CHROMOGENIC COMPOUNDS

Abstract: A chromogenic pyrazine compound of formula: wherein X¹ and X², which may be the same or different, are each selected from hydrogen, alkyl, optionally substituted alkyl, alkoxy, carboxyalkyl, optionally substituted aryl, op­ tionally substituted heteroaromatic, optionally substituted aralkyl or dialkylamino, provided that both X¹ and X² are not both hydrogen at the same time; and A¹ and A², which may be the same or different, are each: (i) a heterocyclic ring system having an aryl group annellated through a conjugated nitrogen linkage; or (ii) a homocyclic aryl group having a substituent -NR₁R₂ wherein R₁ and R₂ are separately hydrogen or an optionally substituted alkyl, aryl or aralkyl group or both R₁ and R₂ together with the nitrogen atom to which they are joined form a nitrogen-linked ring, provided that R₁ and R₂ are not both hydrogen at the same time.

Description: CHROMOGEN IC COMPOUNDS This invention relates to chromogenic compound and in particular to chromogenic pyrazine compounds . A chromogenlc compound is a colourless or nearly colourless organic material which is capable of undergoing a colour-forming reaction on being brought into contact with a suitable co-reactant, for example an electron-accepting co-reactant such as an active clay material. The colour-forming reaction may take place by contacting the chromogenic compound, preferably in the form of a solution in a suitable organic solvent, with the solid co-reactant, which may for example be coated onto or incorporated into a paper material. For many applications, a solution of the chromogenic compound in a suitable organic solvent is separated from the solid co-reactant by a membrane so that the colour develops only when the membrane is ruptured. For example, pressure-sensitive recording materials generally consist of the combination of (i) a base sheet having coated thereon microcapsules containing a solution in an organic solvent of the chromogenic compound and (ii) a receiving sheet coated with a suitable co-reactant. When pressure is applied to the base sheet, as for example by handwriting or typewriting, the membranes of the microcapsules at the point of pressure are ruptured, and a colour-forming reaction takes place as the solution of the chromogenic compound contacts the co-reactant. Variations of this general principle are possible, as for example a single recording sheet having a coating of micro-encapsulated chromogenic compound solution and a coating of co-reactant. Heat-sensitive recording materials function in a similar manner, the chromogenic compound and the co-reactant being separated by a medium which melts on the application of local heat as described for example in United States Patent No 3,539,375. One problem which is frequently encountered in the practical application of chromogenic materials is the development of colour, even in the absence of a co-reactant, when the chromogenic material is in contact with the base paper (see for example GB 2 141 729A - page 4). Thus for example when a nicroencapsulated layer is applied to the base paper during nanufacture it is inevitable that some of the microcapsules will rupture, releasing the solution of the chromogenic material. It is clearly important that no colour is formed st this stage. Chromogenic pyrazine lactone (5,7-dihydrofuro (3,4-bl-pyrazin-5-one) compounds are disclosed in GB f,367,569, but these compounds have been found to suffer from the above-mentioned problem of the development of colour in contact with base papers. According to the present invention, there is provided a chromogenic 5,7-dihydrofuro F3,4-b] pyrazin-5-one compound having substituents in one or both of the 2,3- positions. Thus, the present invention provides a chromogenic pyrazine compound of formula EMI2.1 wherein X1 and X2, which My be the same or different, are each selected from hydrogen, alkyl, optionally substituted alkyl, alkoxy, carboxyalkyl, optionally substituted aryl, optionally substituted heteroaromatic, optionally substituted aralkyl or dialkylamino, provided that both X1 and X2 are not both hydrogen at the same time; and A1 and A2, which may be the same or different, are each: (i) a heterocyclic ring system having an aryl group annellated througb a conjugated nitrogen linkage; or (ii) a homocyclic aryl group having a substituent -NR 1R2 wherein R1 and R2 are separately hydrogen or an optionally substituted alkyl, aryl or aralkyl group or both R1 aid R2 together with the nitrogen atom to which they are joined form a nitrogen-linked ring, provided that R1 and R2 are not both hydrogen at the same time. As optional substituents when R1 andlor R2 are an alkyl, aryl or aralkyl group, there may be mentioned for example -CN, -OH, alkoxy, and -NH2 When R1 and/or R2 are aryl groups optional substituents additionally include for example -NO2 and alkyl. It is preferred that neither X1 nor X2 are hydrogen, and for ease of manufacture, it is especially preferred that XÚ and Xê are the name. Preferred groups XÚ and Xê are alkyl and aryl groups. As examples of alkyl groups, there may be mentioned alkyl containing from 1 to 24, and especially from 1 to 8 carbon atoms. When both X1 and X2 are methyl, the compound of formula (I) is readily prepared from relatively inexpensive starting materials. As substituents which may be present in the substituted alkyl group there may be mentioned for sample halogen, cyano, hydroxy, nitro and amino. As examples of aryl groups, there may be especially mentioned optionally substituted phenyl. As examples of aralkyl groups, there may be mentioned optionally substituted benzyl. As examples of alkoxy groups, there may be mentioned alkoxy groups containing from 1 to 24, and especially from 1 to 8 carbon atoms. As examples of heteroaromatic groups, which may be optionally substituted, there may be mentioned 5- or 6- membered ring nitrogen, oxygen or sulphur heteroaromatic groups, including for example pyridin-2-yl, furan-2-yl and thiophen-2-yl. As examples of carboxyalkyl groups, there may be mentioned carboxylower alkyl groups, for example carboxymethyl. As examples of dialkylamino groups, there may be mentioned dialkylamino groups containing a total of from 2 to 24, for example from 2 to 16 carbon atoms and including dimethylamino. The optional substituents present when X1 and X2 are optionally substituted aryl, aralkyl or heteroaromatic may be substituents which would be conventional to those skilled in the art. Substituents may if desired be selected to improve the solubility of the chromogenic compound in appropriate organic solvents, but it is not necessary that such substituents should be present. As examples of optional substituents there may be mentioned alkyl, especially lower alkyl, alkoxy, halogen, nitro, cyano, hydroxy, amino and alkyl or dialkyl amino. As examples of groups Al or A2 which are a heterocyclic ring system having an aryl group annellated through a conjugated nitrogen linkage, there may be mentioned (1) indolyl, and especially 3-indolyl, for example the group EMI4.1 wherein R3 and R4 are independently hydrogen or more preferably alkyl (which as used herein includes optionally substituted alkyl, for example halogen-substituted alkyl), aryl (which as used herein includes optionally substituted aryl) or aralkyl (which as used herein includes optionally substituted aralkyl); and P is hydrogen, alkyl, alkoxy, or halogen; (2) carbazolyl, for example the group: EMI4.2 wherein P and P', which may be the same or different, are optional substituents having the meaning given above for P; and R5 is hydrogen or more preferably alkyl, aryl or aralkyl; (3) tetrahydroquinolyl, for example the group: EMI5.1 wherein P is an optional substituent having the meaning given above, R6 is hydrogen or more preferably alkyl, aryl or aralkyl, and the groups R7 to Rl2 are hydrogen, alkyl, aryl or eralkyl; and (3a) dihydroquinolyl, for example the group: EMI5.2 wherein P is an optional substituent having the meaning given above, R25 is hydrogen or more preferably alkyl, aryl or aralkyl and the groups R26 and R27 are hydrogen, alkyl, aryl or aralkyl; or the corresponding 1,4-dihydroquinolyl group; and (4) julolidinyl, for example the group: EMI6.1 wherein P is an optional substituent having the meaning given above, and the groups R13 to R24 are hydrogen, alkyl, aryl or aralkyl. As examples of a homocyclic aryl group having a substituent -NR1R2 there may be mentioned: (5) aminophenyl, and especially p aminophenyl, for example the group: EMI6.2 wherein Q is hydrogen, alkyl, alkoxy, acylamino or halogen, and R1 and R2 have the meanings given previously; and (6) aminonaphthyl, for example the group: EMI7.1 wherein Q, and R1 and R2 have the meanings given previously. The groups Y, P and Q will frequently be hydrogen, and very often optional substituents will not be present in groups such as alkyl, aryl, aralkyl, indolyl, carbazolyl, tetrahydroquinolyl and julolidinyl described herein. Where such optional substituents are present they will frequently be simple groups such as alkyl groups containing from 1 to 6 carbon atoms, and unsubstituted phenyl or benzyl groups. However it should be noted that optional substituents may be present for example for convenience of manufacture. Furthermore, the presence of optional substituents may modify the properties of the unsubstituted compound in a desirable manner. Thus, for example, the presence of a higher alkyl substituent may have the effect of increasing the oil-solublility of the chromogenic compound should this be desired. The nitrogen in the group -NR1R2 and in the heterocyclic ring system is preferably a tertiary nitrogen, and R1 and R2 (in formula I), R3 (in formula II) and R5 (in formula III) are preferably not hydrogen. R1, R2, R3, R4, R5, R6 and R25 are conveniently alkyl (for example an alkyl group containing from 1 to 6 carbon atoms), benzyl or (optionally substituted) phenyl. Alternatively R1 and R2 and the nitrogen atom joining them together form a heterocyclic ring, for example pyrrolidinyl, morpholinyl or piperidinyl. In general any combination of groupe AÚ and Aê may be used, however especially preferred cobinations of groups AÚ and Aê are: (1) indolyl (for example the group of formula II) combined with any one of the groups indolyl (formula II), aminophenyl (formula VI), aminonaphthyl (formula VII) carbazolyl (formula III), tetrahydroquinolyl (formula IV), dihydroquinolyl (formula IVa) and julolidinyl (formula V); and (2) aminophenyl (for example the group of formula VI) combined with any one of the groups aminophenyl (formula VI), aminonaphthyl (formula VII), carbazolyl (formula III) tetrahydroquinolyl (formula IV), dihydroquinolyl (formula IVa) and julolidinyl (formula V). As specific examples of the chromogenic compounds of formula I there may be mentioned 2,3-di(4-methoxyphenyl)-7-(1-ethyl-2-methylindol-3-yl)7-(4-N,N-diethylaminophenyl)-5.7-dihydrofuro-[3,4-b]-pyrazin-5-one; 2,3-diphenyl-7,7-di(2-acetylamino-4-N,N-diethylaminophenyl)- 5, 7-dihydrofuro- [3,4-b] -pyrazin-5-one; 2,3-diphenyl-7,7-di(4-N,N-diethylaminophenyl)- 5,7-dihydrofuro-[3,4-b]-pyrazin-5-one; 2, 3-diphenyl-7, 7-di(4-N,N-dipropylaminophenyl)- 5,7-dihydrofuro-[3,4-b]-pyrazin-5-one; 2,3-diethyl-7-(1-ethyl-2-methylindol-3-yl)-7-(4-N,N diethylamlnophenyl)-5,7-dthydrofuro-t3,4-b]-pyrazin-5-one; 3-phenyl-7 , 7-di(4-N,N-diethylaminophenyl)- 5,7-dihydrofuro-[3,4-b] -pyrazin-5-one; 2,3-dimethyl-7-(1-octyl-2-methylindol-3-yl)- 7-(4-N,N-diethylaminophenyl)-5,7-dihydrofuro-[3,4-b]-pyrazin-5-one; ; 2,3-diphenyl-7,7-di(2-methyl-4-N,N-diethylaminophenyl) 5, 7-dihydrofuro-(3,4-b]-pyrszin-5-one; 2,3-diphenyl-7-(1-ethyl-2-methylindol-3-yl) 7- (4-N-ethyl, N- (2-cyanoe thyl) aminophenyl) -5,7-dihydrofuro-[3,4-b]-pyrazin-5-one; 2-methyl-3-ethyl-7-(l-ethyl-2-methylindol-3-yl)7-(4-N,N-dimethylaminophenyl)-5,7-dihydrofuro-[3,4-b]-pyrazin-3-one; and 2-methyl-3-phenyl-7,7-di(4-N,N-diethylaminophenyl)5,7-dihydrofuro-[3,4-b]-pyrazin-5-one. The chromogenic compounds of the present invention may be prepared by known general methods. Thus, for example, compounds of general formula (I) may be prepared by reacting a compound of general formula VIII with a compound of general formula A2H in the presence of an acid condensing agent such as phosphoric acid, sulphuric acid, zinc chloride and especially acetic anhydride. EMI9.1 When the reaction is complete, the reaction mass is suitably neutralised with alkali such as ammonia and if necessary the residue may be treated with dilute mineral acid to remove any basic impurities. The product may be recovered in conventional manner, for example filtration followed by recrystallisation or chromatography. The novel intermediate of general formula VIII may be prepared by reacting the appropriate pyrazine anhydride with a compound of formula A1H: EMI10.1 The reaction preferably takes place in the presence of a suitable solvent, for example toluene, xylene, methylene chloride, acetonitrile, acetic acid or chlorobenzene, and there may optionally be added a salt of a polyvalent metal, for example zinc chloride or aluminium chloride. Compounds of formula (IX) are generally known compounds, available for example by the reaction of the appropriate dike tone with 1,2-diamino-1,2-dicyanoethylene to form the corresponding dicyano pyrazine followed by hydrolysis of the cyano groups and cyclisation in the presence of for example acetic anhydride: EMI10.2 EMI10.3 (X) (XI) (IX) If the two groups AÚ and Aê are the same (A), the pyrazine anhydride of formula (IX) may be reacted with two molecules of the compound AH under more forcing conditions to go directly through to the compound of formula (I). The chromogenic compounds of the present invention, when converted into their coloured form, generally show excellent tinctorial strength, light-fastness and long-term fade resistance. These advantages tend to be combined with a relatively rapid colour development (rate of reaction with the co-reactant) and good moisture resistance giving a very effective balance of colour-forming properties. In particular, the chromogenic compounds of the present invention generally show good stability with respect to the premature development of colour (for example during encapsulation, coating and storage of the coated paper) and generally give colourless emulsions and derived coated papers The chromogenic compounds of the present invention may be used in conventional manner. They may be used in conventional solvents known in the art such as alkylated biphenyls (for example monoisopropyl biphenyl), naphthalenes (for example partially hydrogenated naphthalene), terphenyls (which may be partially or totally hydrogenated), di esters of dicarboxylic acids (for example alkyl oxalates and phthalates) and polyhalogenated paraffins. The solution in a suitable organic solvent may be micro-encapsulated using conventional techniques, and the encapsulated system incorporated into pressure-sensitive or thermal copying materials. Thus, the capsules walls can be formed evenly around the droplets of the colour former solution by coacervation; and the encapsulating material can consist of gelatin and gum arabic, as described e.g. in US patent 2800457. The capsules can also be formed from an aminoplast or a modified aminoplast by polycondensation, as described in British patent specifications 989264, 1156725, 1301052 and 1355124. Other suitable microcapsules are formed by interfacial polymerisation e.g. capsules formed from polyester, polyearbonate, polysulphonamide, polysulphonate, but in particular from polyamide or polyurethane. The microcapsules containing the compounds of formula (1) can be used for the production of a wide variety of known kinds of pressure-sensitive copying material. The various systems differ substantially from one another in the arrangement of the capsules, of the colour reactions, and of the support. A preferred arrangement is that in which the encapsulated chromogenic compound is in the form of a layer on the back of a transfer sheet and the developer is in the form of a layer on the face of a receiver sheet. Another arrangement of the components is that wherein the microcapsules which contain the chromogenic compound, and the developer, are in or on the same sheet, in the form of one or more individual layers, or are present in the paper pulp. Conventional co-reactants may be used for the chromogenic compounds of the present invention and as examples there may be mentioned active clays, (for example acid clay, attapulgite, zeolite or bentonite); a solid organic acid (such as succinic acid,tannic acid or benzoic acid); an acidic polymer (such as phenol-formaldehyde, phenol-acetylene polymer, residual acid group-containing styrene-maleic anhydride polymer or salicylic acid-formaldehyde polymer); and heavy metal salicylates (such as zinc salicylate). Bisphenol A is commonly used as a co-reactant in heat-sensitive applications. The invention is illustrated by the following Examples in which all parts and percentages are by weight unless otherwise stated. Example 1 Preparation of 2,3-diphenyl-7-(1-athyl-2-methylindol-3-yl)-7 (2-methoxy-4-N,N-disthylaminophenyl)-5,7-dihydrofuro[3,4-b]pyrazine-5-one (XII). EMI13.1 A mixture of 5,6-diphenylpyrazine-2,3-dicarboxylic anhydride (4g), 1-ethyl-2-methyllndole (2.lg) and acetonitrile (20ml) was stirred at ambient temperature for 16 hours. The product was isolated by filtration, washed with methanol and dried to yield (1-ethyl-2-methylindol-3-yl)-(2-carboxy-5,6-diphenylpyrazin-3-yl) ketone (4g). A mixture of the above keto acid (1g), 3-methoxy-N,N-diethylaniline (O.4g) and acetic anhydride (lOml) was stirred at 90 C for 2 hours. After cooling, the solution was treated with 15% aqueous ammonia (60ml), stirred I hour and the tarry product was isolated by decantation. After treatment with dilute hydrochloric acid the solid product was isolated by filtration, washed with water and dried to yield compound (XII) (1.1g). A 1Z solution of the product in a polyhalogenated paraffins solvent showed little or no colour formation when applied to base paper. max " 595nm. Examples 2-22 Examples 2-22 shown in Table 1 can be prepared by the method of Example 1. The compounds have the general formula: EMI14.1 and are identified in Table 1 by the substituents. Table 1 Ex. Q R1 R2 P R3 R4 #max. 2 H nC3H7 nC3H7 H C2H5 CH3 610 3 H CH3 CH3 H H " 598 4 H " " H nC4Hg " 608 5 H C2H5 C2H5 H C2H5 " 610 6 H nC4Hg nC4H9 H " " 610 7 H nC3H7 nC3H7 H H " 604 8 H C2H5 CH2C6H5 H C2H5 " 611 9 H " CH2CH2CN H " " 611 10 H CH2CH2OCOCH3 CH2CH2OCOCH3 H " " 608 11 H CH3 C2H5 H " " 610 12 H C2H " H nC8H17 " 611 13 H " " H C2H5 C6H5 615 14 H " " H CH2C6H5 CH3 610 15 H CH3 CH3 CH3 C2H5 " 610 16 OCH3 C2H5 C2H5 H nC4H9 " 595 17 OC2H5 " " H C2H5 " 598 18 OC3H7 " " H " " 598 19 OC4H9 " " H " " 600 20 NHCOCH3 " " H " " 625 21 Cl " " H " " 615 22 CH3 " " " H " " 615 Example 23 Preparation of 2,3-dimethyl-7-(1-ethyl-2-methylindol-3-yl)7-(4-N,N-dimethylaminophenyl)-5,7-dihydrofuro[3,4-b]pyrazin-5-one <RTI ID=16.1> (XIII). EMI16.1 (l-ethyl-2-methylindol-3-yl)-(2-carboxy-5,6-dimethyl- pyrazin-3-yl)ketone was prepared by the method of Example 1 using 5,6-dimethylpyrazin-2,3-dicarboxylic anhydride as starting material. A mixture of the above keto-acid (O.5g), N,N-dimethylaniline (O.2g) and acetic anhydride (6ml) was stirred at 900C for 4 hours. After cooling to room temperature the solution was treated with 15Z aqueous ammonia (50ml), stirred for 1 hour and the tarry product was purified by column chrotatography to yield compound (XIII). A 1% solutlon-of the product in monoisopropyl biphenyl showed little or no colour formation when applied to base paper. #max 602mm. Examples 24-59 Examples 24-59 shown in Table 2 can be prepared by the method of Example 23. The compounds have the general formula: EMI17.1 and are identified in Table 2 by the substituents. Table 2 Ex. Q R1 R2 P R3 R4 #max. 24 H C2H5 C2H5 H C2H5 CH3 602 25 H nC3H7 nC3H7 H " " 602 26 H nC4H9 nC4H9 H " " 602 27 H C2H5 CH2C6H5 H " " 605 28 H " C2H4CN H " " 605 29 H CH2CH2OCOCH3 CH2CH2OCOCH3 H " " 605 30 CH3 C 2H5 C2H5 H It " 610 31 OCH3 " " H " " 590 32 OC2H5 " " H " " 590 33 OC3H5 " " H " " 593 34 OC4H5 " " H " " 593 35 NHCOCH3 " " H " " 615 36 Cl CH3 CH3 H " " 600 31 H " C2H5 H " " 602 38 H nC4Hg nC4H9 H H " 590 39 H C2H5 C2H5 H nC3H7 " 602 40 H " " H nC4H9 " 602 41 H " " H CH3 " 600 42 H " " H C8H17 " 603 43 H C3H7 C3H7 H C2H5 C6H5 610 44 H CH3 CH3 H CH2C6H5 CH3 602 45 H C2H5 C2H5 CH3 C2H5 " 602 46 H CH3 CH3 H nC8H17 " 603 47 H C2H5 CH2C6H5 H " " 606 48 H " " H nC4H9 " 606 Table 2 (continued) Ex. Q R1 R2 P R3 R4 #max. 49 H nC3H7 nC3H7 H nC8H17 CH3 606 SO H nC4Hg nC4Hg H " " 605 51 H " " H nC4Hg " 603 52 H nC5H11 nC5H11 H " " 606 52 H nC5H13 nC6H13 H " " 606 52 H " " H C2H5 " 602 55 H CH3 CH3 H nC6H13 " 604 56 H C2H5 C2H5 H " " 606 57 H nc3H7 nC2H5 H 11 , 606 58 H nC4H9 nC4H9 H " " 605 59 H nC5H11 nC5H11 H " " 606 Example 60 Preparation of 2,3-diphenyl-7-(1-ethyl-2-methylindol-3-yl)-' 7-(4-N,N-dimethylaminophenyl)-5,7-dihydrofuro[3,4-b]pyrazin-5-one (XIV). EMI19.1 N,N-dimethylaniline (15g) and then anhydrous aluminium chloride (15g) were added slowly to ice-cooled methylene chloride (160ml), the temperature was allowed to rise to room temperature and 5,6-diphenylpyrazine-2,3-dicarboxylic anhydride (28.7g) was added gradually. The reaction mixture was stirred under reflux for 72 hours, cooled, steam distilled and the residue was isolated by filtration. After dissolving in aqueous ammonia and screening the product, (4-N,N-dimethylaminophenyl)-(2-carboxy-5,6-diphenylpyrazin-3-yl) ketone (7.5g) was precipitated by the addition of dilute hydrochloric acid. A mixture of the above keto-acid (1.0g), l-ethyl-2-methylindole (0.4g) and acetic anhydride (lOml) was stirred at 95 C for 2 hours. After cooling to room temperature the solution was treated with 15% aqueous ammonia (60ml), stirred for 2 hours. The product was isolated by filtration and washed well with water to yield compound (XIV) (1.2g). A 1% solution of the product in monoisospropyl biphenyl showed little or no colour formation when applied to base paper. Amax = 610nm. Example 61 Preparation of 2 ,3-dimethyl-7- (4-N,N-dimethylaminophenyl)- 7- (4-N,N-dipropylaminophenyl)-5, 7-dihydrofuro [3,4-b] pyrazin-5-one (XV). EMI20.1 (4-N,N-dimethylaminophenyl)-(2-carboxy-5,6-dimethylpyrazin3-yl)ketone was prepared by the method of Example 60 using 5,6-dimethylpyrazin-2,3-dicarboxylic anhydride as starting material. A mixture of the above keto acid (1.Og), N,N-di-n-propylaniline (0.6g) and acetic anhydride (10ml) was stirred at 90 C for 3 hours. After cooling to room temperature, the solution was treated with 15% aqueous ammonia (80r1) and stirred for 3 hours. The product was isolated by filtration and purified by chromatography to yield compound (XV). A 1% solution of the product in polyhalogenated paraffins showed little or no colour formation when applied to base paper. #max = 643 nm. Examples 62-93 Examples 62-93 shown in Table 3 can be prepared by the general method of Example 61. The compounds have the general formula EMI21.1 and are identified in Table 3 by the substituents. Table 3 Ex. Q R1 R2 Q1 R'1 R'2 #max. 62 H CH3 CH3 H CH3 CH3 640 63 H C2H5 C2H5 H C2H5 C2H5 643 64 H nC3H7 nc3H7 H nC3H7 nc3E7 652 65 H nC4H9 nC4H9 H nC4H9 nC4H9 652 66 H C2H5 CH2C6H5 H C2H5 as R2 647 67 H " CH CH2CH2CN H " as R2 640 68 H " CH2CH2OCOCH3 H " as R2 640 69 H CH3 nC4H9 H CH3 nC4H9 643 70 CH3 C2H5 C2H5 CH3 02115 02115 670 71 CH3 " CH2C6H5 CH3 " as R2 668 72 NHCOCH3 " C2H5 NHCOCH3 C2H5 C2H5 668 73 Cl " " Cl " " 660 74 H CH3 CH3 H " " " 641 75 H " " H nC3H7 nC3H7 643 76 H " " H nC4H9 nC4H9 649 77 H C2H5 C2H5 H nC3H7 nc3H7 643 78 H " " H nC4H9 nC4H9 643 79 H CH3 CH3 CH3 C2H5 C2H5 650 80 H " " NHCOCH3 " " 660 81 H " " OCH3 " " 640 82 H " " OC3H7 " " 640 Table 3 (continued) Ex. Q R1 R2 Q1 R'1 R'2 #max. 83 H CH3 CH3 OC2H3 C2H5 C2H5 639 84 H C2H5 C2H5 " " " 639 85 CH3 " " CH3 " CH2CH2CN 660 86 H CH3 CH3 H " " 640 87 H " " H " CH2C6H5 642 88 H " " H " CH2CH2OCOCH2 640 89 H nC3H7 nC3H7 CH3 " C2H5 630 90 H C2H5 C2H5 H " CH2C5H5 642 91 H CH3 CH3 H " " 642 92 H " " CH3 " " 655 93 H C2H5 C2H5 CH3 " " 655 Example 94 Preparation of 2,3-diphenyl-7,7-di(4-N,N-dimethylaminophenyl) 5,7-dihydrofuro[3,4-b]pyrazin-5-one (XVI). EMI24.1 A mixture of the keto-acid of Example 60 (1.Og), N,N-dimethylaniline (0.3g) and acetic anhydride (16ml) was stirred at 900C for 3 hours. After cooling to room eeuperature the product was isolated by filtration, washed vith ethanol and dried to yield compound (XVI) (1.Og). A 12 solution of the product in polyhalogenated paraffins showed little or no colour formation on base paper. #max = 650 nm. Examples 95-121 Example 95-121 shown in Table 4 can be prepared by the method of Example 94. The compounds have the general formula: EMI25.1 and are identified in Table 4 by the substituents. Table 4 Ex. Q R1 R2 Q1 R'1 R'2 #max. 95 H C2H5 C2H5 H C2H5 C2H5 650 96 H nC3H7 nc3H7 H nC3H7 nC3H7 655 97 H nC4H9 nC4H9 H nC4H9 nC4H9 658 98 H 02115 CH2 2C5H5 H 02115 as R2 650 99 H H " CH2CH2CN 11 as R2 650 100 H CH 2CH2OCOCH3 H " as R2 648 101 H CH3 nC4H9 H CH3 nC4H9 655 102 CH3 02115 02115 CH3 C2H5 02115 670 103 CH3 " CH2C6H5 CH3 " as R2 672 104 NHCOCH3 " C2H5 NHCOCH3 " C2H5 670 105 Cl " " Cl " " 665 106 H CH3 CH3 H " " 650 107 H " " H nC3H7 nC3H7 653 108 H " " H nC4H9 nC4H9 655 109 H C2H5 C2H5 H nC3H7 nC3H7 655 110 H " " H nC4H9 nC4H9 655 111 H CH3 CH3 CH3 C2H5 C2H5 665 112 H " " NHCOCH3 " " 660 113 H " " OCH3 " " 645 114 H " " OC3H7 " " 645 115 H " " OC2H5 " " 646 116 H C2H5 C2H5 " " " 646 117 CH3 " " OCH3 " " 650 118 CH3 " " CH3 " CH2CH2CN 666 119 H CH3 CH3 H " " 641 120 H " " H " CH2C6H5 646 121 H " " <RTI ID=26.6> H " CH2CH2OCOCH3 646 Example 122 Preparation of 2,3-diphenyl-7,7-ti(l-ethyl-2-methylindol- 3-yl)-5,7-dShydrofuro[3,4-b]pyrazin-5-one (XVII). EMI27.1 A mixture of keto-acid of Example 1 (l.Og), l-ethyl-2methylindole and acetic anhydride (lOml) was stirred at 750C for 2 hours. After cooling to room temperature the mixture was treated with 15Z aqueous ammonia (60ml), stirred for 2 hours, the product was isolated by filtration and washed with water to yield Compound (XVII). A 1Z solution of the product in polyhalogenated paraffins showed little or no colouration in contact with base paper. max " 562nm. Examples 123-135 Examples 123-135 shown in Table 5 can be prepared by the method of Example 122. The compounds have the general formula EMI28.1 and are identified in Table 5 by the substituents. Table 5 Ex. P R3 R4 P1 R'3 R'4 #max. 123 H C2H5 CH3 H CH3 CH3 360 124 H " " H nC3H7 " 362 125 H " " H nC4H9 " 365 126 H " " H nC8H17 " 370 127 H nC3H7 H nC3H7 568 128 H nC4H9 " H nC4Hg " 570 129 H nC8H17 " H nC8H17 " 572 130 H 2 2H5 " H C2H5 C H 575 131 H " " CH3 " CH3 360 132 CH3 " " CH3 " " 361 133 H OH3 N H CH3 560 134 H CH2C6H5 " H CH2C6H5 " 365 135 H " " H C2H5 " 362 Example 136 Preparation of 2,3-dimethyl-7,7-di(1-ethyl-2-methylndol-3-yl) 5,7-dihydrofuro(3,4-b]pyrazin-5-one (XVIII). EMI30.1 A mixture of the keto acid of Example 2 (1.Og), l-ethyl2-methylindole (0.5g) and acetic anhydride (lOml) was stirred at 750C for 1 1/3 hours. After cooling to room temperature, the mixture was treated with 15Z aqueous ammonia (loom) and stirred 4 hours. The product was isolated by filtration and purified by column chromatography to yield compound (XVIII). A 1% solution of the product in a dialkyl naphthalene solvent showed little or no colouration on base paper. A max " Examples 137-150 Examples 137-150 shown in Table 6 can be prepared by the method of Example 136. The compounds have the general formula EMI31.1 and are identified in Table 6 by the substituents. Table 6 Ex. P R3 R4 P1 R'3 R'4 #max. 137 H C2H5 CH3 H CH3 CH3 553 138 H " " H nC3H7 " 555 139 H " " H nC4H9 " 555 140 H " " H nC8H17 " 560 141 H " " H C2H5 " 553 142 H nC3H7 " H nC3H7 " 555 143 H nC4H9 " H nC4H9 " 557 144 H nC8H17 " H nC8H17 " 560 145 H CH3 " H CH3 " 550 146 H C2H5 " H C2H5 C6H5 555 147 H " " H CH2C6H5 CH3 553 148 H " " CH3 C2H5 " 553 149 CH3 " " CH3 " " 554 150 CH2C6H5 " " H CH2C6H5 " 552 Example 151 Preparation of 2,3-difuryl-7-(1-ethyl-2-ethylindol-3-yl)- 7-(4-N,N-diethylaminophenyl)-5,7-dihydrofuro[3,4-b]pyrazin-5-one (XIX). EMI33.1 (l-ethyl-2-methylindol-3-yl)-(2-carboxy-5,6-difurylpyrazin3-yl)ketone was prepared by the method of Example 1 using 5,6-difurylpyrazine-2,3-dicarboxylic anhydride as starting material. A mixture of the above keto acid (1.Og), N,N-diethylaniline (0.4g) and acetic anhydride (10ml) was stirred at 900C for 3 hours. After cooling to room temperature, the solution was treated with 15X aqueous ammonia (150ml) and stirred for 2 hours. The tarry product was isolated by decantation and was purified by chromatography to yield compound XIX. A 1% solution of the product in a dialkyl naphthalene solvent showed little or no colouration on base paper. max - 610nm. Examples 152-162 Examples 152-162 shown in Table 7 can be prepared by the method of Example 151. The compounds have the general formula: EMI34.1 and are identified in Table 7 by the substituents. Table 7 EMI35.1 <tb> Example <SEP> ; <SEP> ss <SEP> max <tb> 152 <SEP> · <SEP> -¸ <SEP> 608 <tb> 153 <SEP> CH3 <SEP> OH3 <SEP> 610 <tb> 154 <SEP> > <SEP> C1 <SEP> < <SEP> C1 <SEP> 612 <tb> 155C1 <SEP> 0113 <SEP> CH3 <SEP> 611 <tb> 156 <SEP> CH3 <SEP> nC4H9 <SEP> 602 <tb> 157 <SEP> nC4Hg <SEP> II <SEP> 603 <tb> 158 <SEP> CH3 <SEP> isoC3H7 <SEP> 605 <tb> 159 <SEP> CH2Br <SEP> CH2Br <SEP> 610 <tb> 160 <SEP> CH3 <SEP> nC3H7 <SEP> 605 <tb> <SEP> C.CH3 <SEP> OH3 <tb> 161 <SEP> " <SEP> - <SEP> C <SEP> = <SEP> O <SEP> 611 <tb> 162 <SEP> > <SEP> N02 <SEP> > <SEP> NO2 <SEP> 615 <tb> Example 163 Preparation of 2,3-diphenyl-7,7-di(2-methoxy-4-N,N-diethyl aminophenyl)-5,7-dihydrofuro[3,4-b]pyrazin-5-one (XX) EMI36.1 A mixture of 5,6-diphenylpyrazine-2,3-dicarboxylic anhydride (0.5g), 3-methoxy-N,N-diethylaniline (0.6g) and acetic anhydride (7.5ml) was stirred at 850C for 4 1/2 hours. After cooling to room temperature, the solution was treated with 5% aqueous ammonia (60ml), stirred for 1 hour and the tarry product was isolated by decantation. After treatment with dilute hydrochloric acid the solid product was isolated by filtration, washed with water and dried to yield compound (XX) (0.5g). A 1% solution of the product in polyhalogenated paraffins showed little or no colour formation on base paper. By way of comparison a 1% solution in the same solvent of a corresponding compound having no substituents on the pyrazine ring showed extensive and commercially undesirable colour formation when applied in the same manner to base paper. #max = 641 nm. Example 164 Preparation of 2,3-dimethyl-7,7-di(2-methoxy-4-N,N-diethylaminophenyl)-5,7-dihydrofuro[3,4-b]pyrazin-5-one (XXI). EMI37.1 A mixture of 5,6-dimethylpyrazine-2,3-dicarboxylic anhydride (lg), 3-methoxy-N,N-diethylaniline (2g) and acetic anhydride (18ml) was stirred at 85 C for 4 hours. After cooling to room temperature, the solution was treated with 15% aqueous ammonia (100ml), stirred for 1 hour and the tarry product was isolated by decantation. After treatment with dilute hydrochloric acid, the solid was isolated by filtration, washed with water to yield compound (XXI). A 1% solution of the product in polyhalogenated paraffins showed little or no colour formation when applied to base paper. Amax max = 632nm. Example 165 Preparation of 2,3-diphenyl-7-(4-N,N-dimethylaminophenyl)7-(4-methylanilino)naphth-1-yl)-5,7-dihydrofuro[3,4-b]-pyrazin-5one (XXII). EMI38.1 A mixture of (4-N,N-dimethylaminophenyl)-2-(carboxy-5,6- diphenylpyrazin-3-yl)ketone (1.Og), (prepared by the method of Example 60), 4-methylanilinonaphthalene (0.6g) and acetic anhydride (8ml) was stirred at 90 C for 3 hours. After cooling to room temperature, the solution was treated with 15X aqueous ammonia (50ml). stirred for 2 hours. The product was filtered off and purified by column chromatography to yield compound (XXII). A 1% solution of the product in a dialkyl naphthalene solvent showed little or no colouration on base paper. > max = 668nm. Example 166 Preparation of 2,3-dimethyl-7-(4-N,N-dimethylaminophenyl)7-(1,2,2,4,7-pentamethyl -1,2-dihydroquinol-6-yl)-5,7-dihydrofuran [3,4-b]pyran-5-one (XXIII). EMI39.1 A mixture of (4-N,N-dimethylaminophenyl)-(2-carboxy-5,6- dimethylpyrazin-3-yl)ketone (1.0g) (prepared by the method of Example 61), 1 ,2,2,4,7-pentamethyl-1,2-dihydroquinoline (0.7g) and acetic anhydride (8ml) was stirred at 90 C for 2 hours. After cooling to room temperature, the solution was treated with 15% aqueous ammonia (100ml) and stirred fbr 3 hours. The product was isolated by filtration and purified by column chromatography to yield compound (XXIII). A 1Z solution of the product in polyhalogenated paraffins showed little or no colouration on base paper. A max = 651nm. Example 167 Preparation of 2,3-dimethyl-7-(4-N,N-dimethylaminophenyl)7-(1,2,2,4,7-pentamethyl-1,2,3,4-tetrahydroquinol-6-yl)-5,7 dihydrofuro[3,4-b]pyrazin-5-one (XXIV). EMI40.1 A mixture of (4-N,N-dimethylaminophenyl)-(2-carboxy-5,6- dimethylpyrazin-3-yl)ketone (1.0g) (prepared by the method of Example 61), 1,2,2,4,7-pentamethyl-1,2,3,4-tetrahydroquinoline (0.7g) and acetic anhydride (lOml) was stirred at 900C for 2 hours. After cooling to room temperature, the solution was treated with 15% aqueous ammonia (lOOml) and stirred for 5 hours. The product was isolated by filtration and purified by column chromatography to yield compound (XXIV). A 1Z solution of the product in polyhalogenated paraffins showed little or no colouration on base paper. #max = 649 nm. Example 168 Preparation of 2 ,3-dipbenyl-7-(4-N,N-dimethylaminophenyl)- 7-(julolidin-9-yl)-5,7-dihydrofuro [3,4-b]pyrazin-5-one (XXV) > EMI41.1 A mixture of (4-N,N-dimethylaminophenyl)-(2-carboxy-5,6- diphenylpyrazin-3-yl)ketone (0.5g) (prepared by the method of Example 60), julolidine (0.4g) and acetic anhydride (5ml) was stirred at 850C for 3 hours. After cooling to room temperature, the solution was treated with 15Z aqueous ammonia (70ml) and stirred for 3 hours. The product was filtered off and purified by column chromatography to yield compound (XXV). A 1% solution of the product in nionoisopropylbiphenyl showed little or no carbon formation when applied to base paper. Amax 3 650nm. Example 169 Preparation of Heat-Sensitive Recording Paper 4 Parts of the colour former of Example 94 were milled with 10 parts of a 10% aqueous solution of polyvinyl alcohol and 6 parts of water to give Dispersion A. Separately, 4 parts of bisphenol A were milled with 10 parts of a 10% aqueous solution of polyvinyl alcohol and 6 parts of water to give Dispersion B. 1 Part of Dispersion A and 6 parts of Dispersion B were mixed, and the resulting mixture was coated onto a paper sheet support and dried to give heat-sensitive recording paper. When heat was applied by a heat pen to this heat-sensitive recording paper a green coloured image was produced. This coloured image has excellent light-fastness. Example 170 Preparation of Pressure-Sensitive Copy Paper The colour former of Example 23 was dissolved in an alkylnaphthalene solvent, and microencapsulated by a conventional method. The microcapsules were coated onto the surface of a paper sheet support, and dried to give an upper sheet (CB sheet). Correspondingly, a solid phenolic resin was coated onto the surface of a paper sheet support to give a lower sheet (CF sheet). When the CB sheet and the CF sheet were superposed so that both the coated surfaces faced each other, writing pressure on the upper surface of the CB sheet e.g. with a pen, gave a blue copied image on the lower sheet. This copied image is extremely lightfast.

Claims: CLAIMS 1. A chromogenic pyrazine compound of formula: EMI43.1 wherein X and X , which may be the same or different, are each selected from hydrogen, alkyl, optionally substituted alkyl, alkoxy, carboxyalkyl, optionally substituted aryl, optionally substituted heteroaromatic, optionally substituted aralkyl or dialkylamino, provided that both XÚ and Xê are not both hydrogen at the same time; and A1 and A , which may be the same or different, are each: (i) a heterocyclic ring system having an aryl group annellated through a conjugated nitrogen linkage; or (ii) a homocyclic aryl group having a substituent -NR 1R2 wherein R1 and R2 are separately hydrogen or an optionally substituted alkyl, aryl or aralkyl group or both R1 and R2 together with the nitrogen atom to which they are joined form a nitrogen-linked ring, provided that R1 and R2 are not both hydrogen at the same time. 2. A chromogenic pyrazine compound according to claim 1 wherein each of X1 and X2 is optionally substituted C1 8 alkyl or optionally substituted phenyl. 3. A chromogenic pyrazine compound according to claim 2 wherein X1 and X2 are identical. 4. A chromogenic pyrazine compound according to claim 3 where in XÚ and Xê are methyl or phenyl. 5. A chromogenic pyrazine compound according to claim 1 wherein A1 is a group of the formula: EMI44.1 wherein R3 and R4 are each independently hydrogen, optionally substituted alkyl, optionally substituted aryl or optionally substituted aralkyl and P is hydrogen, alkyl, alkoxy, or halogen; and A2 is also a group of Formula (Il) or is a group selected from groups of the formulae: EMI44.2 wherein P and P', which may be the same or different, are optional substituents having the meaning given above for P; and R5 is hydrogen, alkyl, aryl or aralkyl; EMI45.1 wherein P is an optional substituent having the meaning given above, R6 is hydrogen, alkyl, aryl or aralkyl, and the groups R7 to R12 are hydrogen, alkyl, aryl or aralkyl; EMI45.2 wherein P is an optional substituent having the meaning given above, R25 is hydrogen or more preferably alkyl, aryl or aralkyl and the groups R26 and R27 are hydrogen, alkyl, aryl or aralkyl; EMI46.1 wherein P is an optional substituent having the meaning given above, and the groups R13 to R24 are hydrogen, alkyl, aryl or aralkyl; ; EMI46.2 wherein Q is hydrogen, alkyl, alkoxy, acylamino or halogen, and R1 and R2 are each independently hydrogen or an optionally substituted alkyl, aryl or aralkyl group or both R1 and R2 together with the nitrogen atom to which they are joined form a nitrogen-linked ring, provided that R1 and R2 are not both hydrogen at the same time; and EMI47.1 wherein Q, and R1 and R2 have the meanings given above. 6. A chromogenic compound according to claim 5 wherein each of R1, R2, R3, R4, R5, R6 and R25 is C1-6 alkyl, benzyl or phenyl. 7. A chromogenic pyrazine compound according to claim 1 wherein AÚ is a group of the formula: EMI47.2 wherein Q is hydrogen, alkyl, alkoxy, acylamino or halogen, and R1 and R2 are each independently hydrogen or an optionally substituted alkyl, aryl or aralkyl group or both R1 and R2 together with the nitrogen atom to which they are joined form a nitrogen-linked ring, provided that R1 and R2 are not both hydrogen at the same time; and A2 is also a group of formula (VI) or is a group selected from groups of the formulae: EMI48.1 wherein P and P', which may be the same or different, are optional substituents having the meaning given above for P; and R5 is hydrogen, alkyl, aryl or aralkyl; EMI48.2 wherein P is an optional substituent having the meaning given above, R6 is hydrogen, alkyl, aryl or aralkyl, and the groups R7 to R12 are hydrogen, alkyl, aryl or aralkyl; EMI49.1 wherein P is an optional substituent having the meaning given above, R25 is hydrogen or more preferably alkyl, aryl or aralkyl and the groups R26 and R27 are hydrogen, alkyl, aryl or aralkyl; EMI49.2 wherein P is an optional substituent having the meaning given above, and the groups R13 to R24 are hydrogen, alkyl, aryl or aralkyl; and EMI49.3 wherein Q, and R1 and R2 have the meanings given above. 8. A chromogenic compound according to claim 8 wherein each of R1, R2, R3, R4, R5, R6 and R25 is C1-6 alkyl, benzyl or phenyl. 9. A method for the preparation of a chromogenic pyrazine compound as defined in claim 1 which comprises reacting a compound of the formula: EMI50.1 with a compound of the formula A2H in the presence of an acid condensing agent, the symbols X1, X2, A1 and A2 having the meanings given in claim 1. 10. Pressure-sensitive or heat-sensitive recording material which contains a chromogenic pyrazine compound as defined in claim 1.

Inventors: HALL, NIGEL
Applicants: IMPERIAL CHEMICAL INDUSTRIES PLC
Application year: 1986
Main classification: C07D491
IPC codes: C07D519, B41M5, C07D491, C09B11