Heat-sensitive recording material

Abstract

The invention relates to a compound of the formula (I) Ar(NHSO.sub.2Ar.sup.1)l(SO.sub.2NHAr.sup.1).sub.m(NHC(O)NHAr.sup.2).sub.n (I), wherein l and m independently of one another are 0, 1, 2, 3, and/or 4 and the sum of l+m is equal to or more than 1, n is 2, 3, 4, or 5, Ar is a benzol group which is substituted (l+m+n) times, Ar.sup.1 is an unsubstituted or substituted aromatic group, and Ar.sup.2 is an unsubstituted or substituted phenyl group or a benzoyl group. The invention also relates to a heat-sensitive recording material comprising a carrier substrate and a heat-sensitive color-forming layer which contains at least one color former and at least said color developer.

Claims

1. A compound of formula (I), Ar(NHSO.sub.2A.sup.1).sub.l(SO.sub.2NHAr.sup.1).sub.m(NHC(O)NHAr.sup.2).sub.n(I), wherein l and m independently of one another are 0, 1, 2, 3 and/or 4 and the sum of l+m is equal to or greater than 1, n is 2, 3, 4 or 5, Ar is a benzene ring substituted (l+m+n) times, Ar.sup.1 is an unsubstituted or substituted aromatic group, and Ar.sup.2 is an unsubstituted or substituted phenyl group or an unsubstituted or substituted benzoyl group.

2. The compound according to claim 1, wherein l is 0 or 1.

3. The compound according to claim 1, wherein m is 0, 1 or 2.

4. The compound according to claim 1, wherein n is 2.

5. The compound according to claim 1, wherein l is 1, m is 0, and n is 2.

6. The compound according to claim 1, wherein l is 0, m 1, and n is 2.

7. The compound according to claim 1, wherein l is 0, m is 2, and n is 2.

8. The compound according to claim 1, wherein Ar is a benzene ring substituted 3 or 4 times.

9. The compound according to claim 1 wherein Ar.sup.1 is an unsubstituted or substituted phenyl group.

10. The compound according to claim 1, wherein Ar.sup.1 is a monosubstituted phenyl group substituted with a C.sub.1-C.sub.5 alkyl, an alkenyl, an alkynyl, a benzyl, an RO, a halogen, formyl, an ROC, an RO.sub.2C, a CN, NO.sub.2, an R—SO.sub.2O, are RO—SO.sub.2, R—NH—S.sub.02, an R—SO.sub.2—NH, an R—NH—CO—NH, an R—SO.sub.2—NH—CO—NH, n R—NH—CO—NH—R or an R—CO—NH group, wherein R is a C.sub.1-C.sub.5 alkyl, an alkenyl, an alkynyl, a phenyl, a tolyl or a benzyl group.

11. The compound according to claim 10, wherein the monosubstituted phenyl group is substituted with a 4-C.sub.1C.sub.5 alkyl, a 4-RO or a 4-(RO.sub.2C) group, wherein R is a C.sub.1 to C.sub.5 alkyl group.

12. The compound according to claim 10, wherein Ar.sup.2 is a substituted phenyl group which is substituted with C.sub.1-C.sub.4 alkyl, a halogen, a CX.sub.3, formyl, an ROC, an RO.sub.2C, a CN, an NO.sub.2 or an RO group, wherein X is a halogen group and A is a C.sub.1-C.sub.5 alkyl group, a phenyl group or a tolyl group.

13. A heat-sensitive recording material comprising a carrier substrate, at least one colour former, and at least one heat-sensitive colour-forming layer containing at least one phenol-free colour developer, wherein the at least one phenol-free colour developer is a compound of formula (I) according to claim 1 which contains no phenol substituents.

14. The heat-sensitive recording material according to claim 13, wherein the at least one colour former is a dye of the triphenylmethane type, of the fluorane type, of the azaphthalide type and/or of the fluorene type.

15. The heat-sensitive recording material according to claim 13, wherein, besides the compound of formula (l), one or more further non-phenolic colour developer(s) is/are present.

16. The heat-sensitive recording material according to claim 13, wherein the compound of formula (I) is present in an amount of from approximately 3 to approximately 35% by weight, in relation to the total solid content of the heat-sensitive layer.

17. The compound according to claim 1, wherein Ar is a benzene ring substituted 3 times.

18. The compound according to claim 1, wherein Ar.sup.1 is a monosubstituted phenyl group.

19. The heat-sensitive recording material according to claim 13, wherein the compound of formula (I) is present in an amount of from approximately 10 to 25% by weight, in relation to the total solid content of the heat-sensitive layer.

20. The compound according to claim 1, wherein Ar.sup.1 is a 4-alkylester phenyl group.

Description

EXAMPLES

(1) Production of the compounds of formula (I) according to the invention.

(2) The compounds I to XIX (Table 2) were produced as follows:

(3) Step A1—Preparation of the Sulfonamides

(4) A solution of 10 mmol of the corresponding sulfonyl chloride in 75 mL dichloromethane was added dropwise to a solution of 20 mmol aromatic diamine and 20 mmol pyridine in 125 mL dichloromethane at 0° C. under stirring. The reaction solution was stirred for 16 hours at room temperature, before 100 mL water were added. The organic phase was separated and mixed with 250 mL of a 5% aqueous sodium hydroxide solution. The aqueous phase was washed with 100 mL dichloromethane and made neutral by adding 25% hydrochloric acid. After multiple extractions with 100 mL dichloromethane, the combined organic phases were washed with 200 mL water and dried over magnesium sulfate. Following removal of the solvent in a vacuum the sulfonamides were used in step B without further purification.

(5) Step A2—Preparation of the Sulfonamides

(6) A solution of 80 mmol of the corresponding sulfonyl chloride in 150 mL dichloromethane was added dropwise to a solution of 80 mmol aromatic diamine and 240 mmol potassium carbonate in 500 mL dichloromethane at room temperature under stirring. The reaction mixture was refluxed for six hours, and then 300 mL ethyl acetate and 300 mL water were added. The aqueous phase was made acidic by adding 25% hydrochloric acid. The phases were separated. After multiple extractions of the aqueous phase with 200 mL ethyl acetate, the combined organic phases were washed with 200 mL water and dried over magnesium sulfate. Following removal of the solvent in a vacuum the sulfonamide remained as a solid. The sulfonamides were used in step B without further purification.

(7) Step A3—Preparation of the Sulfonamides

(8) A solution of 25.0 mmol of aromatic amine in 35 mL abs. THF was added dropwise to a solution of 27.5 mmol sodium hydride (60% in oil) in 25 mL abs. THF at 0° C. under stirring and protective gas atmosphere. After stirring for two hours at room temperature, a solution of 25.0 mmol of the corresponding sulfonyl chloride in 10 mL abs. THF was added dropwise at 0° C. under stirring. The reaction solution was stirred for 40 hours at room temperature, and then 100 mL water and 100 mL dichloromethane were added. The aqueous phase was made alkaline by adding 5% aqueous sodium hydroxide solution. The phases were separated. The aqueous phase was washed with 100 mL dichloromethane and was made neutral by adding 15% hydrochloric acid. After multiple extractions with 100 mL dichloromethane, the combined organic phases were washed with 200 mL water and dried over magnesium sulfate. Following removal of the solvent in a vacuum the sulfonamide remained as a solid. The sulfonamides were used in step B without further purification.

(9) Step A4—Preparation of the Sulfonamides

(10) 50 mmol of the corresponding sulfonyl chloride were added in portions to a mixture of 55 mmol aromatic amine and 50 mmol pyridine under stirring. The mixture was heated briefly (5-10 min) to 95-100° C., cooled, and rubbed with 100-150 mL hydrochloric acid (2 mol/L). The precipitating sulphonamide was filtered off, washed neutral with water, and dried. The sulfonamides were used in step B without further purification.

(11) Step B—Reduction of the Nitro Group to Give the Primary Amine

(12) 28.0 mmol (products from step A1) or 56.0 mmol (products from steps A2/A3/A4) SnCl.sub.2.2H.sub.2O were added to a solution of 8.0 mmol of the product from step A1/A2/A3/A4 in 140 mL ethyl acetate at room temperature under stirring. The reaction solution was refluxed. The course of the reaction was monitored by means of thin-film chromatography (eluents: cyclohexane/ethyl acetate 1:1). Once the reaction was complete (approximately 2-3 h), the mixture was diluted with 70 mL ethyl acetate, a 10% aqueous potassium carbonate solution was added, and the mixture was stirred for 30 min at room temperature. The Sn compounds were filtered off and in the filtrate the aqueous phase was separated from the organic phase. The organic phase was washed with 100 ml (2×) of a saturated aqueous sodium chloride solution and dried over magnesium sulfate. Following removal of the solvent in a vacuum, purification was performed by recrystallisation from dichloromethane and a few drops of n-hexane.

(13) Step C—Preparation of the Urea Compounds

(14) A solution of 14.0 mmol of the corresponding isocyanate in 10 mL dichloromethane (I-XVIII) or ethyl acetate (XIX) was added dropwise to a solution of 7.0 mmol of the product from step B in dichloromethane (I-XVIII) or ethyl acetate (XIX) (20-40 mL) at room temperature under stirring. The reaction was monitored by means of thin-film chromatography (eluents: cyclohexane/ethyl acetate 1:1). Once the reaction was complete, the precipitated product was filtered off, washed with dichloromethane/ethyl acetate, and dried in a vacuum. In some cases the reaction solution was concentrated in the vacuum and the crystallisation was initiated by adding a few drops of n-hexane.

(15) The compounds I-II (Table 2) were prepared starting from 2,6-dinitroaniline, which was firstly converted into 1,2-diamino-3-nitrobenzene (reaction scheme 2, V. Milata, J. Saloň, Org. Prep. Proceed. Int., 31 (3), 347 (1999)) and finally was converted into the end product in accordance with the general provisions of steps A1, B and C.

(16) The compounds III-XVI (Table 2) were prepared starting from 2,6-dinitroaniline (III), 4-nitro-1,2-phenylenediamine (IV), 2,6-dinitroaniline (V) and 2-nitro-1,4-phenylenediamine (VI-XVI) were prepared in accordance with the general provisions of steps A1 (IV, VI-XVI), A2 (III), A3 (V), B (III-XVI) and C (III-XVI).

(17) The compounds XVII-XVIII (Table 2) were prepared starting from 2,4-dinitrosulfonylchloride in accordance with the general provisions of steps A4, B and C.

(18) The compound XIX (Table 2) was prepared starting from 1,3-phenylenediamine-dihydrochloride, which was firstly converted into 4,6-diamino-1,3-benzenedisulfonyl chloride (reaction scheme 3, G. Barnikow, K. Krüger, G. Hilgetag, Z. Chem., 6(7), 262 (1966)) and finally was converted into the end product in accordance with the general provisions of steps A4 and C.

(19) The starting compounds are commercially available.

(20) TABLE-US-00002 TABLE 2 Compilation of selected compounds of formula (I) Ar Ar.sup.1 Ar.sup.2 l m n I benzene-1,2,3-triyl 4-CH.sub.3—C.sub.6H.sub.4 C.sub.6H.sub.5 1 0 2 II benzene-1,2,3-triyl 4-CH.sub.3—C.sub.6H.sub.4 4-(CO—CH.sub.3)—C.sub.6H.sub.4 1 0 2 III benzene-1,2,3-triyl 4-CH.sub.3—C.sub.6H.sub.4 C.sub.6H.sub.5 1 0 2 IV benzene-1,2,3-triyl 4-CH.sub.3—C.sub.6H.sub.4 C.sub.6H.sub.5 1 0 2 V benzene-1,2,3-triyl 4-CH.sub.3—C.sub.6H.sub.4 C.sub.6H.sub.5 1 0 2 VI benzene-1,2,3-triyl C.sub.6H.sub.5 C.sub.6H.sub.5 1 0 2 VII benzene-1,2,3-triyl 4-CH.sub.3—C.sub.6H.sub.4 C.sub.6H.sub.5 1 0 2 VIII benzene-1,2,3-triyl 4-Cl—C.sub.6H.sub.4 C.sub.6H.sub.5 1 0 2 IX benzene-1,2,3-triyl 4-OCH.sub.3C.sub.6H.sub.4 C.sub.6H.sub.5 1 0 2 X benzene-1,2,3-triyl 4-CH.sub.3—C.sub.6H.sub.4 4-CH.sub.3—C.sub.6H.sub.4 1 0 2 XI benzene-1,2,3-triyl 4-CH.sub.3—C.sub.6H.sub.4 4-OCH.sub.3—C.sub.6H.sub.4 1 0 2 XII benzene-1,2,3-triyl 4-CH.sub.3—C.sub.6H.sub.4 4-OC.sub.6H.sub.5—C.sub.6H.sub.4 1 0 2 XIII benzene-1,2,3-triyl 4-CH.sub.3—C.sub.6H.sub.4 4-Cl—C.sub.6H.sub.4 1 0 2 XIV benzene-1,2,3-triyl 4-CH.sub.3—C.sub.6H.sub.4 4 (CO—CH.sub.3)—C.sub.6H.sub.4 1 0 2 XV benzene-1,2,3-triyl 4-CH.sub.3—C.sub.6H.sub.4 2-CF.sub.3—C.sub.6H.sub.4 1 0 2 XVI benzene-1,2,3-triyl 4-CH.sub.3—C.sub.6H.sub.4 CO—C.sub.6H.sub.4 1 0 2 XVII benzene-1,2,3-triyl C.sub.6H.sub.5 C.sub.6H.sub.5 0 1 2 XVIII benzene-1,2,3-triyl 4-(CO.sub.2C.sub.2H.sub.5)—C.sub.6H.sub.5 C.sub.6H.sub.5 0 1 2 XIX benzene-1,2,3-tetryl C.sub.6H.sub.5 C.sub.6H.sub.5 0 2 2

(21) Analytical data:

(22) I, C.sub.27H.sub.25N.sub.3O.sub.4S, M=515.6, N-(2,3-bis(3-phenylureide)phenyl)tosylamide

(23) MS (ESI): m/z (%)=514.0 (76) [M−H]−, 395.0 (16) [M−H—Ar.sup.2NCO]−.

(24) .sup.1H-NMR (500 MHz, DMSO-d.sub.6): δ (ppm)=9.47 (1H, s), 9.34 (1H, s), 9.23 (1H, s), 8.06 (1H, s), 7.80-7.78 (1H, m), 7.70 (1H, s), 7.64-7.63 (2H, m), 7.54-7.52 (2H, m), 7.48-7.46 (2H, m), 7.33-7.25 (6H, m), 7.09-7.05 (1H, m), 7.01-6.98 (1H, m), 6.97-6.94 (1H, m), 6.63-6.61 (1H, m), 2.33 (3H, s).

(25) .sup.13C-NMR (126 MHz, DMSO-d.sub.6): δ (ppm)=153.66 (NHCONH), 152.61 (NHCONH), 143.14, 139.89, 139.73, 136.92, 136.81, 132.89, 129.53, 128.69, 128.68, 126.76, 125.85, 124.38, 121.80, 121.76, 119.98, 119.17, 118.28, 118.22, 20.95 (CH.sub.3).

(26) II, C.sub.31H.sub.29N.sub.5O.sub.6S, M=599.7, N-(2,3-bis(3-(4-acetylphenyl)ureido)phenyl)tosylamide

(27) MS (ESI): m/z (%)=598.1 (100) [M−H]−.

(28) .sup.1H-NMR (500 MHz, DMSO-d.sub.6): δ (ppm)=9.74 (1H, s), 9.65 (1H, s), 9.52 (1H, s), 8.14 (1H, s), 7.95-7.94 (2H, m), 7.90-7.88 (2H, m), 7.80-7.78 (2H, m), 7.64-7.62 (4H, m), 7.58-7.57 (2H, m), 7.32-7.31 (2H, m), 7.11-7.08 (1H, m), 6.62-6.61 (1H, m), 2.53 (3H, s), 2.50 (3H, s), 2.33 (3H, s).

(29) .sup.13C-NMR (126 MHz, DMSO-d.sub.6): δ (ppm)=196.17 (CO{umlaut over (C)}H.sub.3), 196.13 (CO{umlaut over (C)}H.sub.3), 153.19 (NH{umlaut over (C)}ONH), 152.20 (NH{umlaut over (C)}ONH), 144.50, 144.28, 143.14, 136.81, 136.61, 133.13, 130.46, 130.41, 129.52, 129.52, 129.50, 126.75, 126.19, 124.13, 120.00, 119.42, 117.16, 117.16, 26.21 ({umlaut over (C)}H.sub.3), 26.18 ({umlaut over (C)}H.sub.3), 20.91 ({umlaut over (C)}H.sub.3).

(30) III, C.sub.27H.sub.25N.sub.5O.sub.4S, M=515.6, N-(2,4-bis(3-phenylureido)phenyl)tosylamide

(31) MS (ESI): m/z (%)=514.1 (100) [M−H]−

(32) .sup.1H-NMR (500 MHz, DMSO-d.sub.6): δ (ppm)=9.54 (1H, s), 9.27 (1H, s), 8.78 (1H, s), 8.53 (1H, s), 8.28 (1H, s), 8.15 (1H, d, J=2.2 Hz), 7.61-7.60 (2H, m), 7.53-7.52 (2H, m), 7.46-7.44 (2H m), 7.36-7.34 (2H, m), 7.33-7.30 (2H, m), 7.29-7.26 (2H, m), 7.08 (1H, dd, 8.7, 2.2 Hz), 7.01-6.95 (2H, m), 6.39 (1H, d, 8.6 Hz), 2.34 (3H, s).

(33) .sup.13C-NMR (126 MHz, DMSO-dd: δ (ppm)=152.35 (NH{umlaut over (C)}ONH), 152.31 (NH{umlaut over (C)}ONH), 143.16, 139.84, 139.54, 139.23, 137.78, 136.48, 129.43, 128.78, 128.74, 128.15, 127.26, 121.87, 121.84, 118.38, 118.19, 118.17, 111.23, 109.79, 20.97 ({umlaut over (C)}H.sub.3).

(34) IV, C.sub.27H.sub.25N.sub.5O.sub.4S, M=515.6, N-(2,5-bis(3-phenylureido)phenyl)tosylamide

(35) MS (ESI): m/z (%)=514.0 (100) [M−H].sup.−

(36) .sup.1H-NMR (500 MHz, DMSO-d.sub.6): δ (ppm)=9.47 (1H, s), 9.23 (1H, s), 8.54 (1H, s), 8.49 (1H, s), 8.06 (1H, s), 7.73 (1H, d, J=8.7 Hz), 7.65-7.63 (2H, m), 7.50-7.48 (2H, m), 7.45-7.43 (2H, m), 7.34-7.26 (7H, m), 7.01 (1H, d, 3=2.2 Hz), 6.99-6.95 (2H, m), 2.31 (3H, s).

(37) .sup.13C-NMR (126 MHz, DMSO-d.sub.6): δ (ppm)=152.84 (NH{umlaut over (C)}ONH), 152.25 (NH{umlaut over (C)}ONH), 143.15, 139.92, 139.65, 136.60, 134.86, 129.68, 129.49, 128.73, 128.72, 127.01, 126.78, 122.72, 121.76, 121.70, 118.16, 118.12, 117.01, 116.51, 20.97 ({umlaut over (C)}H.sub.3).

(38) V, C.sub.27H.sub.25N.sub.5O.sub.4S, M=515.6, N-(2,6-bis(3-phenylureido)phenyl)tosylamide

(39) MS (ESI): m/z (%)=514.1 (100) [M−H].sup.−.

(40) .sup.1H-NMR (500 MHz, DMSO-d.sub.6): δ (ppm)=8.92 (2H, s), 8.90 (1H, s), 7.96 (2H, s), 7.44-7.41 (8H, m), 7.31-7.28 (4H, m), 7.22-7.18 (1H, m), 7.13-7.11 (2H, m), 7.00-6.97 (2H, m), 2.00 (3H, s).

(41) .sup.13C-NMR (126 MHz, DMSO-d.sub.6): δ (ppm)=152.59 (NH{umlaut over (C)}ONH), 143.70, 139.66, 137.95, 136.65, 129.51, 128.98, 128.40, 126.90, 122.26, 118.59, 116.47, 116.36, 20.96 ({umlaut over (C)}H.sub.3).

(42) VI, C.sub.26H.sub.23N.sub.5O.sub.4S, M=501.6, N-(3,4-bis(3-phenylureido)phenyl)benzenesulfonamide

(43) MS (ESI):m/z (%)=500.1 (100) [M−H].sup.−.

(44) .sup.1H-NMR (500 MHz, DMSO-d.sub.6): δ (ppm)=10.24 (1H, s), 9.11 (1H, s), 8.96 (1H, s), 8.09 (1H, s), 7.89 (1H, s), 7.85-7.84 (2H, m), 7.65-7.55 (4H, m), 7.50-7.47 (4H, m), 7.36 (1H, d, J=8.6 Hz), 7.31-7.25 (4H, m), 7.00-6.94 (2H, m), 6.85 (1H, dd, J=8.4, 1.4 Hz).

(45) .sup.13C-NMR (126 MHz, DMSO-d.sub.6): δ (ppm)=153.41 (NH{umlaut over (C)}ONH), 152.79 (NH{umlaut over (C)}ONH), 139.86, 139.73, 139.71, 134.15, 132.99, 132.82, 129.21, 128.83, 128.76, 126.75, 126.40, 125.54, 121.92, 121.76, 118.22, 118.14, 115.35, 114.87.

(46) VII, C.sub.27H.sub.25N.sub.5O.sub.4S, M=515.6, N-(3,4-bis(3-phenylureido)phenyl)tosylamide

(47) MS (ESI):m/z (%)=514.1 (88) [M−H].sup.−.

(48) .sup.1H-NMR (500 MHz, DMSO-d.sub.6): δ (ppm)=10.16 (1H, s), 9.11 (1H, s), 8.96 (1H, s), 8.09 (1H, s), 7.88 (1H, s), 7.73-7.72 (2H, m), 7.63 (1H, d, J=2.4 Hz), 7.50-7.46 (4H, m), 7.36-7.33 (3H, m), 7.31-7.25 (4H, m), 7.00-6.94 (2H, m), 6.84 (1H, dd, J=8.7, 2.5 Hz), 2.34 (3H, s).

(49) .sup.13C-NMR (126 MHz, DMSO-d.sub.6): δ (ppm)=153.42 (NH{umlaut over (C)}ONH), 152.79 (NH{umlaut over (C)}ONH), 143.17, 139.87, 139.72, 136.86, 134.34, 133.00, 129.66, 128.83, 128.76, 126.81, 126.23, 125.57, 121.91, 121.75, 118.22, 118.13, 115.13, 114.64, 20.98 ({umlaut over (C)}H.sub.3).

(50) VIII, C.sub.26H.sub.22C1N.sub.5O.sub.4S, M=536.0, N-(3,4-bis(3-phenylureido)phenyl)-4-chlorobenzene-sulfonamide

(51) MS (ESI):m/z (%)=534.1 (100) [M−H].sup.−.

(52) .sup.1H-NMR (500 MHz, DMSO-d.sub.6): δ (ppm)=10.28 (1H, s), 9.10 (1H, s), 8.95 (1H, s), 8.09 (1H, s), 7.90 (1H, s), 7.84-7.82 (2H, m), 7.65-7.63 (2H, m), 7.62 (1H, d, J=2.5 Hz), 7.50-7.47 (4H, m), 7.39 (1H, d, J=8.7 Hz), 7.31-7.25 (4H, m), 6.99-6.94 (2H, m), 6.84 (1H, dd, J=8.7, 2.5 Hz).

(53) .sup.13C-NMR (126 MHz, DMSO-d.sub.6): δ (ppm)=153.36 (NH{umlaut over (C)}ONH), 152.77 (NH{umlaut over (C)}ONH), 139.82, 139.68, 138.50, 137.76, 133.71, 132.95, 129.37, 128.78, 128.72, 128.67, 126.70, 125.48, 121.89, 121.75, 118.22, 118.15, 115.72, 115.23.

(54) IX, C.sub.27H.sub.25N.sub.5O.sub.5S, M=531.6, N-(3,4-bis(3-phenylureido)phenyl)-4-methoxybenzene-sulfonamide

(55) MS (ESI): m/z (%)=530.1 (100) [M−H].sup.−

(56) .sup.1H-NMR (500 MHz, DMSO-d.sub.6): δ (ppm)=10.08 (1H, s), 9.10 (1H, s), 8.96 (1H, s), 8.08 (1H, s), 7.88 (1H, s), 7.78-7.76 (2H, m), 7.62-7.62 (1H, m), 7.50-7.46 (4H, m), 7.35 (1H, d, J=8.6 Hz), 7.31-7.25 (4H, m), 7.08-7.07 (2H, m), 7.00-6.94 (2H, m), 6.85-6.83 (1H, m), 3.80 (3H, s).

(57) .sup.13C-NMR (126 MHz, DMSO-d.sub.6): δ (ppm)=162.40, 153.42 (NH{umlaut over (C)}ONH), 152.79 (NH{umlaut over (C)}ONH), 139.87, 139.72, 134.44, 132.97, 131.35, 128.96, 128.82, 128.75, 126.19, 125.54, 121.90, 121.74, 118.21, 118.13, 115.14, 114.66, 114.35, 55.59 (O{umlaut over (C)}H.sub.3)

(58) X, C.sub.29H.sub.29N.sub.5O.sub.4S, M=543.6, N-(3,4-bis(3-(4-tolyl)ureido)phenyl)tosylamide

(59) MS (ESI): m/z (%)=542.2 (38) [M−H].sup.−.

(60) .sup.1H-NMR (500 MHz, DMSO-d.sub.6): δ (ppm)=10.13 (1H, s), 8.99 (1H, s), 8.84 (1H, s), 8.03 (1H, s), 7.82 (1H, s), 7.72-7.70 (2H, m), 7.61 (1H, d, J=2.2 Hz), 7.37-7.30 (7H, m), 7.11-7.06 (4H, m), 6.81 (1H, dd, J=8.7, 2.2 Hz), 2.34 (3H, s), 2.24 (3H, s), 2.23 (3H, s).

(61) .sup.13C-NMR (126 MHz, DMSO-d.sub.6): δ (ppm)=153.43 (NHCONH), 152.80 (NHCONH), 143.14, 137.29, 137.13, 136.86, 134.19, 132.97, 130.72, 130.52, 129.64, 129.21, 129.15, 126.80, 126.27, 125.44, 118.31, 118.22, 115.05, 114.62, 20.97 (CH.sub.3), 20.34 (CH.sub.3), 20.33 (CH.sub.3).

(62) XI, C.sub.29H.sub.29N.sub.5O.sub.6S, M=575.6, bi-(3,4-bis(3-(4-methoxyphenyl)ureido)phenyl)tosylamide

(63) MS (ESI): m/z (%)=574.2 (80) [M−H].sup.−.

(64) .sup.1H-NMR (500 MHz, DMSO-d.sub.6): δ (ppm)=10.12 (1H, s), 8.91 (1H, s), 8.76 (1H, s), 8.00 (1H, s), 7.79 (1H, s), 7.72-7.70 (2H, m), 7.60 (1H, d, J=2.5 Hz), 7.39-7.30 (7H, m), 6.90-6.84 (4H, m), 6.81 (1H, dd, J=8.7, 2.5 Hz), 3.71 (3H, s), 3.70 (3H, s), 2.34 (3H, s).

(65) .sup.13C-NMR (126 MHz, DMSO-d.sub.6): δ (ppm)=154.52 (NHCONH), 154.40 (NHCONH), 153.59, 152.97, 143.14, 136.87, 134.15, 133.06, 132.91, 132.74, 129.64, 126.80, 126.40, 125.43, 120.03, 119.94, 115.02, 114.65, 114.03, 113.96, 55.16 (OCH.sub.3), 55.13 (OCH.sub.3), 20.97 (CH.sub.3).

(66) XII, C.sub.39H.sub.33N.sub.5O.sub.6S, M=699.8, N-(3,4-bis(3-(4-phenoxyphenyl)ureido)phenyl)tosylamide

(67) MS (ESI): m/z (%)=700.2 (100) [M+H].sup.+, 515.1 (63) [M+H—Ar.sup.2NH.sub.2].sup.+, 489.2 (43) [M+H—Ar.sup.2NH.sub.2—Ar.sup.2NCO].sup.+.

(68) .sup.1H-NMR (500 MHz, DMSO-d0:6 (ppm)=10.14 (1H, s), 9.12 (1H, s), 8.98 (1H, s), 8.07 (1H, s), 7.87 (1H, s), 7.73-7.72 (2H, m), 7.62 (1H, d, J=2.4 Hz), 7.52-7.48 (4H, m), 7.38-7.33 (7H, m), 7.10-7.06 (2H, m), 7.01-6.94 (8H, m), 6.84 (1H, dd, J=8.7, 2.5 Hz), 2.34 (3H, s).

(69) .sup.13C-NMR (126 MHz, DMSO-d.sub.6): δ (ppm)=157.61, 157.58, 153.47 (NHCONH), 152.86 (NHCONH), 150.77, 150.60, 143.09, 136.87, 135.84, 135.65, 134.32, 132.99, 129.85, 129.83, 129.59, 126.76, 126.30, 125.53, 122.75, 122.70, 119.94, 119.86, 119.69, 119.67, 117.65, 117.57, 115.16, 114.69, 20.93 (CH.sub.3).

(70) XIII, C.sub.27H.sub.23Cl.sub.2N.sub.5O.sub.4S, M=584.5, N″-(3,4-bis(3-(4-chiorophenyl)ureido)phenyl)tosylamide

(71) MS (ESI): m/z (%)=582.1 (54) [M−H].sup.−.

(72) .sup.1H-NMR (500 MHz, DMSO-d.sub.6): δ (ppm)=10.16 (1H, s), 9.24 (1H, s), 9.11 (1H, s), 8.10 (1H, s), 7.89 (1H, s), 7.72-7.70 (2H, m), 7.60 (1H, d, J=2.2 Hz), 7.51-7.48 (4H, m), 7.35-7.29 (7H, m), 6.83 (1H, dd, J=8.7, 2.3 Hz), 2.34 (3H, s).

(73) .sup.13C-NMR (126 MHz, DMSO-d.sub.6): δ (ppm)=153.30 (NHCONH), 152.67 (NHCONH), 143.17, 138.86, 138.69, 136.82, 134.51, 132.93, 129.64, 128.65, 128.58, 126.79, 126.09, 125.74, 125.45, 125.27, 119.72, 119.64, 115.23, 114.62, 20.97 (CH.sub.3).

(74) XIV, C.sub.31H.sub.29N.sub.5O.sub.6S, M=599.7, N-(3,4-bis(3-(4-acetylphenyl)ureido)phenyl)tosylamide

(75) MS (ESI): m/z (%)=598.1 (82) [M−H].sup.−, 463.1 (23) [M−H—Ar.sup.2NH.sub.2].sup.−, 302.0 (11) [M−H—Ar.sup.2NH.sub.2—Ar.sup.2NCO].sup.−.

(76) .sup.1H-NMR (500 MHz, DMSO-d.sub.6): δ (ppm)=10.21 (1H, s), 9.53 (1H, s), 9.40 (1H, s), 8.22 (1H, s), 8.01 (1H, s), 7.93-7.91 (2H, m), 7.91-7.89 (2H, m), 7.73-7.71 (2H, m), 7.64 (1H, d, J=2.3 Hz), 7.62-7.58 (4H, m), 7.37-7.34 (3H, m), 6.86 (1H, dd, J=8.7, 2.3 Hz), 2.52 (3H, s), 2.50 (3H, s), 2.34 (3H, s).

(77) .sup.13C-NMR (126 MHz, DMSO-d.sub.6): δ (ppm)=196.28, 196.26, 153.09 (NHCONH), 152.44 (NHCONH), 144.49, 144.31, 143.23, 136.80, 134.75, 132.88, 130.54, 130.39, 129.69, 129.69, 129.65, 126.82, 125.94, 125.89, 117.19, 117.11, 115.35, 114.60, 26.33 (CH.sub.3), 26.31 (CH.sub.3), 20.99 (CH.sub.3).

(78) XV, C.sub.29H.sub.23F.sub.6N.sub.5O.sub.4S, M=651.6, N-(3,4-bis(3-(2-(trifluoromethyl)phenyl)ureido)phenyl)tosylamide

(79) MS (HSI): m/z (%)=650.1 (100) [M−H].sup.−, 489.1 (20) [M−H—Ar.sup.2NH.sub.2].sup.−, 302.1 (16) [M−H—Ar.sup.2NH.sub.2—Ar.sup.2NCO].sup.−.

(80) .sup.1H-NMR (500 MHz, DMSO-d.sub.6): δ (ppm)=10.15 (1H, s), 8.77 (1H, s), 8.66 (1H, s), 8.46 (1H, s), 8.26 (1H, s), 7.98-7.92 (2H, m), 7.71-7.57 (7H, m), 7.37-7.33 (3H, m), 7.30-7.27 (1H, m), 7.25-7.22 (1H, m), 6.85 (1H, dd, J=8.7, 2.3 Hz), 2.33 (3H, s).

(81) .sup.13C-NMR (126 MHz, DMSO-d.sub.6): δ (ppm)=153.39 (NHCONH), 153.00 (NHCONH), 143.17, 136.80, 136.59, 136.35, 134.41, 132.81, 132.54, 129.62, 126.77, 126.28, 126.09, 125.92, 125.40, 125.07, 123.88, 123.49, 122.90, 120.31, 119.65, 115.30, 20.93 (CH.sub.3).

(82) XVI, C.sub.29H.sub.25N.sub.5O.sub.6S, M=571.6, N,N′-(((4-tosylamido-1,2-phenylene)bis(azandiyl))bis(carbonyl))dibenzamide

(83) MS (ESI): m/z (%)=570.1 (25) [M−H].sup.−, 449.0 (100) [M−H—Ar.sup.2NH.sub.2].sup.−, 302.0 (63) [M−H—Ar.sup.2NH.sub.2—Ar.sup.2NCO].sup.−.

(84) .sup.1H-NMR (500 MHz, DMSO-d.sub.6): δ (ppm)=11.09 (1H, s), 11.08 (1H, s), 10.85 (1H, s), 10.45 (1H, s), 10.37 (1H, s), 8.01-7.99 (2H, m), 7.96-7.94 (2H, m), 7.83 (1H, d, J=2.5 Hz), 7.77-7.75 (2H, m), 7.65-7.60 (2H, m), 7.53-7.46 (5H, m), 7.37-7.36 (2H, m), 6.97 (1H, dd, J=8.7, 2.5 Hz), 2.34 (3H, s).

(85) .sup.13C-NMR (126 MHz, DMSO-d.sub.6): δ (ppm)=168.70, 168.64, 152.23 (NHCONH), 151.43 (NHCONH), 143.30, 136.79, 135.88, 132.97, 132.90, 132.57, 132.39, 132.21, 129.69, 128.47, 128.47, 128.24, 128.23, 126.81, 126.44, 124.87, 115.83, 114.38, 20.96 (CH.sub.3).

(86) XVII, C.sub.26H.sub.23N.sub.5O.sub.4S, M=501.6, N-phenyl-2,4-bis(3-phenylureido)benzenesulfonamide

(87) MS (ESI): m/z (%)=500.1 (100) [M−H].sup.−, 381.1 (22) [M−H—Ar.sup.2NCO].sup.−.

(88) .sup.1H-NMR (500 MHz, DMSO-d.sub.6): δ (ppm)=10.28 (1H, s), 9.65 (1H, s), 9.15 (1H, s), 8.67 (1H, s), 8.48 (1H, s), 8.15 (1H, d, J=1.2 Hz), 7.67 (1H, d, J=8.8 Hz), 7.56-7.54 (2H, m), 7.47-7.46 (2H, m), 7.37-7.27 (5H, m), 7.24-7.21 (2H, m), 7.13-7.12 (2H, m), 7.03-6.98 (3H, m).

(89) .sup.13C-NMR (126 MHz, DMSO-d.sub.6): δ (ppm)=152.04 (NHCONH), 151.75 (NHCONH), 144.48, 139.68, 139.18, 138.16, 137.24, 130.32, 129.13, 128.81, 128.77, 124.34, 122.28, 122.16, 120.67, 119.07, 118.54, 118.47, 111.07, 110.68.

(90) XVIII, C.sub.29H.sub.27N.sub.5O.sub.6S, M=573.6, ethyl 4-(2,4-bis(3-phenylureido)phenylsulfonamido)benzoate

(91) MS (ESI):m/z (%)=572.1 (100) [M−H].sup.−.

(92) .sup.1H-NMR (500 MHz, DMSO-d.sub.6): δ (ppm)=10.77 (1H, s), 9.60 (1H, s), 9.15 (1H, s), 8.66 (1H, s), 8.38 (1H, s), 8.07 (1H, d, J=2.1 Hz), 7.81-7.80 (2H, m), 7.74 (1H, d, J=8.9 Hz), 7.50-7.48 (2H, m), 7.45-7.43 (2H, m), 7.37 (1H, dd, J=8.9, 2.1 Hz), 7.32-7.26 (4H, m), 7.24-7.22 (2H, m), 7.02-6.97 (2H, m), 4.19 (2H, q, J=7.1 Hz), 1.24 (3H, t, J=7.1 Hz).

(93) .sup.13C-NMR (126 MHz, DMSO-d.sub.6): δ (ppm)=165.02, 151.95 (NHCONH), 151.59 (NHCONH), 144.72, 141.88, 139.54, 139.11, 138.09, 130.46, 130.33, 128.77, 128.70, 124.94, 122.26, 122.10, 118.99, 118.82, 118.43, 118.43, 111.23, 111.01, 60.41 (CH.sub.3), 14.08 (CH.sub.3).

(94) XIX, C.sub.32H.sub.28N.sub.6O.sub.6S.sub.2, M=656.7, N.sup.1,N.sup.3-diphenyl-4,6-bis(3-phenylureido)benzene-1,3-disulfonamide

(95) MS (ESI): m/z (%)=655.1 (100) [M−H].sup.−, 536.1 (18) [M−H—Ar.sup.2NCO].sup.−.

(96) .sup.1H-NMR (500 MHz, DMSO-d.sub.6): δ (ppm)=10.47 (2H, s), 9.75 (2H, s), 8.85 (1H, s), 8.52 (2H, s), 8.15 (1H, s), 7.48-7.47 (4H, m), 7.32-7.29 (4H, m), 7.21-7.18 (4H, m), 7.04-7.02 (8H, m).

(97) .sup.13C-NMR (126 MHz, DMSO-d.sub.6): δ (ppm)=150.92 (NHCONH), 141.38, 139.07, 136.38, 131.09, 129.19, 128.70, 124.80, 122.50, 121.03, 118.82, 118.75, 113.36.

(98) An aqueous application suspension for forming the heat-sensitive colour-forming layer of a heat-sensitive recording paper was applied on a laboratory scale by means of a doctor bar to one side of a synthetic base paper (Yupo® FP680) with a grammage of 63 g/m.sup.2. Once dry, a thermal recording material sheet was obtained. The applied amount of the heat-sensitive colour-forming layer was between 3.8 and 4.2 g/m.sup.2.

(99) A heat-sensitive recording material or thermal paper was produced on the basis of the details provided above, wherein the following formulation of aqueous application suspension was used to form a composite structure on a carrier substrate, and then the further layers, especially a protective layer, were formed in the usual manner, which will not be detailed separately here.

(100) Preparation of the dispersions (in each case for 1 part by weight) for the application suspensions

(101) An aqueous dispersion A (colour former dispersion) was prepared by grinding 20 parts by weight of 3-N-n-dibutylamino-6-methyl-7-anilinofluorane (ODB-2) with 33 parts by weight of a 15% aqueous solution of Ghosenex™ L-3266 (sulfonated polyvinyl alcohol, Nippon Ghosei) in a bead mill.

(102) An aqueous dispersion B (colour developer dispersion) was prepared by grinding 40 parts by weight of the colour developer together with 66 parts by weight of a 15% aqueous solution of Ghosenex™ L-3266 in the bead mill.

(103) An aqueous dispersion C (sensitisation agent dispersion) was prepared by grinding 40 parts by weight of sensitisation agent with 33 parts by weight of a 15% aqueous solution of Ghosenex™ L-3266 in a bead mill.

(104) All dispersions produced by grinding had a mean particle size D.sub.(4,3) of from 0.80 to 1.20 μm. The particle size distribution of the dispersions was measured by laser diffraction using a Coulter LS230 apparatus from Beckman Coulter.

(105) The dispersion D (slip additive dispersion) was a 20% zinc stearate dispersion consisting of 9 parts by weight of Zn stearate, 1 part by weight of Ghosenex™ L-3266, and 40 parts by weight of water.

(106) Pigment P was a 72% coating kaolin suspension (Lustra® S, BASF).

(107) The binder consisted of a 10% aqueous polyvinyl alcohol solution (Mowiol 28-99, Kuraray Europe).

(108) The heat-sensitive application suspension was prepared by mixing, under stirring, of 1 part A, 1 part B, 1 part C, 56 parts D, 146 parts pigment P, and 138 parts binder solution (all parts by weight) under consideration of the order of introduction B, D, C, P, A binder, and by bringing the mixture with water to a solid content of approximately 25%.

(109) The heat-sensitive coating suspensions thus obtained were used to produce composite structures of paper carrier and thermal reaction layer.

(110) The thermal recording materials were assessed as described hereinafter (Tables 3, 4 and 5).

(111) (1) Dynamic Colour Density:

(112) The papers (strips 6 cm wide) were thermally printed with use of an Atlantek 200 test printer (Atlantek, USA) with a Kyocera printhead of 200 dpi and 560 ohms with an applied voltage of 20.6 V and a maximum pulse width of 0.8 ms with a chequered pattern with 10 energy gradations. The image density (optical density (o.d.)) was measured using a Macbeth densitometer RD-914 from Gretag at an energy stage of 0.45 mJ/dot. The measurement uncertainty of the o.d. values was estimated at ≥2%.

(113) (2) Static Colour Density (Starting Temperature):

(114) The recording material sheet was pressed against a series of thermostatically controlled metal dies heated to different temperatures with a press-on 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 density (optical density) of the images thus produced was measured using a Macbeth densitometer RD-914 from Gretag. The static starting point, according to definition, is the lowest temperature at which an optical density of 0.2 is achieved. The accuracy of the measurement method was ≥±0.5° C.

(115) (3) Resistance Test of the Printed Image:

(116) a) Resistance of the printed image under conditions of artificial ageing:

(117) Each sample of the thermal recording paper recorded dynamically in accordance with the method under (1) was stored for 7 days under the following conditions: i) 50° C. (dry ageing), ii) 40° C., 85% relative humidity (moist ageing) and iii) under artificial light of fluorescent tubes, illuminance 16000 Lux (light ageing)

(118) Once the test period had elapsed, the image density was measured at an energisation energy of 0.45 mJ/dot and was set in relation to the corresponding image density values before the artificial ageing in accordance with the formula (Eq. 1).

(119) b) plasticiser resistance:

(120) A plasticiser-containing cling film (PVC film with 20-25% dioctyl adipate) was brought into contact with the sample of the thermal recording paper, which had been dynamically recorded in accordance with the method under (1), avoiding folds and inclusions of air, then rolled up into a roll and stored for 16 hours. One sample was stored at room temperature (20-22° C.), and a second sample was stored at 40° C. After removal of the film, the image density (o.d.) was measured and set in relation to the corresponding image density values before the action of the plasticiser in accordance with formula (Eq. 1).

(121) c) resistance to adhesive:

(122) A strip of transparent self-adhesive tape from Tesa (tesafilm® crystal-clear, #57315), and separately therefrom a strip of packaging adhesive tape from Tesa (#04204) were adhered to the sample of the thermal recording paper, which had been dynamically recorded in accordance with the method under (1), avoiding folds and inclusions of air. After storage at room temperature (20-22° C.), the image density (o.d.) was measured after 24 hours and after 7 days-through the particular adhesive tape—and, in accordance with the formula (Eq. 1), was set in relation to the similarly determined image density values of a freshly adhered specimen.

(123) $\begin{array}{cc}\%\mathrm{remaining}\mathrm{image}\mathrm{density}=\frac{\mathrm{image}\mathrm{density}\mathrm{after}\mathrm{test}}{\mathrm{image}\mathrm{density}\mathrm{before}\mathrm{test}}*100& \left(\mathrm{Eq}.1\right)\end{array}$

(124) The scattering of the % values calculated by (Eq. 1) was ≤±2 percentage points.

(125) 4) Storage Suitability of the Unprinted Thermal Paper:

(126) A sheet of recording paper was cut into three identical strips. One strip was recorded dynamically in accordance with the method under (1) and the image density was determined. The two other strips were stored in the unprinted (white) state for 4 weeks in a climate of a) 40° C. and 85% relative humidity (r.h.) and b) 60° C. and 50% relative humidity (r.h.).

(127) After climatisation of the papers at room temperature, they were dynamically printed in accordance with the method under (1) and the image density with an energisation energy of 0.45 mJ/dot was determined using the densitometer. The remaining writing performance (%) of the stored specimens in relation to the fresh (un-aged) specimens was calculated in accordance with the following equation (Eq. 1).

(128) Tables 3 to 5 summarise the evaluation of the finished recording materials.

(129) TABLE-US-00003 TABLE 3 Image density, starting temperature and artificial ageing o.d. Colour (0.45 Starting point Artificial ageing* developer mJ/dot) (° C.) dry moist light III 1.19 79  97  98 86 IV 1.17 82  96  98 80 XIV 1.18 85 100  98 87 XVII 1.19 82  97 100 74 XVIII 1.22 81  98 100 76 XIX 1.29 80  98  99 80 Y 1.23 82 100  98 72 Z 1.25 84  99  98 80 PF201 1.23 76 100  96 82 *Percentage of remaining image density in accordance with Eq. 1

(130) TABLE-US-00004 TABLE 4 Resistance of the printed image Plasticiser Tesa adhesive tape* film* Colour 24 h 7 days 16 h developer #57315 #04204 #57315 #04204 R.T. 40° C. III 85 80 65 38 96 75 IV 92 89 73 60 95 71 XIV 90 95 75 79 99 91 XVII 78 54 50 14 96 78 XVIII 80 66 51 30 97 80 XIX 81 61 58 21 99 80 Y 32 11 9 7 67 7 Z 54 31 13 16 88 32 PF201 71 43 29 11 96 68 *Percentage of remaining image density in accordance with Eq. 1

(131) TABLE-US-00005 TABLE 5 Writing performance after storage o.d. 4 weeks 40° C./85% r.h. 4 weeks 60° C./50% r.h. Colour before o.d. after remaining o.d. after remaining developer storage storage o.d. (%) storage o.d. (%) III 1.19 1.18  99 1.05 88 IV 1.17 1.12  96 1.05 90 XIV 1.18 1.16  98 1.01 86 XVII 1.19 1.18  99 1.02 86 XVIII 1.22 1.16  95 1.04 85 XIX 1.29 1.29 100 1.11 86 Y 1.23 — — 1.05 85 Z 1.25 1.25 100 1.11 89 PF201 1.23 1.19  97 0.74 60

(132) It can be seen from the examples above that the heat-sensitive recording material of the present invention presents the following advantageous properties especially:

(133) (1) The recorded image of the heat-sensitive papers with the colour developers according to the invention has a print density (optical density) which is comparable to that of the developers of the comparison specimens (Table 3).

(134) (2) The temperature from which a visually noticeable greying of the papers according to the invention occurred (static starting point) is comparable to or higher than that for the comparison papers and satisfies the requirements of marketable heat-sensitive recording materials (Table 3).

(135) (3) The papers subjected to the ageing test demonstrate a high image resistance. This is better than or comparable to that of the comparison papers (Table 3).

(136) (4) The printed image is practically not faded following the action hydrophobic agents (adhesives, plasticisers).

(137) The image resistance is better or comparable to the performance of the known non-phenolic colour developers (Table 4).

(138) (5) The printing of the recording materials stored over several weeks under extreme conditions leads to image densities which are practically identical to those of unstored (fresh) paper (Table 5).

(139) (6) A heat-sensitive recording material of high quality in respect of all key application properties can be obtained with the colour developers according to the invention. No heat-sensitive recording material obtained using colour developers according to the prior art has a comparable balanced performance profile across all properties.

(140) (7) The comparison of the heat-sensitive recording material containing the colour developer Y with heat-sensitive recording materials containing the colour developers XVII and XIX, and of the heat-sensitive recording material containing the colour developer Z with heat-sensitive recording materials containing the colour developers III and IV reveals the increase in image resistance, which, with otherwise comparable chemistry, is due to the increase in the density of the functional groups involved in the colour-forming and stabilisation process (Table 4).