub.3O.sub.7S.sub.2, M=503.5, methyl 4-(2-(3-tosylureide)phenyl sulfonamide) benzoate
[0168] MS (ESI):m/z (%)=502.0 (1) [M-H].sup.−, 331.0 (100) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 305.1(73) [M-H—Ar.sup.2SO.sub.2NCO].sup.−.
[0169] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=11.55 (1H, s), 10.93 (1H, s), 8.67 (1H, s), 7.90-7.86 (2H, m), 7.81 (1H, dd, J=8.2, 1.6 Hz), 7.76 (1H, dd, J=8.5, 1.2 Hz), 7.76-7.72 (2H, m), 7.51 (1H, ddd, J=8.4, 7.3, 1.6 Hz), 7.43-7.41 (2H, m), 7.20(1H, ddd, J=7.9, 7.4, 1.2 Hz), 7.09 (2H, m), 3.77 (3H, s), 2.39 (3H, s).
[0170] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=165.45 (CO.sub.2R), 149.13 (NHC(O)NH), 143.97, 141.46, 136.80, 135.14, 133.96, 130.51, 129.47, 129.07, 127.99, 127.50, 124.81, 124.18, 124.05, 118.31, 51.84 (OCH.sub.3), 20.96(CH.sub.3).
[0171] XVI, C.sub.20H.sub.18CIN.sub.3O.sub.5S.sub.2, M=479.9, N-(2-chlorphenyl)-2-(3-tosylureide)benzene sulfonamide
[0172] MS (ESI):m/z (%)=307.0 (100) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 281.0 (90) [M-H—Ar.sup.2SO.sub.2NCO].sup.−.
[0173] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=11.64 (1H, s), 10.00 (1H, s), 8.65 (1H, s), 7.89 (1H, dd, J=8.5, 1.2 Hz), 7.87-7.83 (2H, m), 7.64 (1H, dd, J=8.0, 1.6 Hz), 7.52 (1H, ddd, J=8.5, 7.2, 1.5 Hz), 7.41 (2H, d, J=8.0 Hz), 7.32 (1H, dd, J=8.0, 1.5 Hz), 7.27 (1H, dd, J=8.0, 1.7 Hz), 7.22 (1H, ddd, J=7.7, 1.5 Hz), 7.13 (1H, ddd, J=8.1,7.2, 1.0 Hz), 7.12 (1H, ddd, J=7.7, 1.2 Hz), 2.38 (3H, s)
[0174] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=148.94 (NHC(O)NH), 143.89, 136.86, 135.37, 133.89, 132.51, 129.81, 129.43, 129.01, 128.96, 127.94, 127.90, 127.69, 127.38, 127.25, 123.34, 122.73, 20.99(CH.sub.3).
[0175] XVII, C.sub.20H.sub.18CIN.sub.3O.sub.5S.sub.2, M=479.9, N-(3-chlorphenyI)-2-(3-tosylureide)benzene sulfonamide
[0176] MS (ESI):m/z (%)=477.9 (2) [M-H].sup.−, 307.0 (100) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 281.0 (40) [M-H—Ar.sup.2SO.sub.2NCO].sup.−.
[0177] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=11.63 (1H, s), 10.68 (1H, s), 8.70 (1H, s), 7.90-7.87 (2H, m), 7.78 (1H, dd, J=8.5, 1.2 Hz), 7.76 (1H, dd, J=8.0, 1.6 Hz), 7.51 (1H, ddd, J=8.4, 7.4, 1.6 Hz), 7.43-7.39 (2H, m), 7.19 (1H, ddd, J=8.1, 7.4, 1.2 Hz), 7.18 (1H, dd, J=8.2 Hz), 7.08 (1H, dd, J=2.1 Hz), 7.04 (1H, ddd, J=8.1, 2.1, 0.9 Hz), 6.99 (1H, ddd, J=8.2, 2.2, 0.9 Hz), 2.37 (3H, s)
[0178] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=149.14 (NHC(O)NH), 143.91, 138.37, 136.90, 135.35, 133.88, 133.46, 130.75, 129.45, 128.90, 127.77, 127.40, 124.29, 123.90, 123.81, 119.76, 118.55, 20.98(CH.sub.3).
[0179] XVIII, C.sub.20H.sub.18CIN.sub.3O.sub.5S.sub.2, M=479.9, N-(4-chlorphenyl)-2-(3-tosylureide)benzene sulfonamide
[0180] MS (ESI):m/z (%)=307.0 (100) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 281.0 (23) [M-H—Ar.sup.2SO.sub.2NCO].sup.−.
[0181] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=11.63 (1H, s), 10.56 (1H, s), 8.72 (1H, s), 7.91-7.86 (2H, m), 7.78 (1H, dd, J=8.4, 1.1 Hz), 7.72 (1H, dd, J=8.0, 1.5 Hz), 7.50 (1H, ddd, J=8.4, 7.4, 1.6 Hz), 7.42 (2H, d, J=8.0 Hz), 7.22-7.15 (3H, m), 7.02-7.00 (2H, m), 2.38 (3H, s)
[0182] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=149.15 (NHC(O)NH), 143.91, 136.88, 135.76, 135.27, 133.78, 129.48, 129.46, 129.07, 128.94, 128.70, 127.74, 127.43, 123.75, 121.92, 20.98(CH.sub.3).
[0183] XIX, C.sub.22H.sub.23N.sub.3O.sub.6S.sub.2, M=489.5, N-(4-ethoxyphenyl)-2-(3-tosylureide)benzene sulfonamide
[0184] MS (ESI):m/z (%)=488.0 (3) [M-H].sup.−, 317.1 (100) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−.
[0185] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=11.66 (1H, s), 10.03 (1H, s), 8.74 (1H, s), 7.90-7.86 (2H, m), 7.80 (1H, dd, J=8.4, 1.2 Hz), 7.65 (1H, dd, J=8.0, 1.6 Hz), 7.48 (1H, ddd, J=8.4, 7.4, 1.6 Hz), 7.45-7.41 (2H, m), 7.14 (1H, ddd, J=7.9, 7.5, 1.2 Hz), 6.93-6.88 (2H, m), 6.75-6.71 (2H, m), 3.91 (2H, q, J=7.0 Hz), 2.39 (3H, s), 1.26 (3H, t, J=7.0 Hz).
[0186] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=156.19 (C-OC.sub.2H.sub.5), 149.11(NHC(O)NH), 143.82, 136.97, 135.33, 133.43, 129.43, 128.98, 128.81, 127.67, 127.36, 123.92, 123.46, 123.08, 114.73, 63.05(OCH.sub.2CH.sub.3), 20.94(CH.sub.3), 14.48 (OCH.sub.2CH.sub.3).
[0187] XX, C.sub.21H.sub.21N.sub.3O.sub.6S.sub.2, M=475.5, N-(2-methoxyphenyl)-2-(3-tosylureido)benzene sulfonamide
[0188] MS (ESI):m/z (%)=473.9 (3) [M-H].sup.−, 303.0 (100) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 277.0 (10) [M-H—Ar.sup.2SO.sub.2NCO].sup.−.
[0189] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=11.68 (1H, s), 9.42 (1H, s), 8.61 (1H, s), 7.96 (1H, dd, J=8.5, 1.2 Hz), 7.92-7.86 (2H, m), 7.58 (1H, dd, J=7.9, 1.6 Hz), 7.47 (1H, ddd, J=8.5, 7.4, 1.6 Hz), 7.43 (2H, d, J=8.1 Hz), 7.24 (1H, dd, J=7.8, 1.6 Hz), 7.07 (1H, dd, J=5.1, 1.6 Hz), 7.06 (1H, ddd, J=7.8, 5.9, 1.8 Hz), 6.86-6.78 (2H, m), 3.33 (3H, s), 2.38 (3H, s)
[0190] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=152.30 (C—OCH.sub.3), 148.97 (NHC(O)NH), 143.97, 136.85, 135.40, 133.56, 129.45, 129.13, 127.60, 127.44, 127.17, 125.22, 124.05, 122.82, 121.92, 120.36, 111.56, 55.22 (OCH.sub.3), 20.97(CH.sub.3).
[0191] XXI, C.sub.27H.sub.25N.sub.3O.sub.8S.sub.2, M=615.7, 3-(2-(3-tosylureide)phenyl sulfonamide)phenyl 4-methyl benzene sulfonate
[0192] MS (ESI):m/z (%)=614.1(100) [M-H].sup.−, 443.0 (95) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 417.0 (25) [M-H—Ar.sup.2SO.sub.2NCO].sup.−.
[0193] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=11.64 (1H, s), 10.70 (1H, s), 8.68 (1H, s), 7.91-7.85 (2H, m), 7.81 (1H, d, J=8.3 Hz), 7.64 (3H,m), 7.52 (1H, ddd, J=8.5, 7.2, 1.5 Hz), 7.40 (4H, t, J=8.3 Hz,), 7.18 (1H, ddd, J=7.7, 1.2 Hz), 7.13 (1H, dd, J=8.2, Hz), 6.93 (1H, dd, J=8.1, 2.0 Hz), 6.89 (1H, dd, J=2.2 Hz), 6.61 (1H, dd, J=8.1, 2.3 Hz), 2.37 (6H, s).
[0194] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=149.32, 149.19(NHC(O)NH), 145.71, 143.88, 138.30, 136.93, 135.33, 133.85, 131.19, 130.46, 130.09, 129.43, 128.77, 127.97, 127.50, 127.37, 125.58, 123.56, 118.57, 117.58, 113.36, 21.08(CH.sub.3), 20.96(CH.sub.3).
[0195] XXII, C.sub.27H.sub.25N.sub.5O.sub.6S.sub.2, M=579.6, 4-methyl-N-((4-(N-(2-(3-phenylureide)phenyl) sulfamoyl)phenyl)carbamoyl)benzene sulfonamide
[0196] MS (ESI):m/z (%)=578.1(100) [M-H].sup.−, 407.1 (55), [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 381.0 (8) [M-H—Ar.sup.2SO.sub.2NCO].sup.−.
[0197] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=11.63 (1H, s), 9.75 (1H, s), 9.45 (1H, s), 8.69 (1H, s), 8.30 (1H, s), 8.00 (1H, dd, J=8.4, 1.3 Hz), 7.84 (1H, dd, J=8.4, 1.2 Hz), 7.86-7.83 (2H, m), 7.65 (1H, dd, J=8.0, 1.6 Hz), 7.55 (1H, ddd, J=8.6, 7.2, 1.7 Hz), 7.52-7.49 (2H, m), 7.44-7.40 (2H, m), 7.33-7.29 (2H, m), 7.16 (1H, ddd, J=8.1, 7.2, 1.2 Hz), 7.07 (1H, ddd, J=8.3, 7.4, 1.6 Hz), 7.00 (1H, tt, J=7.4, 1.1Hz), 6.68 (1H, ddd, J=7.7, 1.5 Hz), 6.40 (1H, dd, J=8.0, 1.6 Hz), 2.40 (3H, s).
[0198] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=152.62 (NHC(O)NH, 149.17(NHC(O)NH), 146.49, 143.86, 141.76, 141.40, 139.63, 136.95, 135.55, 129.43, 129.19, 128.74, 128.70, 127.53, 127.35, 125.56, 124.16, 121.92, 118.54, 118.30, 118.28, 116.84, 20.82(CH.sub.3).
[0199] XXIII, C.sub.27H.sub.25N.sub.3O.sub.7S.sub.2, M=517.6, ethyl 4-(2-(3-tosylureide)phenyl) sulfonamide)benzoate
[0200] MS (ESI):m/z (%)=516.9 (4) [M-H].sup.−, 345.0 (100) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 319.1(70) [M-H—Ar.sup.2SO.sub.2NCO].sup.−.
[0201] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=11.53 (1H, s), 10.91 (1H, s), 8.66 (1H, s), 7.92-7.87 (2H, m), 7.82 (1H, dd, J=8.0, 1.6 Hz), 7.76 (1H, dd, J=8.4,1.1 Hz), 7.77-7.72 (2H, m), 7.51 (1H, ddd, J=8.3, 7.4, 1.6 Hz), 7.43 (2H, d, J=8.1 Hz), 7.22-7.18 (1H, m), 7.13-7.10 (2H, m), 4.24 (3H, q, J=7.2 Hz), 2.39 (3H, s), 1.26 (3H, t, J=7.1 Hz)
[0202] .sup.13C NMR (126 MHz, DMSO-d.sub.6):δ(ppm)=164.94 (CO.sub.2R), 149.14 (NHC(O)NH), 143.93, 141.38, 136.82, 135.14, 133.94, 130.45, 129.44, 129.13, 127.98, 127.52, 125.12, 124.18, 124.02, 118.31, 60.45 (OCH.sub.2CH.sub.3), 20.96(CH.sub.3), 14.06 (OCH.sub.2CH.sub.3).
[0203] XXIV, C.sub.20H.sub.19N.sub.3O.sub.5S.sub.2, M=445.5, N-phenyl-3-(3-tosylureide)benzene sulfonamide
[0204] MS (ESI):m/z (%)=444.0 (100) [M-H].sup.−, 273.1 (20) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 247.0 (8) [M-H—Ar.sup.2SO.sub.2NCO].sup.−.
[0205] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=10.82 (1H, s), 10.29 (1H, s), 9.17 (1H, s), 8.05-8.02 (1H, m), 7.92-7.88 (2H, m), 7.46 (1H, m), 7.44-7.40 (4H, m), 7.22-7.17 (2H, m), 7.12-7.08 (2H, m), 6.99 (1H, tt, 7.4, 1.2 Hz), 2.36 (3H, s).
[0206] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=149.42 (NHC(O)NH), 143.95, 140.29, 138.90, 137.58, 137.01, 129.63, 129.48, 129.06, 127.53, 124.05, 122.91, 121.22, 120.13, 116.67, 21.01(CH.sub.3).
[0207] XXV, C.sub.27H.sub.25N.sub.5O.sub.6S.sub.2, M=579.6, N-(2-(3-phenylureide)phenyl)-3-(3-tosylureide)benzene sulfonamide
[0208] MS (ESI):m/z (%)=578.1 (95) [M-H].sup.−, 407.1 (100) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−.
[0209] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=9.56 (1H, s), 9.47 (1H, s), 9.16 (1H, s), 8.29 (1H, s), 8.05 (1H, dd, J=8.3, 1.4 Hz), 7.93 (1H, t, J=2.0 Hz, dd), 7.89 (2H, d, J=8.2 Hz), 7.53 (1H, dd, J=8.0, 2.1 Hz), 7.52-7.49 (2H, m), 7.44 (1H, t, J=8.1 Hz),7.44 (2H, d, J=8.1 Hz) 7.33 (1H, ddd, J=7.8, 1.4 Hz), 7.31-7.27 (2H, m), 7.16 (1H, ddd, J=8.0, 1.6 Hz), 6.98 (1H, t), J=7.3 Hz), 6.76 (1H, ddd, J=7.6, 1.5 Hz), 6.49 (1H, dd, J=8.0, 1.6 Hz), 2.39 (3H, s)
[0210] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=152.49(NHC(O)NH), 149.38 (NHC(O)NH), 143.91, 139.94, 139.76, 138.78, 136.98, 136.95, 129.47, 129.44, 128.73, 127.58, 127.49, 127.13, 124.88, 122.94, 121.88, 121.84, 121.70, 120.95, 118.25, 117.06, 21.00 (CH.sub.3).
[0211] XXVI, C.sub.20H.sub.19N.sub.3O.sub.5S.sub.2, M=445.5, N-phenyl-4-(3-tosylureide)benzene sulfonamide
[0212] MS (ESI):m/z (%)=444.1(100) [M-H].sup.−, 273.0 (40) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 247.1(68) [M-H—Ar2SO.sub.2NCO].sup.−.
[0213] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=10.88 (1H, s), 10.11 (1H, s), 9.18 (1H, s), 7.88-7.84 (2H, m), 7.68-7.64 (2H, m), 7.50-7.47 (2H, m), 7.40 (2H, d, J=8.1 Hz), 7.22-7.17 (2H, m), 7.10-7.06 (2H, nn), 6.99 (1H, tt, J=7.4, 1.3 Hz), 2.36 (3H, s)
[0214] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=149.25 (NHC(O)NH), 143.93, 142.02, 137.71, 136.83, 133.34, 129.44, 129.00, 127.92, 127.47, 123.93, 120.09, 118.51, 20.97 (CH.sub.3).
[0215] XXVII, C.sub.21H.sub.21N.sub.3O.sub.5S.sub.2, M=459.5, N-(3-tolyl)-4-(3-tosylureide)benzene sulfonamide
[0216] MS (ESI):m/z (%)=458.0(100) [M-H].sup.−, 287.0 (23) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 261.1 (47) [M-H—Ar.sup.2SO.sub.2NCO].sup.−.
[0217] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=10.84 (1H, s), 10.04 (1H, s), 9.17 (1H, s), 7.89-7.84 (2H, m), 7.69-7.64 (2H, m), 7.51-7.47 (2H, m), 7.42-7.38 (2H, m), 7.07 (1H, t, J=7.7 Hz), 6.92-6.86 (2H, m), 6.80 (1H, ddt, J=7.4, 1.7, 0.9 Hz), 2.37 (3H, s), 2.17 (3H, s)
[0218] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=149.26 (NHC(O)NH), 143.93, 141.99, 138.33, 137.67, 136.84, 133.45, 129.44, 129.41, 128.80, 127.91, 127.47, 124.61, 120.48, 118.51, 116.98, 20.95(CH.sub.3).20.93 (CH.sub.3).
[0219] XXVIII, C.sub.22H.sub.21N.sub.3O.sub.7S.sub.2, M=503.5, methyl 4-(4-(3-tosylureide)phenyl sulfonamide)benzoate
[0220] MS (ESI):m/z (%)=502.0(100) [M-H].sup.−, 331.0 (12) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 305.1(45) [M-H—Ar.sup.2SO.sub.2NCO].sup.−.
[0221] .sup.1H NMR (500 MHz, DMSO-d.sub.6):δ(ppm)=10.88 (1H, s), 10.70 (1H, s), 9.20 (1H, s), 7.86 (2H, d, J=8.0 Hz), 7.81 (2H, d, J=8.6 Hz), 7.74 (2H, d, J=8.6 Hz), 7.51 (2H, d, J=8.7 Hz), 7.39 (2H, d, J=8.0 Hz), 7.21 (2H, d, J=8.6 Hz), 3.76 (3H, s), 2.35 (3H, s).
[0222] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=165.58 (CO.sub.2R), 149.26(NHC(O)NH), 143.93, 142.40, 142.37, 136.81, 132.93, 130.49, 129.41, 128.00, 127.46, 124.35, 118.64, 118.16, 51.76(OCH.sub.3), 20.95(CH.sub.3).
[0223] XXIX, C.sub.20H.sub.18N.sub.3O.sub.5S.sub.2, M=479.9, N-(4-chlorphenyl)-4-(3-tosylureido)benzene sulfonamide
[0224] MS (ESI):m/z (%)=478.0(100) [M-H].sup.−, 306.9(18) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 281.1(52) [M-H—Ar.sup.2SO.sub.2NCO].sup.−.
[0225] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=10.86 (1H, s), 10.27 (1H, s), 9.19 (1H, s), 7.90-7.85 (2H, m), 7.70-7.65 (2H, m), 7.53-7.49 (2H, m), 7.40 (2H, d, J=8.1 Hz), 7.29-7.23 (2H, m), 7.11-7.07 (2H, m), 2.35 (3H, s).
[0226] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=149.28 (NHC(O)NH), 143.95, 142.24, 136.84, 136.73, 132.98, 129.43, 129.01, 128.16, 127.96, 127.50, 121.67, 118.59, 20.98(CH.sub.3).
[0227] XXX, C.sub.27H.sub.15N.sub.2O.sub.6S.sub.2, M=579.6, 4-methyl-N-((4-(N-(4-(3-phenylureide)phenyl)sulfamoyl)phenyl)carbamoyl)benzene sulfonamide
[0228] MS (ESI):m/z (%)=578.1(100) [M-H].sup.−, 407.0 (18) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 381.0(4) [M-H—Ar.sup.2SO.sub.2NCO].sup.−.
[0229] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=10.91 (1H, s), 9.43 (2H, d, J=30.4 Hz), 9.22 (1H, s), 8.28 (1H, s), 8.01 (1H, dd, J=8.2, 1.3 Hz), 7.89 (2H, d, J=8.1 Hz), 7.61 (2H, d, J=8.9 Hz), 7.51 (4H, m), 7.43 (2H, d, J=8.1 Hz), 7.29 (2H, t, J=7.8 Hz), 7.16 (1H, ddd, J=7.8, 1.5 Hz), 6.97 (1H, t, J=7.4 Hz), 6.78 (1H, ddd, J=7.9, 1.4 Hz), 6.50 (1H, dd, J=7.9, 1.4 Hz), 2.39 (3H, s).
[0230] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=152.53(NHC(0)NH), 149.26(NHC(O)NH), 143.96, 142.18, 139.72, 136.86, 136.83, 133.00, 129.47, 129.43, 128.71, 128.39, 127.52. 125.17, 121.96, 121.85, 120.99, 118.29, 118.28, 118.26, 20.99 (CH.sub.3).
[0231] XXXI, C.sub.23H.sub.23N.sub.3O.sub.7S.sub.2, M=517.6, ethyl 4-(4-(3-tosylureide)phenyl sulfonamide)benzoate
[0232] MS (ESI):m/z (%)=516.0(100) [M-H].sup.−, 345.0 (12) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 319.0(43) [M-H—Ar.sup.2SO.sub.2NCO].sup.31
[0233] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=10.87 (1H, s), 10.69 (1H, s), 9.20 (1H, s), 7.89-7.84 (2H, m), 7.83-7.79 (2H, m), 7.77-7.73 (2H, m), 7.557.50 (2H, m), 7.39 (2H, d, J=8.1 Hz), 7.25-7.20 (2H, m), 4.22 (2H, q, J=7.1 Hz), 2.34 (3H, s), 1.24 (3H, t, J=7.1 Hz)
[0234] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=165.10 (CO.sub.2R), 149.27(NHC(O)NH), 143.93, 142.41, 142.33, 136.83, 132.95, 130.45, 129.41, 128.03, 127.49, 124.68, 118.64, 118.20, 60.38 (OCH.sub.2CH.sub.3), 20.95(CH.sub.3), 14.07 (OCH.sub.2CH.sub.3).
[0235] XXXII, C.sub.28H.sub.27N.sub.5O.sub.8S.sub.2, M=657.7, N,N′-(((4-(N-phenyl sulfamoyl)-1,3-phenylene)bis(azanediyl))bis(carbonyl))bis(4-methyl benzene sulfonamide)
[0236] MS (ESI):m/z (%)=656.1 (100) [M-H].sup.−, 485.1 (60) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 459.0 (2) [M-H—Ar.sup.2SO.sub.2NCO].sup.−, 314.0 (13) [M-H-2x Ar.sup.2SO.sub.2NH.sub.2].sup.−, 288 (4) [M-H—Ar.sup.2SO.sub.2NCO— Ar.sup.2SO.sub.2NH.sub.2].sup.−.
[0237] .sup.1H NMR (500 MHz, ACN-d.sub.3): δ(ppm)=8.92 (1H, s), 8.64 (1H, s), 8.06 (1H, s), 7.94 (1H, s), 7.88-7.82 (5H, m), 7.59 (1H, d, J=8.8 Hz), 7.38-7.31 (4H, m), 7.15 (1H, dd), 7.14-7.10 (2H, m), 7.02-6.98 (1H, m), 6.98-6.95 (2H, m), 2.39 (3H, s), 2.37 (3H,s)
[0238] .sup.13C NMR (126 MHz, ACN-d.sub.3): δ(ppm)=149.76(NHC(O)NH), 149.61(NHC(O)NH), 146.07, 146.06, 143.80, 137.48, 137.34, 137.29, 137.04, 131.79, 130.66, 130.58, 130.21, 128.68, 128.60, 126.74, 123.08, 122.39, 114.66, 113.28, 21.68(CH.sub.3), 21.65(CH.sub.3).)
[0239] XXXIII, C.sub.32H.sub.28N.sub.6O.sub.10S.sub.4, M=784.8, N.sup.1,N.sup.3-diphenyl-4,6-bis(3-(phenyl sulfonyl)ureide)benzene-1,3-disulfonamide
[0240] MS (ESI):m/z (%)=783.1 (100) [M-H].sup.−, 626.0 (75) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 600.0 (5) [M-H—Ar.sup.2SO.sub.2NCO].sup.−, 469.0 (50) [M-H-2x Ar.sup.2SO.sub.2NH.sub.2].sup.−, 442.9 (8) [M-H—Ar.sup.2SO.sub.2NCO—Ar.sup.2SO.sub.2NH.sub.2].sup.−.
[0241] NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=11.93 (2H, s), 10.45 (2H, s), 8.71 (2H, s), 8.48 (1H, s), 8.15 (1H, s), 7.88-7.84 (4H, m), 7.77-7.71 (2H, m), 7.61-7.55 (4H, m), 7.13-7.07 (4H, m), 7.00-6.92 (6H, m).
[0242] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=148.46(NHC(O)NH), 139.76, 139.36, 135.87, 133.58, 129.17, 129.12, 128.84, 127.41, 125.54, 121.12, 120.98, 119.09.
[0243] XXXIV, C.sub.34H.sub.32N.sub.6O.sub.10S.sub.4, M=812.9, N.sup.1,N.sup.3-diphenyl-4,6-bis(3-tosylureide)benzene-1,3-disulfonamide
[0244] MS (ESI):m/z (%)=811.0(100) [M-H].sup.−, 640.0 (70) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 614.1(8) [M-H—Ar.sup.2SO.sub.2NCO].sup.−.
[0245] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=11.85 (2H, s), 10.44 (2H, s), 8.70 (2H, s), 8.52 (1H, s), 8.15 (1H, s), 7.88 - 7.83 (4H, m), 7.48-7.42 (4H, m), 7.13 - 7.07 (4H, m), 6.99-6.93 (6H, m), 2.43 (6H, s),
[0246] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=148.44(NHC(O)NH), 144.14, 139.81, 136.51, 135.88, 129.54, 129.22, 129.17, 127.49, 125.58, 121.01, 120.92, 119.08, 21.04(CH.sub.3).
[0247] XXXV, C.sub.40H.sub.40N.sub.6O.sub.14S.sub.4, M=957.03, diethyl 4-4′-((4,6-bis(3-tosylureide tosylureide)-1,3-phenylene disulfonyl)bis(azanediyl))dibenzoate
[0248] MS (ESI):m/z (%)=955.1(55) [M-H].sup.−, 784.1 (100) [M-H—Ar.sup.2SO.sub.2NH.sub.2].sup.−, 758.1(7) [M-H—Ar.sup.2SO.sub.2NCO].sup.−, 613.0 (40) [M-H-2x Ar.sup.2SO.sub.2NH.sub.2].sup.−, 587.0 (8) ([M-H—Ar.sup.2SO.sub.2NCO—Ar.sup.2SO.sub.2NH.sub.2].sup.−.
[0249] .sup.1H NMR (500 MHz, DMSO-d.sub.6): δ(ppm)=11.80 (2H, s), 11.06 (2H, s), 8.77 (2H, s), 8.52 (1H, s), 8.28 (1H, s), 7.89-7.81 (4H, m), 7.71-7.65 (4H, m), 7.44-7.39 (4H, m), 7.04-6.98 (4H, m), 4.28 (4H, q, J=7.0 Hz), 2.42 (6H, s), 1.30 (6H, t, J=7.0 Hz).
[0250] .sup.13C NMR (126 MHz, DMSO-d.sub.6): δ(ppm)=164.78(CO.sub.2R), 148.51(NHC(0)NH), 144.16, 140.61, 139.98, 136.43, 130.43, 129.55, 129.21, 127.50, 125.59, 125.53, 121.13, 118.44, 60.52 (OCH.sub.2CH.sub.3), 21.01(CH.sub.3), 14.04 (OCH.sub.2CH.sub.3).
[0251] An aqueous application suspension to form the heat-sensitive color-forming layer of a heat-sensitive recording paper was applied in the laboratory standard using a rode blade to one side of a synthetic base paper (Yupo® FP680) of 63 g/m.sup.2. After drying, a thermic recording sheet was obtained. The application quantity of the heat-sensitive color-forming layer was between 4.0 and 4.5 g/m.sup.2.
[0252] The application of the aqueous application suspension in the production standard to a roll of paper with a base weight of 43 g/m.sup.2 using the curtain-coating method. The viscosity of the aqueous application layer was 450 mPas (according to Brookfield, 100 rpm, 20° C.) (deaerated). Its surface tension was 46 mN/m (statistic ring method). The coating apparatus was arranged inline. The curtain coating method was operated at a speed of 1550 m/min.
[0253] After applying the aqueous application suspension, the drying process of the layered paper backing took place in the usual way. The base weight application of the dried heat-sensitive layer was 4.0-4.5 g/m.sup.2.
[0254] Based on the previously stated specifications, a heat-sensitive recording material or thermal paper was produced, wherein the following recipes of aqueous application suspensions were used to form a compound structure on a supporting substrate and then the further layers, in particular a protective layer, were formed in the typical way, about which greater details need not be provided here.
[0255] Production of the dispersions (each for 1 weight percent) for the application suspensions.
[0256] The aqueous Dispersion A (color former dispersion) is produced by grinding 20 weight percent of 3-N-n-dibutylamine-6-methyl-7-anilinofluoran (ODB-2) with 33 weight percent of a 15% aqueous solution of Ghosenex™ L-3266 (sulfonated polyvinyl alcohol, Nippon Ghosei) in a pearl mill.
[0257] The aqueous Dispersion B (color developer dispersion) is produced by grinding 40 weight percent of the color developer together with 66 weight percent of a 15% aqueous solution of Ghosenex™ L-3266 in the pearl mill.
[0258] The aqueous Dispersion C (sensitizer dispersion) is produced by grinding 40 weight percent of sensitizers with 33 weight percent of a 15% aqueous solution of Ghosenex™ L-3266 in a pearl mill.
[0259] The aqueous Dispersion D (anti-aging agent or stabilizer dispersion) is produced by grinding 12.5 weight percent UU (urea-urethane) with 10 weight percent of a 15% aqueous solution of Ghosenex™ L-3266 in a pearl mill.
[0260] All dispersions obtained by grinding have an average grain size D.sub.(4,3) of 0.80-1.20 μm.
[0261] The Dispersion E (lubricant dispersion) is a 20% zinc stearate dispersion consisting of 9 weight percent Zn-stearate, 1 weight percent Ghosenex™ L-3266 and 40 parts water.
[0262] Pigment P is a 72% coating kaolin suspension (Lustra® S, BASF).
[0263] The Binder consists of a 10% aqueous polyvinyl alcohol solution (Mowiol 28-99, Kuraray Europe).
[0264] The application suspension is produced by mixing the dispersions while stirring according to the quantity specifications in Table 3 taking into consideration the order B, E, C, D, P, A, Binder and brought with water to a solid content of approx. 25%.
[0265] The measurement of the grain size distribution of the application dispersions took place using laser diffraction with a Coulter LS230 device from Beckman Coulter.
TABLE-US-00003 TABLE 3 Summary of the recipes for the application dispersions (weight percent) Recipe Components R1 R2 A 1 1 B 1 1 C 1 1 D 0 1 E 56 56 P 146 126 Binder 138 138
[0266] The heat-sensitive layering suspensions thus obtained were used to produce compound structures of paper backing and thermoreactive layers.
[0267] The thermic recording materials according to Table 3 were evaluated as described below.
(1) The paper whiteness on the coating side was determined according to DIN/ISO 2470 with an Elrepho 3000 spectral photometer (uncertainty of whiteness value measurements ≤50.5%).
(2) Dynamic color thickness:
[0268] The papers (6-cm wide strips) were thermically printed upon using the Atlantek 200 test printer (Atlantek, USA) with a 200-dpi, 560-Ohm Kyocera pressure bar with an applied voltage of 20.6 V and a maximum pulse width of 0.8 ms with a chessboard pattern with 10 energy phases. The image thickness (optical thickness, opt. thickness) was measured with a Macbeth densitometer RD-914, from Gretag, wherein the value “½” corresponds to the the o.t. with an energy level of 0.4 ms and the value “max.” corresponds to the energy level of 0.8 ms. The uncertainty of the o.t. value measurements was estimated at ±0.02 optical thickness units.
(3) Statistic color thickness (start temperature):
[0269] The recording sheet is pressed against a row of temperature-regulated metallic stamps heated to different temperatures with a pressure of 0.2 kg/cm.sup.2 and a contact time of 5 sec (thermal tester TP 3000QM, Maschinenfabrik Hans Rychiger AG, Steffisburg, Switzerland). The image thickness (opt. thickness) of the images produced in this way is measured with a Macbeth densitometer RD-914 from Gretag. The static starting point is by definition the lowest temperature at which an optical thickness of 0.2 is achieved. The precision of the measurement method is ≤±0.5° C.).
(4) Durability test of the printed image:
(4.1) Plasticizer durability:
[0270] A plasticizer-containing plastic wrap (PVC wrap with 20-25% dioctyl adipate) was brought into contact with the thermic recording paper sample dynamically recorded according to the method of (2), avoiding folding and air bubbles, wrapped into a roll and stored for 16 hours. A sample is stored at room temperature (20-22° C.), a second at 40° C. After removing the plastic, the image thickness (opt. thickness) was measured and related to the corresponding image thickness values before the plasticizer action according to the formula (IV).
(4.2) Durability vis-à-vis adhesive:
[0271] A strip of Tesa transparent self-adhesive tape (tesafilm® crystal-clear, #57315) and separately a strip of Tesa packaging tape (#04204) were each adhered to the thermic recording paper sample dynamically recorded according to the method of (2), avoiding folding and air bubbles. After 24-hour storage at room temperature (20-22° C.), the image thickness (opt. thickness) was measured—through the respective tape—and related to the analogously determined image thickness values of the freshly adhered pattern according to the formula (IV). The value thus obtained corresponds to the % decrease in the original image intensity.
[0272] The mean variation in the % values calculated according to (IV) are ±2 percent points.
[0273] LC-MS: Device type HPLC: Agilent 1200 series, column: Synergi 4μ Fusion-RP80A (250×4.6 mm, Phenomenex Inc.).
[0274] Eluent A: acetonitrile/water±0.1% formic acid (60/40, v/v).
[0275] Eluent B: acetonitrile+0.1% formic acid.
[0276] Gradient: 0.0 min 100% A.fwdarw.8.0 min 100% A (0.4 ml/min).fwdarw.10.0 min 100% A (1.0 ml/min).fwdarw.11 min 20% A (1.0 ml/min).fwdarw.20.0 min 20% A (1.0 ml/min).fwdarw.22.0 min 100% A (0.4 ml/min).
[0277] DAD Detector G1315C (Agilent), scanned wavelength range 200-400 nm.
[0278] Single Quadrupole Mass Spectrometer, Type 6120B (Agilent) with electrospray ionization (ESI), positive and negative ion mode, scanned mass range 100-1000 m/z.
[0279] Table 4 summarizes the evaluation of the manufactured recording materials.
[0280] Table 5 presents, for chosen developer substances of the compound class according to the invention, possibilities, by way of example, to improve the image stability with anti-aging agents without hindering other performance properties.
TABLE-US-00004 TABLE 4 Evaluation of the paper pattern with recipe R1 Background Durability of the printed image whiteness Plasticizer (%) Static foil, 16 h, 1 7 Opt. starting TESA, 24 h, (at (at max. day day thickness point max. o.t.) o.t.) No. Developer R.T. R.T. ½ Max. (° C.) #57315 #04204 RT 40° 1 I 87 87 1.36 1.35 80.5 −43 −70 −7 −40 2 III 89 89 1.26 1.32 85.5 −38 −67 −9 −76 3 IV 89 88 1.25 1.27 81.5 −37 −66 −6 −34 4 VII 86 86 1.28 1.31 76.5 −36 −60 −5 −27 5 X 89 90 1.25 1.27 85.0 −45 −70 −9 −63 6 XII 89 89 1.27 1.29 81.0 −37 −60 −6 −40 7 XV 89 89 1.30 1.30 81.5 −25 −48 −5 −20 8 XVIII 88 88 1.32 1.31 78.0 −37 −57 −8 −42 9 XXIII 89 89 1.25 1.29 81.5 −26 −50 −5 −26 10 XXXII 87 87 1.15 1.20 80.0 −14 −13 −4 −10 11 XXXV 87 87 1.23 1.26 82.5 −6 −5 −2 −9 12 FE A* 88 88 1.26 1.29 76.5 −32 −57 −5 −31 13 FE B* 89 89 1.25 1.28 85.5 −50 −70 −15 −91 *non-phenolic developers of the prior art
TABLE-US-00005 TABLE 5 Evaluation of the paper pattern without/with anti-aging agents (AAA) with recipe R2 Background Durability of the printed image whiteness Plasticizer (%) Static foil, 16 h, 1 7 Opt. starting TESA, 24 h, (at (at max. day day thickness point max. o.t.) o.t.) No. Developer R.T. R.T. ½ Max. (° C.) #57315 #04204 RT 40° 14 II 89 89 1.21 1.28 86 −44 −75 −15 −67 15 II/AS 90 88 1.21 1.21 83 −32 −59 −4 −18 16 IX 89 89 1.25 1.21 81 −53 −78 −6 −47 17 IX/AS 82 87 1.21 1.22 80 −29 −54 −2 −20 18 XIV 90 90 0.54 0.55 81 −49 −69 −85 −87 19 XIV/AS 88 90 0.84 0.95 78 −43 −45 −13 −40 20 XXVI 78 78 1.20 1.31 81 −18 −41 −4 −19 21 XXVI/AS 87 82 1.24 1.24 81 −16 −37 −3 −9
[0281] The heat-sensitive recording material of the present invention exhibits in particular the following advantageous properties:
[0282] (1) The surface whiteness of the heat-sensitive recording papers according to the invention is better than or comparable to the reference sample with color developers of the prior art both when fresh and after storage.
[0283] (2) The recorded image of the heat-sensitive papers according to the invention with the color developers according to the invention have a print thickness (optical thickness values “½” and “max”), which is in no way inferior to the color developers of the reference sample.
[0284] (3) The temperature starting at which a visually noticeable graying of the heat-sensitive recording materials according to the invention appears (static starting point) is comparable to or higher than in known heat-sensitive recording materials and meets the requirements for marketable heat-sensitive recording materials. A higher starting point is necessary for labeling applications in the field of groceries/medicine (thermic laminability, microwave and sterilizer suitability).
[0285] (4) The printed image (max. opt. thickness values from Table 4) is hardly faded after the action of hydrophobic agents (adhesives, plasticizers). The image durability is better than or comparable to when using known non-phenolic color developers.
[0286] (5) With typical anti-aging agents, if necessary, the image durability vis-à-vis hydrophobic agents of the papers according to the invention may be increased without disadvantages with regards to poor surface whiteness or low starting temperature (Table 5).
[0287] (6) With the production method according to the invention, a heat-sensitive recording material of top quality in all important application-specific regards may be produced in economically advantageous conditions.