Dyes and dye-donor elements for use in thermal dye sublimation transfer

The present invention relates to dye-donor elements for use according to thermal dye sublimation transfer and to novel dyes for use in said dye-donor elements.
Thermal dye sublimation transfer is a recording method in which a dye-donor element provided with a dye layer containing sublimable dyes having heat transferability is brought into contact with a receiver sheet and selectively, in accordance with a pattern information signal, heated with a thermal printing head provided with a plurality of juxtaposed heat-generating resistors, whereby dye from the selectively heated regions of the dye-donor element is transferred to the receiver sheet and forms a pattern thereon, the shape and density of which is in accordance with the pattern and intensity of heat applied to the dye-donor element.
A dye-donor element for use according to thermal dye sublimation transfer usually comprises a very thin support e.g. a polyester support, one side of which is covered with a dye layer, which contains the printing dyes. Usually an adhesive or subbing layer is provided between the support and the dye layer. Normally the opposite side is covered with a slipping layer that provides a lubricated surface against which the thermal printing head can pass without suffering abrasion. An adhesive layer may be provided between the support and the slipping layer.
The dye layer can be a monochrome dye layer or it may comprise sequential repeating areas of different dyes like e.g. cyan, magenta and yellow dyes. When a dye-donor element containing three or more primary color dyes is used, a multicolor image can be obtained by sequentially performing the dye transfer process steps for each color
Any dye can be used in such a dye layer provided it is easily transferable to the dye-image-receiving layer of the receiver sheet by the action of heat.
Typical and specific examples of dyes for use in thermal dye sublimation transfer have been described in, e.g., EP 209990, EP 209991, EP 216483, EP 218397, EP 227095, EP 227096, EP 229374, EP 235939. EP 247737, EP 257577, EP 257580, EP 258856, EP 279330, EP 279467. EP 285665, U.S. Pat. Nos. 4,743,582, 4,753,922, 4,753,923, 4,757,046, 4,769,360, 4,771,035, JP 84/78894, JP 84/78895, JP 84/78896, JP 84/227490, JP 84/227948, JP 85/27594, JP 85/30391, JP 85/229787, JP 85/229789, JP 85/229790, JP 85/229791, P 85/229792, JP 85/229793, JP 85/229795, JP 86/41596, JP 86/268493, JP 86/268494, JP 86/268495 and JP 86/284489.
It is an object of the present invention to provide novel dye-donor elements for use according to thermal dye sublimation transfer printing.
It is another object of the present invention to provide novel dyes which may be used in said dye-donor elements.
Other objects will become apparent from the description hereinafter.
In accordance with the present invention a dye-donor element for use according to thermal dye sublimation transfer is provided, said dye-donor element comprising a support having thereon a dye layer containing a dye characterized in that said dye corresponds to the following formula ##STR2## wherein Z represents CN, COOR.sup.1 or CONR.sup.2 R.sup.3 ;
R.sup.1 R.sup.2 and R.sup.3 each independently represent hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, or R.sup.2 and R.sup.3 together represent the necessary atoms to close a heterocyclic nucleus or substituted heterocyclic nucleus;
Y represents OR.sup.4 NR.sup.5 R.sup.6 or CN;
R.sup.4 represents hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, SO.sub.2 R.sup.7, COR.sup.7, CSR.sup.7, POR.sup.7 R.sup.8 ;
R.sup.5 and R.sup.6 each independently has one of the significances given to R.sup.4 or represent substituted or unsubstituted amino, or R.sup.5 and R.sup.6 together represent the necessary atoms to close a heterocyclic nucleus or substituted heterocyclic nucleus, including a heterocyclic nucleus with an aliphatic or aromatic ring fused-on;
R.sup.7 and R.sup.8 each independently represent substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl, substituted or unsubstituted alkyloxy, substituted or unsubstituted aryloxy, substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio, substituted or unsubstituted amino or a substituted or unsubstituted heterocyclic group or R.sup.7 and R.sup.8 together represent the necessary atoms to close 5- or 6-membered ring;
X represents N--Ar, N--Het, CR.sup.9 R.sup.1O, N--NR.sup.11 R.sup.12 or N--N.dbd.CR.sup.13 R.sup.14 ;
Ar represents an aromatic nucleus substituted in para position by a substitutent chosen from the group consisting of substituted or unsubstituted amino, substituted or unsubstituted alkyloxy, substituted or unsubstituted aryloxy, substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio, hydroxy, mercapto;
Het represents a substituted or unsubstituted heterocyclic ring;
R.sup.9 and R.sup.10 each independently represents hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, a substituted or unsubstituted heterocyclic ring, cyano, halogen SO.sub.2 R.sup.7, COR.sup.7, CSR.sup.7, POR.sup.7 R.sup.8 or R.sup.9 and R.sup.10 together represent the necessary atoms to close a substituted or unsubstituted ring including a substituted or unsubstituted heterocyclic ring;
R.sup.11 represents a substituted or unsubstituted aromatic ring, including a substituted or unsubstituted aromatic heterocyclic ring;
R.sup.12 has one of the significances given to R.sup.4 and
R.sup.13 and R.sup.14 each independently represent hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, or R.sup.13 and R.sup.14 together represent the necessary atoms to close a substituted or unsubstituted heterocyclic nucleus, including a heterocyclic nucleus with an aliphatic or aromatic ring fused-on.
According to a special embodiment of this invention wherein X represents N--Ar, the dyes correspond to general formula (I) ##STR3## wherein Z and Y are defined as hereinbefore;
R.sup.15, R.sup.16, R.sup.18 and R.sup.19 each independently represent hydrogen substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted alkyloxy, substituted or unsubstituted aryloxy, substituted or unsubstituted carbonamido, substituted or unsubstituted sulfamido, hydroxy, halogen, NH--SO.sub.2 R.sup.7, NH--COR.sup.7, O--SO.sub.2 R.sup.7, O--COR.sup.7, R.sup.7 being as defined hereinbefore, or R.sup.15 and R.sup.16 together and/or R.sup.18 and R.sup.19 together represent the necessary atoms to close (a) substituted or unsubstituted ring(s) fused-on the benzene ring or R.sup.16 and/or R.sup.18 together with R.sup.21 and/or R.sup.22 represent the necessary atoms to close a substituted or unsubstituted heterocyclic ring fused-on the benzene ring;
R.sup.17 represents OR.sup.20, SR.sup.20 or NR.sup.21 R.sup.22 ;
R.sup.20 represents hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl and
R.sup.21 and R.sup.22 each independently has one of the significances given to R.sup.20 or represent a substituted or unsubstituted heterocyclic group or R.sup.21 and R.sup.22 together represent the necessary atoms to close a substituted or unsubstituted heterocyclic ring or R.sup.21 and/or R.sup.22 together with R.sup.16 and/or R.sup.18 represent the necessary atoms to close a substituted or unsubstituted heterocyclic ring fused-on the benzene ring.
Hereinafter * represents the linking position.
Representative examples of dyes according to formula (I) are listed below in table 1.
TABLE 1__________________________________________________________________________Z Y R.sup.15 R.sup.16 R.sup.17 R.sup.18 R.sup.19 no.__________________________________________________________________________CN N(CH.sub.2 C.sub.6 H.sub.5).sub.2 H H N(C.sub.2 H.sub.5).sub.2 H H I.1CN ##STR4## CH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.2CN OCH.sub.3 CH.sub.3 CH.sub.3 N(C.sub.2 H.sub.5).sub.2 CH.sub.3 CH.sub.3 I.3CN NHSO.sub.2 C.sub.6 H.sub.4 CH.sub.3 CH.sub.3 H ##STR5## H H I.4CN ##STR6## CH.sub.3 H ##STR7## H H I.5CN ##STR8## NHCOCH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.6CN ##STR9## H H ##STR10## H H I.7CN N(COOC.sub.2 H.sub.5).sub.2 CH.sub.3 H ##STR11## H H I.8COOCH.sub.3 ##STR12## CH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H CH.sub.3 I.9COOC.sub.2 H.sub.5 ##STR13## H H N(C.sub.4 H.sub.9).sub.2 H H I.10CN OSO.sub.2 N(CH.sub.3).sub.2 H H N(C.sub.3 H.sub.7).sub.2 H H I.11CN NHCOCHCH.sub.2 H H ##STR14## H H I.12CN NH.sub.2 NHCOCH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.13CN OCH.sub.2 C.sub.6 H.sub.5 H ##STR15## H I.14CN ##STR16## H ##STR17## H H I.15CN N(COOC.sub.2 H.sub.5).sub.2 H H N(C.sub.2 H.sub.5).sub.2 H H I.16CN CN NHCOC(CH.sub.3).sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.17CN NHCOC(CH.sub.3)CH.sub.2 CH.sub.3 CH.sub.3 N(C.sub.2 H.sub.5).sub.2 CH.sub.3 CH.sub.3 I.18CN N(COOC.sub.2 H.sub.5).sub.2 CH.sub.3 H ##STR18## H H I.19CN ##STR19## CH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.20CN ##STR20## H H N(C.sub.2 H.sub.5).sub.2 H H I.21CN ##STR21## NHCOCH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.22CN NHCOOCH.sub.3 H H ##STR22## H H I.23CN ##STR23## CH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H CH.sub.3 I.24CN NH.sub.2 NHCOCH(CH.sub.3).sub.2 H N(C.sub.2 H.sub.5).sub.2 H H I.25CN NH.sub.2 H H N(C.sub.3 H.sub.7).sub.2 H H I.26CN NHCOC.sub.6 H.sub.5 H H ##STR24## H H I.27CN N(COOC.sub.2 H.sub.5).sub.2 NHCOCH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.28CN N(CH.sub.3).sub.2 H ##STR25## H I.29CN NHSO.sub.2 CH.sub.3 H H N(C.sub.2 H.sub.5).sub.2 H H I.30CN NH.sub.2 N(SO.sub.2 CH.sub.3).sub.2 H N(C.sub.2 H.sub.5).sub.2 H H I.31CN NH.sub.2 CH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.32CN OCH(CH.sub.3).sub.2 CH.sub.3 CH.sub.3 N(C.sub.2 H.sub.5).sub.2 CH.sub.3 CH.sub.3 I.33CN ##STR26## CH.sub.3 H ##STR27## H H I.34CN ##STR28## NHCOCH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.35CN N(COOC.sub.16 H.sub.33).sub.2 NHCOCH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.36CN N(COOC.sub.2 H.sub.5).sub.2 H ##STR29## H I.37CN ##STR30## H H N(C.sub.2 H.sub.5).sub.2 H H I.38CN NHCOOC.sub.4 H.sub.9 CH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H CH.sub.3 I.39CN NHCOC.sub.2 H.sub.5 H H N(C.sub.4 H.sub.9).sub.2 H H I.40CN OC.sub.6 H.sub.4 CH.sub.3 H H N(C.sub.3 H.sub.7).sub.2 H H I.41CN NH.sub.2 H H ##STR31## H H I.42CN OC(CH.sub.3).sub.3 NHCOCH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.43CN NHSO.sub.2 C.sub.6 H.sub.5 H ##STR32## H I.44CN NHCOOC(CH.sub.3).sub.3 H ##STR33## H H I.45CN NH.sub.2 NHCOC.sub.5 H.sub.11 H N(C.sub.2 H.sub.5).sub.2 H H I.46CN OCOCH.sub.3 CH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.47CN N(C.sub.3 H.sub.7).sub.2 CH.sub.3 CH.sub.3 N(C.sub.2 H.sub. 5).sub.2 CH.sub.3 CH.sub.3 I.48CN NH.sub.2 CH.sub.3 H ##STR34## H H I.49CN NHCOCH.sub.3 CH.sub.3 H ##STR35## H H I.50CN NH.sub.2 H H N(C.sub.2 H.sub.4 OH).sub.2 H H I.51CN ##STR36## H ##STR37## H I.52CN ##STR38## H H N(C.sub.4 H.sub.9).sub.2 H H I.53CN NHCOOCH.sub.2 C.sub.6 H.sub.5 CH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H CH.sub.3 I.54CN N(PO(OC.sub.6 H.sub.5).sub.2).sub. 2 H H N(C.sub.4 H.sub.9).sub.2 H H I.55COOCH.sub.3 NHCOCHCH.sub.2 H H N(C.sub.3 H.sub.7).sub.2 H H I.56CN OCOC.sub.3 H.sub.7 H H ##STR39## H H I.57COOC.sub.2 H.sub.5 N(COOC.sub.4 H.sub.9).sub.2 NHCOCH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.58COOCH.sub.3 N(CH.sub.3).sub.2 H ##STR40## H I.59CN N(COOCH.sub.3).sub.2 H ##STR41## H H I.60CN NH.sub.2 H H N(C.sub.2 H.sub.5).sub.2 H H I.61CN NH.sub.2 NHCOC.sub.7 H.sub.15 H N(C.sub.2 H.sub.5).sub.2 H H I.62CN NHPO(OC.sub.6 H.sub.5).sub.2 CH.sub.3 CH.sub.3 N(C.sub.2 H.sub.5).sub.2 CH.sub.3 CH.sub.3 I.63CN NH.sub.2 H H ##STR42## H H I.64CN N(COOC.sub.4 H.sub.9).sub.2 H H ##STR43## H H I.65COOC.sub.2 H.sub.5 N(C.sub.2 H.sub.4 OH).sub.2 H H N(C.sub.2 H.sub.4 OH).sub.2 H H I.66COOCH.sub.3 NHCOOCH.sub.3 H H ##STR44## H H I.67CN ##STR45## H H ##STR46## H H I.68CN N(COOC.sub.2 H.sub.5).sub.2 CH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H CH.sub.3 I.69CN NH.sub.2 CH(CH.sub.3).sub.2 H N(CH.sub.3).sub.2 H H I.70COOCH.sub.3 OH H H N(C.sub.3 H.sub.7).sub.2 H H I.71COOC.sub.2 H.sub.5 NHCOOCH.sub.2 C.sub.6 H.sub.5 H H ##STR47## H H I.72CN NHC.sub.6 H.sub.5 NHCOCH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.73CN N(COOC.sub.4 H.sub.9).sub.2 H ##STR48## H I.74CN OCOC.sub.15 H.sub.31 H ##STR49## H H I.75CN ##STR50## H H N(C.sub.2 H.sub.5).sub.2 H H I.76CN N(COOC.sub.2 H.sub.5).sub.2 CH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.77COOC.sub.2 H.sub.5 ##STR51## CH.sub.3 CH.sub.3 N(C.sub.2 H.sub.5).sub.2 CH.sub.3 CH.sub.3 I.78CN OSO.sub.2 C.sub.6 H.sub.5 CH.sub.3 H ##STR52## H H I.79COOCH.sub.3 NHCOC.sub.2 H.sub.5 CH.sub.3 H ##STR53## H H I.80CN NHSO.sub.2 C.sub.6 H.sub.4 NHCOCH.sub.3 H H N(C.sub.2 H.sub.5).sub.2 H H I.81CN NH.sub.2 H H ##STR54## H H I.82CN ##STR55## NHCOCH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.83CN N(COOC(CH.sub.3).sub.3).sub.2 CH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H CH.sub.3 I.84CN NH.sub.2 H H N(C.sub.4 H.sub.9).sub.2 H H I.85CN OSO.sub.2 C.sub.6 H.sub.4 CH.sub.3 H H N(C.sub.3 H.sub.7).sub.2 H H I.86CN NHC.sub.2 H.sub.4 OH H H ##STR56## H H I.87COOCH.sub.3 NHSO.sub.2 CH.sub.3 NHCOCH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.88COOC.sub.2 H.sub.5 NHCOOC(CH.sub.3).sub.3 H ##STR57## H I.89CN N(COOCH.sub.2 C.sub.6 H.sub.5).sub.2 H ##STR58## H H I.90CN ##STR59## H H N(C.sub.2 H.sub.5).sub.2 H H I.91CN N(COOC.sub.4 H.sub.9).sub.2 NHCOCH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.92CN N(COOC.sub.4 H.sub.9).sub.2 NHCOC.sub.5 H.sub.11 H N(C.sub.2 H.sub.5).sub.2 H H I.93CN ##STR60## NHCOC.sub.5 H.sub.11 H N(C.sub.2 H.sub.5).sub.2 H H I.94CN ##STR61## NHCOC.sub.5 H.sub.11 H N(C.sub.2 H.sub.5).sub.2 H H I.95CN N(COOCH.sub.2 CH(CH.sub.3).sub.2).sub.2 NHCOCH.sub.3 H N(C.sub.2 H.sub.5).sub. H H I.96CN NH.sub.2 H ##STR62## H I.97CN ##STR63## H H N(C.sub.2 H.sub.5).sub.2 H H I.98CN ##STR64## CH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H CH.sub.3 I.99CN N(COOC.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCO).sub.2 H H N(C.sub.4 H.sub.9).sub.2 H H I.100COOCH.sub.3 NHCOC.sub.6 H.sub.5 H H N(C.sub.3 H.sub.7).sub.2 H H I.101COOC.sub.2 H.sub.5 ##STR65## H H ##STR66## H H I.102CN NHCOOC.sub.4 H.sub.9 NHCOCH.sub.3 H N(C.sub.2 H.sub. 5).sub.2 H H I.103CN N(C.sub.2 H.sub.4 OH).sub.2 H ##STR67## H I.104CN N(COO(C.sub.2 H.sub.4 O).sub.3 CO).sub.2 H ##STR68## H H I.105CN ##STR69## H H N(C.sub.2 H.sub.5).sub.2 H H I.106CN N(COOCH.sub.2 CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9).sub.2 NHCOCH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.107CN ##STR70## NHCOC(CH.sub.3).sub.3 H N(C.sub.2 H.sub.5).sub. H H I.108CN ##STR71## H H ##STR72## H H I.109CN ##STR73## CH.sub.3 H ##STR74## H H I.110CN N(COOC.sub.4 H.sub.9).sub.2 NHCOCH(CH.sub.3).sub.2 H N(C.sub.2 H.sub.5).sub.2 H H I.111CN NH.sub.2 CH.sub.3 ##STR75## H I.112CN ##STR76## NHCOCH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.113CN ##STR77## N(SO.sub.2 CH.sub.3).sub.2 H N(C.sub.2 H.sub.5).sub.2 H H I.114CN ##STR78## H H ##STR79## H H I.115CN ##STR80## H H N(C.sub.2 H.sub.5).sub.2 H H I.116CN ##STR81## NHCOC.sub.5 H.sub.11 H N(C.sub.2 H.sub.5).sub.2 H H I.117COOC.sub.2 H.sub.5 NH.sub.2 NHCOCH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.118CN ##STR82## CH.sub.3 ##STR83## H I.119COOCH.sub.3 NHCOC.sub.4 H.sub.9 H ##STR84## H H I.120CN NH.sub.2 H H ##STR85## H H I.121CN NH.sub.2 OC.sub.2 H.sub.5 H N(C.sub.2 H.sub.5).sub.2 H H I.122CN N(COCH.sub.3).sub.2 H H N(C.sub.2 H.sub.5).sub.2 H H I.123CN ##STR86## H H N(C.sub.2 H.sub.5).sub.2 H H I.124CN ##STR87## NHCOCH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.125CN ##STR88## H H N(C.sub.2 H.sub.5).sub.2 H H I.126CN ##STR89## CH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.127CN ##STR90## CH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.128CN NHCOOC.sub.2 H.sub.5 H H N(C.sub.2 H.sub.5).sub.2 H H I.129CN ##STR91## NHCOC(CH.sub.3).sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.130CN N(COOC.sub.2 H.sub.5).sub.2 NHCOC(CH.sub.3).sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.131CN N(COOCH.sub.2 C.sub.6 H.sub.5).sub.2 NHCOC(CH.sub.3).sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.132CN N(COOCH.sub.2 C.sub.6 H.sub.5).sub.2 H H N(C.sub.2 H.sub.5).sub. H H I.133CN ##STR92## NHCOCH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.134CN ##STR93## NHCOCH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.135CN ##STR94## NHCOC(CH.sub.3).sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.136CN ##STR95## NHCOC(CH.sub.3).sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.137CN ##STR96## NHCOCH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.138CN ##STR97## NHCOC(CH.sub.3).sub.3 H N(C.sub.2 H.sub.5).sub. H H I.139CN NH.sub.2 NHCOC(CH.sub.3).sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.140CN NH.sub.2 OC.sub.2 H.sub.5 H N(C.sub.4 H.sub.9).sub.2 H H I.141CN ##STR98## NHCOCH.sub.3 H N(C.sub.2 H.sub.5).sub.2 H H I.142CN ##STR99## NHCOCH.sub.3 ##STR100## H I.143__________________________________________________________________________
Dyes according to formula (I) can be obtained by oxidative coupling between a malononitrile dimer and a p-phenylenediamine compound or by condensation of a malononitrile dimer and a nitrosoaryl compound.
The synthesis of malononitrile dimers is described by A. J. Fatiadi in Synthesis, 1978, pages 165 to 204 and by F. Freeman in Chemical Reviews, Vol. 69, 1969, pages 519 to 624.
The synthesis of dyes according to formula (I) wherein Y represents NH.sub.2 is described by H. Junek, B. Thierrichter and P. Wibmer in Monatshefte fur Chemie, Vol. 110, 1979, pages 483 to 492 and in U.S. Pat. No. 2,926,187. Dyes according to formula (I) wherein Y is not NH.sub.2 have not been described before.
Among the dyes according to formula (I) those wherein Z is CN and Y is NR.sup.5 R.sup.6 are preferred; and among those the dyes wherein R.sup.17 is NR.sup.21 R.sup.22 are preferred.
The dyes according to the present invention wherein X represents CR.sup.9 R.sup.10, can be represented by the following formula (II) ##STR101## wherein Z, Y, R.sup.9 and R.sup.10 are defined as hereinbefore.
In a particular type of dye according to formula (II), R.sup.9 and R.sup.10 together with the C atom to which they are attached represent the necessary atoms to close a pyrone-type nucleus represented by ##STR102## wherein V represents O, S, Se, Te, NR.sup.27, preferably O or NR.sup.27 ;
R.sup.23, R.sup.24, R.sup.25 and R.sup.26 each independently represent hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, alkyloxycarbonyl, aryloxycarbonyl, substituted or unsubstituted carbonamido, or R.sup.23 and R.sup.24 together and/or R.sup.25 and R.sup.26 together represent the necessary atoms to close (a) substituted or unsubstituted ring(s) fused-on the pyrone-type nucleus and
R.sup.27 represents hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl or amino.
Representative examples of dyes according to formula (II) are listed below in table 2.
TABLE 2__________________________________________________________________________Z Y R.sup.9 R.sup.10 no.__________________________________________________________________________COOCH.sub.3 OCOC(CH.sub.3).sub.3 COC.sub.6 H.sub.5 C.sub.6 H.sub.5 II.1CN NHCOOC(CH.sub.3).sub.3 COC.sub.6 H.sub.4 N(CH.sub.3).sub.2 C.sub.6 H.sub.5 II.2CN ##STR103## COC.sub.6 H.sub.4 N(C.sub.2 H.sub.5).sub.2 C.sub.6 H.sub.5 II.3CN NH.sub.2 ##STR104## H II.4CN ##STR105## ##STR106## H II.5CN NH.sub.2 C.sub.6 H.sub.4 N(CH.sub.3).sub.2 H II.6CN NH.sub.2 C.sub.6 H.sub.4 N(C.sub.2 H.sub.5).sub.2 H II.7CN NH.sub.2 ##STR107## H II.8CN NH.sub.2 CHCHC.sub.6 H.sub.4 N(CH.sub.3).sub.2 H II.9CN ##STR108## CHCHC.sub.6 H.sub.4N(CH.sub.3).sub.2 H II.10CN ##STR109## ##STR110## CN II.11CN NHCOCH.sub.3 ##STR111## H II.12CN ##STR112## ##STR113## II.13CN ##STR114## ##STR115## II.14CN N(COOC.sub.2 H.sub.5).sub.2 ##STR116## II.15COOCH.sub.3 N(COOCH.sub.3).sub.2 ##STR117## H II.16CN NH.sub.2 ##STR118## H II.17CN ##STR119## ##STR120## II.18CN ##STR121## ##STR122## II.19CN ##STR123## ##STR124## II.20CN N(COOC.sub.2 H.sub.5).sub.2 ##STR125## II.21CN ##STR126## ##STR127## II.22CN ##STR128## ##STR129## H II.23CN NH.sub.2 C.sub.6 H.sub.4 OCH.sub.3 H II.24COOC.sub.2 H.sub.5 N(COOC.sub.2 H.sub.5).sub.2 ##STR130## H II.25CN N(COOC.sub.2 H.sub.5).sub.2 ##STR131## H II.26CN N(COOC.sub.16 H.sub.33).sub.2 ##STR132## II.27CN ##STR133## ##STR134## II.28COOC.sub.2 H.sub.5 NHSO.sub.2 C.sub.6 H.sub.5 ##STR135## H II.29CN NH.sub.2 C.sub.6 H.sub.4 N(CH.sub.2 COOCH.sub.3).sub.2 H II.30CN OSO.sub.2 CH.sub.3 ##STR136## H II.31CN N(COOCH.sub.3).sub.2 ##STR137## H II.32CN NHCH.sub.2 CH(CH.sub.3).sub.2 ##STR138## H II.33CN ##STR139## ##STR140## H II.34CN N(COOC.sub.2 H.sub.5).sub.2 CHCHC.sub.6 H.sub.4 N(CH.sub.3).sub.2 H II.35CN N(COOC.sub.4 H.sub.9).sub.2 ##STR141## II.36CN ##STR142## ##STR143## II.37CN N(COOC.sub.2 H.sub.5).sub.2 ##STR144## II.38CN N(COOC.sub.2 H.sub.5).sub.2 ##STR145## II.39CN ##STR146## ##STR147## II.40CN ##STR148## ##STR149## II.41CN ##STR150## COC.sub.6 H.sub.5 C.sub.6 H.sub.5 II.42CN ##STR151## COC.sub.6 H.sub.4 N(CH.sub.3).sub.2 C.sub.6 H.sub.5 II.43CN N(COOC(CH.sub.3).sub.3).sub.2 COC.sub.6 H.sub.4 N(C.sub.2 H.sub.5).sub.2 C.sub.6 H.sub.5 II.44CN N(COOC.sub.2 H.sub.5).sub.2 C.sub.6 H.sub.4 N(C.sub.2 H.sub.5).sub.2 H II.45CN ##STR152## COC.sub.6 H.sub.4 N(CH.sub.3).sub.2 C.sub.6 H.sub.4 N(CH.sub.3).sub .2 II.46COOCH.sub.3 NH(C.sub.2 H.sub.4 OH).sub.2 C.sub.6 H.sub.4 N(CH.sub.3).sub.2 H II.47COOCH.sub.3 ##STR153## C.sub.6 H.sub.4 N(C.sub.2 H.sub.5).sub.2 H II.48COOC.sub.2 H.sub.5 N(COOC.sub.4 H.sub.9).sub.2 ##STR154## H II.49CN ##STR155## ##STR156## II.50CN ##STR157## ##STR158## CN II.51CN ##STR159## ##STR160## H II.52CN OH ##STR161## H II.53COOCH.sub.3 ##STR162## ##STR163## H II.54CN N(COOC.sub.2 H.sub.5).sub.2 ##STR164## II.55COOC.sub.2 H.sub.5 OH ##STR165## H II.56CN NHPO(OC.sub.6 H.sub.5).sub.2 ##STR166## H II.57COOCH.sub.3 NHSO.sub.2 CH.sub.3 C.sub.6 H.sub.4 N(C.sub.6 H.sub.5).sub.2 H II.58CN N(COOC.sub.2 H.sub.5).sub.2 ##STR167## H II.59CN ##STR168## C.sub.6 H.sub.4 OCH.sub.3 H II.60CN N(COOCH.sub.2 CH(CH.sub.3).sub.2).sub.2 ##STR169## H II.61CN OC(CH.sub.3).sub.3 ##STR170## H II.62CN NH.sub.2 ##STR171## H II.63CN ##STR172## ##STR173## H II.64CN N(COOC.sub.2 H.sub.5).sub.2 C.sub.6 H.sub.4 N(CH.sub.3).sub.2 H II.65CN OCH.sub.3 ##STR174## H II.66CN NH.sub.2 ##STR175## H II.67CN NHCO(CH.sub.3)CH.sub.2 ##STR176## H II.68CN OSO.sub.2 CH.sub.3 ##STR177## H II.69CN N(COOCH.sub.2 CH(CH.sub.3).sub.2).sub.2 C.sub.6 H.sub.4 N(CH.sub.2 COOCH.sub.3).sub.2 H II.70CN NH.sub.2 ##STR178## H II.71CN N(COOCH.sub.2 C.sub.6 H.sub.5).sub.2 ##STR179## II.72CN ##STR180## ##STR181## II.73CN ##STR182## ##STR183## II.74CN NH.sub.2 ##STR184## II.75CN ##STR185## ##STR186## II.76CN NH.sub.2 COC.sub.6 H.sub.5 C.sub.6 H.sub.5 II.77CN ##STR187## COC.sub.6 H.sub.4 N(CH.sub.3).sub.2 C.sub.6 H.sub.5 II.78CN NHSO.sub.2 C.sub.6 H.sub.4 CH.sub.3 COC.sub.6 H.sub.4 N(C.sub.2 H.sub.5).sub.2 C.sub.6 H.sub.5 II.79CN N(COOC.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCO).sub.2 COC.sub.6 H.sub.4 Cl C.sub.6 H.sub.4 Cl II.80COOC.sub.2 H.sub.5 NHCOC(CH.sub.3).sub.3 COC.sub.6 H.sub.4 N(CH.sub.3).sub.2 C.sub.6 H.sub.4 N(CH.sub.3).sub .2 II.81CN NH.sub.2 ##STR188## II.82CN OC.sub.6 H.sub.4 C.sub.16 H.sub.33 C.sub.6 H.sub.4 N(C.sub.2 H.sub.5).sub.2 H II.83CN ##STR189## ##STR190## H II.84CN ##STR191## ##STR192## H II.85CN NHCOOC.sub.2 H.sub.5 ##STR193## H II.86CN NHCOOC.sub.2 H.sub.5 ##STR194## H II.87CN NHCOCHCH.sub.2 ##STR195## H II.88CN ##STR196## ##STR197## H II.89CN N(CH.sub.2 C.sub.6 H.sub.5).sub.2 ##STR198## H II.90CN N(COOC.sub.2 H.sub.5).sub.2 C.sub.6 H.sub.4 N(CH.sub.2 COOCH.sub.3).sub.2 H II.91CN N(COOC.sub.2 H.sub.5).sub.2 ##STR199## H II.92CN N(CH.sub.2 C.sub.6 H.sub.5).sub.2 ##STR200## II.93CN N(C.sub.3 H.sub.7).sub.2 ##STR201## H II.94CN NHCOC.sub.15 H.sub.31 ##STR202## H II.95CN ##STR203## ##STR204## H II.96CN N(COO(C.sub.2 H.sub.4 O).sub.3 CO).sub.2 ##STR205## H II.97CN ##STR206## ##STR207## H II.98CN NHCOOC.sub.2 H.sub.5 ##STR208## H II.99CN N(COOC.sub.2 H.sub.5).sub.2 ##STR209## H II.100CN N(CH.sub.2 C.sub.6 H.sub.5).sub.2 ##STR210## H II.101COOCH.sub.3 ##STR211## ##STR212## H II.102CN N(COOC.sub.2 H.sub.5).sub.2 ##STR213## H II.103COOC.sub.2 H.sub.5 ##STR214## ##STR215## II.104CN NHCOOC(CH.sub.3).sub.3 ##STR216## II.105CN ##STR217## ##STR218## II.106CN ##STR219## ##STR220## II.107CN NH.sub.2 ##STR221## II.108CN ##STR222## ##STR223## II.109CN NH.sub.2 ##STR224## H II.110CN NH.sub.2 ##STR225## H II.111CN NH.sub.2 ##STR226## H II.112CN NH.sub.2 ##STR227## H II.113CN ##STR228## ##STR229## II.114CN N(COOC.sub. 4 H.sub.9).sub.2 ##STR230## II.115CN N(COOCH.sub.2 CH(CH.sub.3).sub.2).sub.2 ##STR231## II.116CN NHCOOCH.sub.2 CH(CH.sub.3).sub.2 ##STR232## II.117CN N(COOCH.sub.2 CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9).sub.2 ##STR233## II.118CN ##STR234## ##STR235## II.119CN ##STR236## ##STR237## II.120CN ##STR238## ##STR239## II.121CN ##STR240## ##STR241## II.122CN ##STR242## ##STR243## II.123CN N(COOC.sub.2 H.sub.5).sub.2 ##STR244## II.124CN N(COOC.sub.2 H.sub.5).sub.2 ##STR245## II.125CN NH.sub.2 ##STR246## II.126CN NH.sub.2 ##STR247## H II.127CN NH.sub.2 ##STR248## H II.128CN NH.sub.2 ##STR249## H II.129CN NH.sub.2 ##STR250## H II.130CN N(COOC.sub.2 H.sub.5).sub.2 ##STR251## H II.131CN ##STR252## C.sub.6 H.sub.4 N(C.sub.2 H.sub.5).sub.2 H II.132CN ##STR253## C.sub.6 H.sub.4 N(C.sub.2 H.sub.5).sub.2 H II.133__________________________________________________________________________
Dyes according to formula (II) can be obtained by addition of a malononitrile dimer to an electrophilic center R.sup.9 --CO--R.sup.10 such as aldehydes, ketones, enonen, esters, etc. This addition can be carried out using a base as catalyst.
The synthesis of dyes according to formula (II) wherein Y represents NH.sub.2, is described by H. Junek, B. Hornischer and H. Hambock in Monatshefte fur Chemie, Vol. 100, 1969, pages 503 to 509.
Dyes according to formula (II) wherein Y is not NH.sub.2 or wherein R.sup.9 and R.sup.10 together with the C atom to which they are attached represent the necessary atoms to close a pyrone-type nucleus have not been described before. The synthesis of pyrones is described in Organic Synthesis, Vol. 46, 1966 pages 57 to 62.
Among the dyes according to formula (II) those wherein Z is CN and Y is NR.sup.5 SR.sup.6 are preferred; and among those the dyes wherein R.sup.9 and R.sup.10 together with the C atom to which they are attached represent the necessary atoms to close a pyrone-type nucleus are preferred.
The dyes according to the present invention wherein X represents N--NR.sup.11 R.sup.12, can be represented by the following formula (III) ##STR254## wherein Z, Y, R.sup.11 and R.sup.12 are defined as hereinbefore.
Representative examples of dyes according to formula (III) are listed below in table 3.
TABLE 3__________________________________________________________________________Z Y R.sup.11 R.sup.12 no.__________________________________________________________________________CN NH.sub.2 ##STR255## H III.1CN NH.sub.2 ##STR256## H III.2CN NH.sub.2 ##STR257## H III.3CN NH.sub.2 ##STR258## H III.4CN NH.sub.2 ##STR259## H III.5CN NH.sub.2 ##STR260## H III.6CN NH.sub.2 ##STR261## H III.7CN NH.sub.2 ##STR262## H III.8CN NH.sub.2 ##STR263## H III.9CN N(COOC.sub.2 H.sub.5).sub.2 ##STR264## COOC.sub.2 H.sub.5 III.10CN NHCOOC.sub.2 H.sub.5 ##STR265## COOC.sub.2 H.sub.5 III.11CN NHCH(CH.sub.3).sub.2 ##STR266## SO.sub.2 C.sub.6 H.sub.5 III.12CN NHCOCH.sub.3 ##STR267## H III.13CN NHCOOC.sub.4 H.sub.9 ##STR268## COOC.sub.4 H.sub.9 III.14CN ##STR269## ##STR270## CH.sub.3 III.15CN ##STR271## ##STR272## CH.sub.3 III.16CN NHCOC.sub.2 H.sub.5 ##STR273## COC.sub.2 H.sub.5 III.17CN ##STR274## ##STR275## H III.18CN N(COOC.sub.2 H.sub.5).sub.2 ##STR276## COOC.sub.2 H.sub.5 III.19CN N(COOCH.sub.3).sub.2 ##STR277## COOCH.sub.3 III.20CN ##STR278## ##STR279## H III.21CN N(COOC.sub.4 H.sub.9).sub.2 ##STR280## COOC.sub.4 H.sub.9 III.22CN NHCOCH.sub.3 ##STR281## COCH.sub.3 III.23CN N(CH.sub.3).sub.2 ##STR282## CH.sub.3 III.24CN ##STR283## ##STR284## H III.25__________________________________________________________________________
Dyes according to formula (III) can be obtained by addition of a malononitrile dimer to a diazonium compound. This addition can be carried out using a base as catalyst.
The synthesis of these dyes is described in DE 2922227 and in Zeitschrift fur Chemie, Vol. 29, 1989, pages 66 to 67 for reactions with malononitrile.
The dyes according to the present invention wherein X represents N--N.dbd.CR.sup.13 R.sup.14, can be represented by the following formula (IV) ##STR285## wherein Z, Y, R.sup.13 and R.sup.14 are defined as hereinbefore.
In a particular type of dye according to formula (IV), R.sup.13 and R.sup.14 together with the C atom to which they are attached represent the necessary atoms to close a heterocyclic nucleus represented by ##STR286## wherein n represents 0, 1 or 2;
P and Q (same or different) represent a methine group or a substituted methine group;
R.sup.28 represents substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl and
A represents a bond or the necessary atoms to close a nitrogen-containing heterocyclic nucleus including said nucleus in substituted form.
Representative examples of dyes according to formula (IV) are listed below in table 4.
TABLE 4__________________________________________________________________________Z Y R.sup.13 R.sup.14 no.__________________________________________________________________________CN NH.sub.2 ##STR287## IV.1CN ##STR288## ##STR289## IV.2CN ##STR290## ##STR291## IV.3CN ##STR292## ##STR293## IV.4CN ##STR294## ##STR295## IV.5CN ##STR296## ##STR297## IV.6CN N(COOC.sub.2 H.sub.5).sub.2 ##STR298## IV.7CN ##STR299## ##STR300## IV.8CN ##STR301## ##STR302## IV.9COOC.sub.2 H.sub.5 ##STR303## ##STR304## IV.10COOC.sub.2 H.sub.5 ##STR305## ##STR306## IV.11CN N(COOCH.sub.2 C.sub.6 H.sub.5).sub.2 ##STR307## IV.12CN ##STR308## ##STR309## IV.13CN OCH.sub.2 C.sub.6 H.sub.5 ##STR310## IV.14CN NH.sub.2 ##STR311## IV.15CN ##STR312## ##STR313## IV.16CN ##STR314## ##STR315## IV.17CN ##STR316## ##STR317## IV.18CN ##STR318## ##STR319## IV.19CN ##STR320## ##STR321## IV.20CN N(COOC.sub.2 H.sub.5).sub.2 ##STR322## IV.21CN ##STR323## ##STR324## IV.22CN ##STR325## ##STR326## IV.23COOC.sub.2 H.sub.5 ##STR327## ##STR328## IV.24COOC.sub.2 H.sub.5 ##STR329## ##STR330## IV.25CN N(COOCH.sub.2 C.sub.6 H.sub.5).sub.2 ##STR331## IV.26CN ##STR332## ##STR333## IV.27CN OCH.sub.2 C.sub.6 H.sub.5 ##STR334## IV.28CN NH.sub.2 ##STR335## IV.29CN ##STR336## ##STR337## IV.30CN ##STR338## ##STR339## IV.31CN ##STR340## ##STR341## IV.32CN ##STR342## ##STR343## IV.33CN ##STR344## ##STR345## IV.34CN N(COOC.sub.2 H.sub.5).sub.2 ##STR346## IV.35CN ##STR347## ##STR348## IV.36CN ##STR349## ##STR350## IV.37COOC.sub.2 H.sub.5 ##STR351## ##STR352## IV.38COOC.sub.2 H.sub.5 ##STR353## ##STR354## IV.39CN N(COOCH.sub.2 C.sub.6 H.sub.5).sub.2 ##STR355## IV.40CN ##STR356## ##STR357## IV.41CN OCH.sub.2 C.sub.6 H.sub.5 ##STR358## IV.42CN NH.sub.2 ##STR359## IV.43CN ##STR360## ##STR361## IV.44CN ##STR362## ##STR363## IV.45CN ##STR364## ##STR365## IV.46CN ##STR366## ##STR367## IV.47CN ##STR368## ##STR369## IV.48CN N(COOC.sub.2 H.sub.5).sub.2 ##STR370## IV.49CN ##STR371## ##STR372## IV.50CN ##STR373## ##STR374## IV.51COOC.sub.2 H.sub.5 ##STR375## ##STR376## IV.52COOC.sub.2 H.sub.5 ##STR377## ##STR378## IV.53CN N(COOCH.sub.2 C.sub.6 H.sub.5).sub.2 ##STR379## IV.54CN ##STR380## ##STR381## IV.55CN OCH.sub.2 C.sub.6 H.sub.5 ##STR382## IV.56CN NH.sub.2 ##STR383## IV.57CN ##STR384## ##STR385## IV.58CN ##STR386## ##STR387## IV.59CN ##STR388## ##STR389## IV.60CN ##STR390## ##STR391## IV.61CN ##STR392## ##STR393## IV.62CN N(COOC.sub.2 H.sub.5).sub.2 ##STR394## IV.63CN ##STR395## ##STR396## IV.64CN ##STR397## ##STR398## IV.65COOC.sub.2 H.sub.5 ##STR399## ##STR400## IV.66COOC.sub.2 H.sub.5 ##STR401## ##STR402## IV.67CN N(COOCH.sub.2 C.sub.6 H.sub.5).sub.2 ##STR403## IV.68CN ##STR404## ##STR405## IV.69CN OCH.sub.2 C.sub.6 H.sub.5 ##STR406## IV.70CN NH.sub.2 ##STR407## IV.71CN ##STR408## ##STR409## IV.72CN ##STR410## ##STR411## IV.73CN ##STR412## ##STR413## IV.74CN ##STR414## ##STR415## IV.75CN ##STR416## ##STR417## IV.76CN N(COOC.sub.2 H.sub.5).sub.2 ##STR418## IV.77CN ##STR419## ##STR420## IV.78CN ##STR421## ##STR422## IV.79COOC.sub.2 H.sub.5 ##STR423## ##STR424## IV.80COOC.sub.2 H.sub.5 ##STR425## ##STR426## IV.81CN N(COOCH.sub.2 C.sub.6 H.sub.5).sub.2 ##STR427## IV.82CN ##STR428## ##STR429## IV.83CN OCH.sub.2 C.sub.6 H.sub.5 ##STR430## IV.84CN NH.sub.2 ##STR431## IV.85CN ##STR432## ##STR433## IV.86CN ##STR434## ##STR435## IV.87CN ##STR436## ##STR437## IV.88CN ##STR438## ##STR439## IV.89CN ##STR440## ##STR441## IV.90CN N(COOC.sub.2 H.sub.5).sub.2 ##STR442## IV.91CN ##STR443## ##STR444## IV.92CN ##STR445## ##STR446## IV.93COOC.sub.2 H.sub.5 ##STR447## ##STR448## IV.94COOC.sub.2 H.sub.5 ##STR449## ##STR450## IV.95CN N(COOCH.sub.2 C.sub.6 H.sub.5).sub.2 ##STR451## IV.96CN ##STR452## ##STR453## IV.97CN OCH.sub.2 C.sub.6 H.sub.5 ##STR454## IV.98CN NH.sub.2 ##STR455## IV.99CN ##STR456## ##STR457## IV.100CN ##STR458## ##STR459## IV.101CN ##STR460## ##STR461## IV.102CN ##STR462## ##STR463## IV.103CN ##STR464## ##STR465## IV.104CN N(COOC.sub.2 H.sub.5).sub.2 ##STR466## IV.105CN ##STR467## ##STR468## IV.106CN ##STR469## ##STR470## IV.107COOC.sub.2 H.sub.5 ##STR471## ##STR472## IV.108CN ##STR473## ##STR474## IV.109CN OCH.sub.2 C.sub.6 H.sub.5 ##STR475## IV.110CN NH.sub.2 ##STR476## IV.111__________________________________________________________________________
Dyes according to formula (IV) can be obtained by addition of a malononitrile dimer to a hydrazone compound in the presence of an oxidizing agent. The synthesis of hydrazone compounds is described in FR-P 1444971 and in GB-P 13016757.
Dyes according to formula (IV) have not been described before.
According to another embodiment of this invention wherein X represents N-Het with Het being a heterocyclic nucleus, the dyes correspond to general formula (V) ##STR477## wherein Z and Y are as defined hereinbefore;
R.sup.29 represents hydrogen or any substituent e.g. substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, carboxyl esters, carboxyl amides, amino, acylamino;
R.sup.30 represents hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl or a heterocyclic residue and
R.sup.31 represents hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, acyl or a heterocyclic residue.
Representative examples of dyes according to formula (V) are listed below in table 5.
TABLE 5______________________________________Z Y R.sup.29 R.sup.30 R.sup.31 no.______________________________________CN NH.sub.2 CH.sub.3 CH.sub.3 C.sub.6 H.sub.5 V.1CN ##STR478## CH.sub.3 CH.sub.3 C.sub.6 H.sub.5 V.2CN ##STR479## CH.sub.3 CH.sub.3 C.sub.6 H.sub.5 V.3CN ##STR480## CH.sub.3 CH.sub.3 C.sub.6 H.sub.5 V.4CN ##STR481## CH.sub.3 CH.sub.3 C.sub.6 H.sub.5 V.5CN ##STR482## CH.sub.3 CH.sub.3 C.sub.6 H.sub.5 V.6CN N(COOC.sub.2 H.sub.5).sub.2 CH.sub.3 CH.sub.3 C.sub.6 H.sub.5 V.7CN ##STR483## CH.sub.3 CH.sub.3 C.sub.6 H.sub.5 V.8CN ##STR484## CH.sub.3 CH.sub.3 C.sub.6 H.sub.5 V.9COOC.sub.2 H.sub.5 ##STR485## CH.sub.3 CH.sub.3 C.sub.6 H.sub.5 V.10COOC.sub.2 H.sub.5 ##STR486## CH.sub.3 CH.sub.3 C.sub.6 H.sub.5 V.11CN N(COOCH.sub.2 C.sub.6 H.sub.5).sub.2 CH.sub.3 CH.sub.3 C.sub.6 H.sub.5 V.12CN ##STR487## CH.sub.3 CH.sub.3 C.sub.6 H.sub.5 V.13CN OCH.sub.2 C.sub.6 H.sub.5 CH.sub.3 CH.sub.3 C.sub.6 H.sub.5 V.14CN NH.sub.2 C.sub.13 H.sub.25 CH.sub.3 CH.sub.3 V.15CN ##STR488## C.sub.13 H.sub.25 CH.sub.3 CH.sub.3 V.16CN ##STR489## C.sub.13 H.sub.25 CH.sub.3 CH.sub.3 V.17CN ##STR490## C.sub.13 H.sub.25 CH.sub.3 CH.sub.3 V.18CN ##STR491## C.sub.13 H.sub.25 CH.sub.3 CH.sub.3 V.19CN ##STR492## C.sub.13 H.sub.25 CH.sub.3 CH.sub.3 V.20CN N(COOC.sub.2 H.sub.5).sub.2 C.sub.13 H.sub.25 CH.sub.3 CH.sub.3 V.21CN ##STR493## C.sub.13 H.sub.25 CH.sub.3 CH.sub.3 V.22CN ##STR494## C.sub.13 H.sub.25 CH.sub.3 CH.sub. 3 V.23COOC.sub.2 H.sub.5 ##STR495## C.sub.13 H.sub.25 CH.sub.3 CH.sub.3 V.24COOC.sub.2 H.sub.5 ##STR496## C.sub.13 H.sub.25 CH.sub.3 CH.sub.3 V.25CN N(COOCH.sub.2 C.sub.6 H.sub.5).sub.2 C.sub.13 H.sub.25 CH.sub.3 CH.sub.3 V.26CN ##STR497## C.sub.13 H.sub.25 CH.sub.3 CH.sub.3 V.27CN OCH.sub.2 C.sub.6 H.sub.5 C.sub.13 H.sub.25 CH.sub.3 CH.sub.3 V.28CN NH.sub.2 C.sub.3 H.sub.7 CH.sub.3 C.sub.6 H.sub.5 V.29CN ##STR498## C.sub.3 H.sub.7 CH.sub.3 C.sub.6 H.sub.5 V.30CN N(COOC.sub.2 H.sub.5).sub.2 C.sub.3 H.sub.7 CH.sub.3 C.sub.6 H.sub.5 V.31CN ##STR499## C.sub.3 H.sub.7 CH.sub.3 C.sub.6 H.sub.5 V.32CN NH.sub.2 CH.sub.3 C.sub.3 H.sub.7 C.sub.6 H.sub.5 V.33CN ##STR500## CH.sub.3 C.sub.3 H.sub.7 C.sub.6 H.sub.5 V.34CN N(COOC.sub.4 H.sub.9).sub.2 CH.sub.3 C.sub.3 H.sub.7 C.sub.6 H.sub.5 V.35______________________________________
Dyes according to formula (V) can be obtained by addition of a malononitrile dimer to an antipyrine nucleus in the presence of an oxidizing agent. Derivatization of the --NH.sub.2 group is done by methods as described below in the examples. These dyes have not been described before.
The present dyes are of cyan, magenta or yellow hue.
These dyes can be used in inks e.g. for laser applications and in inkjet, in textile, in lacquers and in paints.
These dyes are particularly useful in thermal dye sublimation or diffusion transfer applications including laser-induced transfer and resistive ribbon transfer. However, they can also be used in thermal dye melt transfer.
According to a particular embodiment of this invention the present dyes are used in the dye layer of a dye-donor element for thermal dye sublimation transfer.
For improving the stability of the dyes to light, the use of a metal complex of the dye, e.g. a Ni or Co complex, is also effective.
The dye layer is formed preferably by adding the dyes, the polymeric binder medium, and other optional components to a suitable solvent or solvent mixture, dissolving or dispersing the ingredients to form a coating composition that is applied to a support, which may have been provided first with an adhesive or subbing layer, and dried.
The dye layer thus formed has a thickness of about 0.2 to 5.0 .mu.m, preferably 0.4 to 2.0 .mu.m, and the amount ratio of dye to binder is between 9:1 and 1:3 by weight, preferably between 2:1 and 1:2 by weight.
As polymeric binder the following can be used: cellulose derivatives, such as ethyl cellulose, hydroxyethyl cellulose, ethylhydroxy cellulose, ethylhydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, nitrocellulose, cellulose acetate formate, cellulose acetate hydrogen phthalate, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate pentanoate, cellulose acetate benzoate, cellulose triacetate; vinyl-type resins and derivatives, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, copolyvinyl butyral-vinyl acetal-vinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetoacetal, polyacrylamide; polymers and copolymers derived from acrylates and acrylate derivatives, such as polyacrylic acid, polymethyl methacrylate and styrene-acrylate copolymers; polyester resins; polycarbonates; copolystyrene-acrylonitrile; polysulfones; polyphenylene oxide; organosilicones, such as polysiloxanes; epoxy resins and natural resins, such as gum arabic.
Particularly preferred dyes or dye mixtures for use in a dye-donor element for thermal dye sublimation are: for yellow a mixture of dye II.116 and a dye corresponding to the formula ##STR501## in a ratio of 1:10 to 10:1, for magenta a mixture of a dye corresponding to the formula ##STR502## and a dye corresponding to the formula ##STR503## in a ratio of 1:10 to 10:1, or a mixture of a dye corresponding to the formula ##STR504## and a dye corresponding to the formula ##STR505## in a ratio of 1:10 to 10:1, and for cyan a mixture of dye I.134 and dye I.92 or dye I.96 in a ratio of 1:10 to 10:1. The binder that is preferably used in the dye layer is a mixture of co-styrene-acrylonitrile and co-styrene-acrylonitrile-butadieen in a ratio ranging from 0 to 100% of either of the constituents. Preferably the binder/dye ratio is between 5:1 and 1:5.
The coating layer may also contain other additives, such as curing agents, preservatives, etc., these and other ingredients being described more fully in EP 133011, EP 133012, EP 111004 and EP 279467.
Any material can be used as the support for the dye-donor element provided it is dimensionally stable and capable of withstanding the temperatures involved, up to 400.degree. C. over a period of up to 20 msec, and is yet thin enough to transmit heat applied on one side through to the dye on the other side to effect transfer to the receiver sheet within such short periods, typically from 1 to 10 msec. Such materials include polyesters such as polyethylene terephthalate, polyamides, polyacrylates, polycarbonates, cellulose esters, fluorinated polymers, polyethers, polyacetals, polyolefins, polyimides, glassine paper and condenser paper. Preference is given Lo a support comprising polyethylene terephthalate. In general, the support has a thickness of 2 to 30 .mu.m. The support may also be coated with an adhesive or subbing layer, if desired.
The dye layer of the dye-donor element may be coated on the support or printed thereon by a printing technique such as a gravure process.
A dye-barrier layer comprising a hydrophilic polymer may also be employed in the dye-donor element between its support and the dye layer to improve the dye transfer densities by preventing wrong-way transfer of dye towards the support. The dye barrier layer may contain any hydrophilic material which is useful for the intended purpose. In general, good results have been obtained with gelatin, polyacryl amide, polyisopropyl acrylamide, butyl methacrylate grafted gelatin, ethyl methacrylate grafted gelatin, ethyl acrylate grafted gelatin, cellulose monoacetate, methyl cellulose, polyvinyl alcohol, polyethylene imine, polyacrylic acid, a mixture of polyvinyl alcohol and polyvinyl acetate, a mixture of polyvinyl alcohol and polyacrylic acid or a mixture of cellulose monoacetate and polyacrylic acid. Suitable dye barrier layers have been described in e.g. EP 227091 and EP 228065. Certain hydrophilic polymers, for example those described in EP 227091, also have an adequate adhesion to the support and the dye layer, thus eliminating the need for a separate adhesive or subbing layer. These particular hydrophilic polymers used in a single layer in the donor element thus perform a dual function, hence are referred Lo as dye-barrier/subbing layers.
Preferably the reverse side of the dye-donor element can be coated with a slipping layer to prevent the printing head from slicking to the dye-donor element. Such a slipping layer would comprise a lubricating material such as a surface active agent, a liquid lubricant, a solid lubricant or mixtures thereof, with or without a polymeric binder. The surface active agents may be any agents known in the art such as carboxylates, sulfonates, phosphates, aliphatic amine salts, aliphatic quaternary ammonium salts, polyoxyethylene alkyl ethers, polyethylene glycol fatty acid esters, fluoroalkyl C.sub.2 -C.sub.20 aliphatic acids. Examples of liquid lubricants include silicone oils, synthetic oils, saturated hydrocarbons and glycols. Examples of solid lubricants include various higher alcohols such as stearyl alcohol, fatty acids and fatty acid esters. Suitable slipping layers are described in e.g. EP 138483, EP 227090, U.S. Pat. Nos. 4,567,113, 4,572,860, 4,717,711. Preferably the slipping layer comprises as binder a styrene-acrylonitrile copolymer or a styrene-acrylonitrile-butadiene copolymer or a mixture hereof and as lubricant in an amount of 0.1 to 10% by weight of the binder (mixture) a polysiloxane-polyether copolymer or polytetrafluoroethylene or a mixture hereof.
The support for the receiver sheet that is used with the dye-donor element may be a transparent film of e.g. polyethylene terephthalate, a polyether sulfone, a polyimide, a cellulose ester or a polyvinyl alcohol-co-acetal. The support may also be a reflective one such as baryta-coated paper, polyethylene-coated paper or white polyester i.e. white-pigmented polyester.
To avoid poor adsorption of the transferred dye to the support of the receiver Sheet this support must be coated with a special surface, a dye-image-receiving layer, into which the dye can diffuse more readily. The dye-image-receiving layer may comprise, for example, a polycarbonate, a polyurethane, a polyester, a polyamide, polyvinyl chloride, polystyrene-co-acrylonitrile, polycaprolactone or mixtures thereof. Suitable dye-receiving layers have been described in e.g. EP 133011, EP 133012, EP 144247, EP 227094, EP 228066.
In order to improve the light resistance and other stabilities of recorded images, UV absorbers, singlet oxygen quenchers such as HALS-compounds (Hindered Amine tight Stabilizers) and/or antioxidants may be incorporated into the receiving layer.
The dye layer of the dye-donor element or the dye-image-receiving layer of the receiver sheet may also contain a releasing agent that aids in separating the dye-donor element from the dye-receiving element after transfer. The releasing agents can also be applied in a separate layer on at least part of the dye layer or of the receiving layer. For the releasing agent solid waxes, fluorine- or phosphate-containing surfactants and silicone oils are used. Suitable releasing agents are described in e.g. EP 133012, JP 85/19138, EP 227092.
The dye-donor elements according to the invention are used to form a dye transfer image. Such a process comprises placing the dye layer of the donor element in face-to-face relation with the dye-receiving layer of the receiver sheet and imagewise heating from the back of the donor element. The transfer of the dye is accomplished by heating for about several milliseconds at a temperature of 400.degree. C.
When the process is performed for but one single color, a monochrome dye transfer image is obtained. A multicolor image can be obtained by using a donor element containing three or more primary color dyes and sequentially performing the process steps described above for each color. The above sandwich of donor element and receiver sheet is formed on three occasions during the time when heat is applied by the thermal printing head. After the first dye has been transferred, the elements are peeled apart. A second dye-donor element (or another area of the donor element with a different dye area) is then brought in register with the dye-receiving element and the process repeated. The third color and optionally further colors are obtained in the same manner.
In order to accomplish a perfect register when the process is performed for more than one color and in order to detect what color is existing at the printing portion of the donor element, detection marks are commonly provided on one surface of the donor element. Generally optically detectable marks are used that can be detected by a light source and a photo sensor; detection being done by measuring the light transmitted through the detection mark or reflected from said mark. The marks being in the form of a light-absorbing or light-reflecting coating are formed in a preassigned position on the donor element by e.g. gravure printing. The detection marks can comprise an infrared shielding compound such as carbon black. The detection mark can also comprise one of the image dyes that are used for the image formation, with the detection being in the visible range.
The receiving element can also have detection marks provided on one surface, preferably the back surface so that the receiving element can be accurately set at a desired position during transfer, whereby the image can be formed always at a correct desired position.
In addition to thermal heads, laser light, infrared flash or heated pens can be used as the heat source for supplying heat energy. Thermal printing heads that can be used to transfer dye from the dye-donor elements of the present invention to a receiver sheet are commercially available. In case laser light is used, the dye layer or another layer of the dye element has to contain a compound that absorbs the light emitted by the laser and converts it into heat, e.g. carbon black.
Alternatively, the support of the dye-donor element may be an electrically resistive ribbon consisting of, for example, a multi-layer structure of a carbon loaded polycarbonate coated with a thin aluminum film. Current is injected into the resistive ribbon by electrically adressing a print head electrode resulting in highly localized heating of the ribbon beneath the relevant electrode. The fact that in this case the heat is generated directly in the resistive ribbon and that it is thus the ribbon that gets hot leads to an inherent advantage in printing speed using the resistive ribbon/electrode head technology compared to the thermal head technology where the various elements of the thermal head get hot and must cool down before the head can move to the next printing position.

The following examples are provided to illustrate the invention in more detail without limiting, however, the scope thereof.
EXAMPLE 1
Synthesis of dye I.1
2.92 g of dye I.61, 60 ml of acetone, 6.9 g of potassium carbonate and 4.76 ml of benzylbromide were added together and the mixture was refluxed for 1 hour. The potassium carbonate was filtered and washed with dichloromethane. The filtrate was concentrated by evaporation and was dried under vacuum. 3 g of dye I.1 was obtained.
EXAMPLE 2
Synthesis of dye I.6
6.98 g of dye I.13, 50 ml of dichloromethane, 150 ml of toluene. 22.3 ml of triethylamine and 8 g of succinic anhydride were added together and were stirred for 4 hours at room temperature. The mixture was left overnight. The residue was filtered and the filtrate was diluted with 750 ml of ethylacetate. The mixture was extracted four times with 1 l of water and two times with 500 ml of saturated sodium chloride and dried over sodium sulfate. After filtration the solution was concentrated by evaporation. 3 g of dye I.6 was obtained. Dye I.6 was purified by column chromatography using as eluent dichloromethane/ethylacetate 96:4.
EXAMPLE 3
Synthesis of dye I.13
31.2 g of 3-acetamido-4-nitroso-diethylaniline and 19 g of malononitrile dimer and 360 ml of ethanol were added together and heated while stirring. Triethylamine (16.7 ml) was added. The mixture was stirred for 24 hours at 25.degree. C. The precipitate was filtered, washed with ethanol, methanol and hexane. 33 g of dye I.13 was obtained.
EXAMPLE 4
Synthesis of dye I.22
6.98 g of dye I.13, 50 ml of dichloromethane, 150 ml of toluene, 22.3 ml of triethylamine and 11.9 g of phthalic anhydride were added together and were stirred for 10 minutes at room temperature. The reaction mixture was diluted with 1 l of ethylacetate. The mixture was extracted with 1 l of 1N hydrogen chloride, five times with 1 1 of water and two times with 500 ml of saturated sodium chloride and dried over sodium sulfate. After filtration the solution was concentrated by evaporation. After purification by column chromatography (eluent dichloromethane) 7.4 g of dye I.22 was obtained.
EXAMPLE 5
Synthesis of dye I.28
2.5 g of dye I.13, 40 ml of dichloromethane and 2.9 ml of pyridine were added together at 10.degree.-20.degree. C. while stirring. 3.43 ml of ethylchloroformate was added dropwise and the mixture was stirred for 2 hours at room temperature. An extra amount of 0.29 ml of pyridine and 0.343 ml of ethylchloroformate was added. The mixture was stirred for hours at room temperature. 300 ml of ethylacetate was added. The mixture was extracted with 250 ml of i N hydrogen chloride, five times with 400 ml of water and two times with 250 ml of saturated sodium chloride and dried over sodium sulfate. After filtration the solution was concentrated by evaporation and dried under vacuum. After recrystallization (solvent mixture: 20 ml of methylethylketone and 60 ml of ethanol) 2.33 g of dye I.28 was obtained.
EXAMPLE 6
Synthesis of dye I.30
4 g of dye I.61, 60 ml of dichloromethane and 5.74 ml of triethylamine were added together and 3.2 ml of methanesulfonyl chloride was added dropwise hereto at 0.degree.-10.degree. C. After 15 minutes of stirring at room temperature an extra amount of 5.74 ml of triethylamine was added. After 1 hour of stirring at room temperature the reaction mixture was diluted with 300 ml of ethylacetate. The mixture was extracted four times with 300 ml of water and two times with 300 ml of saturated sodium chloride and dried over sodium sulfate. After filtration the solution was concentrated by evaporation and dried under vacuum. 4.5 g of dye I.30 was obtained.
EXAMPLE 7
Synthesis of dye I.37
2 g of dye I.97 was dissolved in 30 ml of dichloromethane and 3 ml pyridine were added. Subsequently 3.4 ml of ethyl chloroformate was added dropwise hereto while stirring at 5.degree.-10.degree. C. After 24 hours of stirring at room temperature 200 ml of dichloromethane was added to the reaction mixture and extracted with 500 ml of 0.1N hydrogen chloride and washed with water till neutral and dried on magnesium sulfate. After filtration the solution was concentrated by evaporation, recrystallized using 40 ml of ethanol and dried under vacuum. 1.3 g of dye I.37 was obtained.
EXAMPLE 8
Synthesis of dye I.61
20 g of 4-nitroso-N-diethylaniline and 18.92 g of malononitrile dimer and 240 ml of ethanol were added together and were heated while stirring. 20 drops of piperidine were added. The mixture was refluxed for 2 hours while stirring and was then left overnight at room temperature without stirring. The crystals were filtered and washed three times with 100 ml of ethanol and three times with 100 ml of n-hexane and dried under vacuum. 28.5 g of dye I.61 were obtained.
EXAMPLE 9
Synthesis of dye I.77
21.5 g of 3-methyl-4-nitroso-N-diethylaniline and 15.52 g of malononitrile dimer and 240 ml of ethanol were added together and were heated while stirring. 26 drops of piperidine were added. An extra amount of 100 ml of ethanol were added to facilitate the stirring. The mixture was refluxed for 2 hours and was then left overnight at room temperature without stirring. The crystals were filtered and washed five times with 50 ml of ethanol and three times with 100 ml of n-hexane and dried under vacuum. 30 g of dye I.32 were obtained.
2.1 g of dye I.32, 30 ml of dichloromethane and 6 ml of pyridine were added together at 0.degree. C. While stirring 6 ml of ethylchloroformate were added dropwise. The mixture was stirred for 36 hours at room temperature. The reaction mixture was diluted with 300 ml of ethylacetate. The mixture was extracted with 250 ml of 1N hydrogen chloride, five times with 250 ml of water and two times with 250 ml of saturated sodium chloride and dried over magnesium sulfate. After filtration the solution was concentrated by evaporation and dried under vacuum. After recrystallization with ethanol (60 ml) 2.25 g of dye I.77 was obtained.
EXAMPLE 10
Synthesis of dye I.91
6 g of dye I.61, 100 ml of dichloromethane, 200 ml of toluene, 22.2 ml of triethylamine and 24.32 g of tetrachlorophthalic anhydride were added together and the mixture was stirred for 2.5 hours at room temperature. The reaction mixture was diluted with 1 l of ethylacetate. The mixture was extracted five times with 500 ml of water and two times with 250 ml of saturated sodium chloride and dried over magnesium sulfate. After filtration the solution was concentrated by evaporation and dried under vacuum to obtain pure dye I91.
EXAMPLE 11
Synthesis of dye I.97
5 g of the below identified compound and 2.8 g of malononitrile dimer were added in 100 ml of methanol. 10 g of sodium carbonate dissolved in 30 ml of water were added to this mixture while stirring. Subsequently a solution of 8.2 g of iodine in 75 ml of methanol was added very slowly (in approximately 30 minutes). After stirring for 2 hours at room temperature the precipitate was filtered and washed with water till neutral and subsequently washed with methanol. The reaction product was purified by column chromatography using dichloromethane/ethyl-acetate (99:1) as eluent. ##STR506##
EXAMPLE 12
Synthesis of dye I.106
1.3 g of dye I.129, 25 ml of acetone, 4.9 g of potassium carbonate and 5.8 ml of benzylbromide were added together and were refluxed while stirring for 8 hours. Potassium carbonate was filtered and the filtrate was concentrated under reduced pressure. The residual oil was purified by column chromatography. 1.1 g of dye I.106 was obtained.
EXAMPLE 13
Synthesis of dye I.116
1 g of dye I.76 (prepared analogously to dye I.6) was dissolved in 5 ml of morpholine at 25.degree. C. The solution was stirred for 30 minutes and thereafter poured into 40 ml of water. The precipitate was filtered, washed with water and purified by column chromatography (eluent dichloromethane/ethylacetate 95:5) to obtain 0.9 g of dye I.116.
EXAMPLE 14
Synthesis of dye I.126
4.5 g of dye I.30, 60 ml of dichloromethane and 2.95 ml of pyridine were added together and 3.48 ml of ethylchloroformate were added dropwise hereto at 0.degree. C. After 4 hours of stirring at room temperature the reaction mixture was diluted with 500 ml of ethylacetate. The mixture was extracted with 500 ml of 0.1N hydrogen chloride, with water till neutral end with 500 ml of saturated sodium chloride and dried over magnesium sulfate. After filtration the solution was concentrated by evaporation to yield 3.8 g of dye I.126. After purification by column chromatography (eluent dichloromethane) 1 g of pure dye I.126 was obtained.
EXAMPLE 15
Synthesis of dye I.127
5 g of dye I.32, 80 ml of dichloromethane, 160 ml of toluene, 17.7 ml of triethylamine and 19.4 g of phthalic anhydride were added together and the mixture was stirred for 24 hours at room temperature. The mixture was thereafter left over-weekend in the refrigerator. The reaction mixture was diluted with 750 ml of ethylacetate. The mixture was extracted six times with 500 ml of water and two times with 250 ml of saturated sodium chloride and dried over sodium sulfate. After filtration the solution was concentrated by evaporation and dried under vacuum. After column chromatography 3 g of pure dye I.127 was obtained.
EXAMPLE 16
Synthesis of dye I.128
5 g of dye I.32, 80 ml of dichloromethane, 160 ml of toluene, 17.7 ml of triethylamine and 13.1 g of succinic anhydride were added together and the mixture was left overnight at room temperature while stirring and was thereafter left over-weekend in the refrigerator. The reaction mixture was diluted with 750 ml of ethylacetate. The mixture was extracted six times with 500 ml of water and two times with 250 ml of saturated sodium chloride and dried over sodium sulfate. After filtration the solution was concentrated by evaporation and dried under vacuum. 4.5 g of dye I.128 was obtained.
EXAMPLE 17
Synthesis of dye I.129
2.0 g of dye I.61 were dissolved in 30 ml of dichloromethane. At 0.degree. C. 2.9 ml of triethylamine were added, followed by 2 ml of ethylchloroformate. The reaction mixture was stirred for 30 minutes at room temperature. 250 ml of ethylacetate were added and subsequently the mixture was washed with 1N hydrogen chloride (200 ml), water (3.times.500 ml) and brine (300 ml). The organic layer was dried over sodium sulfate, filtered and concentrated under reduced pressure to obtain 2.1 g of dye I.129.
EXAMPLE 18
Synthesis of dye II.11
2.3 g of dye II.23 was dissolved in 23 ml of dimethylsulfoxide and 0.31 g of potassium cyanide was added. The reaction mixture was stirred for 1 hour at room temperature. Subsequently 1.2 g of iodine were added. The reaction mixture was poured out into water and extracted with dichloromethane. The organic phase was dried over sodium sulfate and concentrated by evaporation. The reaction product was purified by column chromatography. 0.65 g of dye II.134 was obtained.
EXAMPLE 19
Synthesis of dye II.13
2 g of dye II.75, 80 ml of toluene and 40 ml of dichloromethane were added together while stirring. 1.3 g of triethylamine and 6.7 g of succinic anhydride were added. The mixture was stirred for 24 hours. Thereafter the mixture was diluted with ethylacetate, washed with 1N hydrogen chloride, with saturated sodium hydrogen carbonate and with saturated sodium chloride and dried over sodium sulfate. The mixture was concentrated by evaporation and thereafter crystallized from ethanol. 1.2 g of dye II.13 were obtained.
EXAMPLE 20
Synthesis of dye II.15
2 g of dye I.75, 50 ml of dichloromethane and 7.25 ml of pyridine were stirred at 0.degree. C. 9.5 g of ethylchloroformate were added dropwise. The mixture was stirred for 30 minutes. Thereafter the mixture was diluted with dichloromethane, washed twice with 1N hydrogen chloride, four times with saturated sodium chloride, once with saturated sodium hydrogen carbonate, twice with saturated sodium chloride. The organic phase was dried over magnesium sulfate. The organic phase was concentrated by evaporation and thereafter crystallized from ethanol. 1.5 g of dye II.15 were obtained.
EXAMPLE 21
Synthesis of dye II.23
5 g of dye II.8 was dissolved in 100 ml of dichloromethane and 5.52 g of methyl succinic anhydride were added. At room temperature 7.76 g of triethylamine were added slowly. The mixture was stirred for 15 minutes. The reaction product was purified by column chromatography using dichloromethane as eluent. 5.5 g of dye II.23 were obtained.
EXAMPLE 22
Synthesis of dye II.51
1 g of dye II.132 was dissolved in 10 ml of dimethylsulfoxide and 0.15 g of potassium cyanide was added hereto. The mixture was stirred for 20 minutes at room temperature. Subsequently 0.6 g of iodine was added and the mixture was stirred for another 20 minutes at room temperature. The mixture was poured out into 100 ml of dichloromethane and washed with a saturated sodium chloride solution. The organic phase was dried over sodium sulfate and concentrated by evaporation. The reaction product was boiled in 20 ml of methanol, cooled and subjected to ultrasonic treatment for 5 minutes. The precipitate was filtered and washed with methanol. 0.4 g of dye II.51 was obtained.
EXAMPLE 23
Synthesis of dye II.75
5 g of 2,6-dimethyl-4H-pyran-4-one, 5.325 g of malononitrile dimer and 50 ml of acetic anhydride were heated to 120.degree. C. for 30 minutes. The mixture was left overnight. Thereafter the precipitate was filtered, washed with water and dried at 50.degree. C. 7.3 g of dye II.75 were obtained.
EXAMPLE 24
Synthesis of dye II.92
3 g of dye II.130 was dissolved in 50 ml of dichloromethane and 3.1 ml of pyridine. The reaction mixture was cooled and 3.6 ml of ethylchloroformate were added dropwise. The mixture was stirred at room temperature for 1 hour. Subsequently the reaction mixture was extracted with ethylacetate and 1N hydrogen chloride, washed neutral, dried and concentrated by evaporation. The reaction product was purified by recrystallisation from ethanol.
EXAMPLE 25
Synthesis of dye II.108
5 g of 2,6-diphenyl-4H-pyran-4-one, 2.7 g of malononitrile dimer and 50 ml of acetic anhydride were heated to 120.degree. C. while stirring. After 30 minutes the mixture was cooled to room temperature. The precipitate was filtered, washed with water and methanol and dried at 50.degree. C. After purification by crystallization from ethanol 4.4 g of dye II.108 were obtained.
EXAMPLE 26
Synthesis of dye II.116
50 g of dye II.75 was dissolved in 500 ml of dichloromethane and stirred at room temperature. 109 ml of i-butylchloroformate were added slowly. The mixture was stirred at room temperature and 68 ml of dry pyridine were added dropwise in approximately 15 minutes. The temperature increased to 42.degree. C. After stirring for 30 minutes dichloromethane was evaporated. The reaction product was recrystallized using 400 ml of ethanol and 200 ml of water and was left overnight in the refrigerator. The crystals were filtered, washed twice with a mixture of 50 ml of water and 75 ml of ethanol and twice with 125 ml of water, and dried at 50.degree. C. 62.6 g of dye II.116 were obtained.
EXAMPLE 27
Synthesis of dye II.128
To 15 g of the below identified compound in 100 ml of ethanol was added 8.76 g of malononitrile dimer. Three drops of piperidine were added and the mixture was refluxed for 3 hours. The precipitate was filtered, washed with ethanol and dried. 18.7 g of dye II.128 was obtained. ##STR507##
EXAMPLE 28
Synthesis of dye II.130
10 g of the below identified compound, 6 g of malononitrile dimer, 60 ml of ethanol and 3 drops of piperidine were added together and were refluxed for 4 hours. The mixture was left overnight to crystallize. The crystals were filtered, washed with ethanol and dried. 7.1 g of dye II.130 was obtained. ##STR508##
EXAMPLE 29
Synthesis of dye II.132
5 g of dye II.7 was dissolved in 125 ml of toluene and 40 ml of dichloromethane. 19.2 ml of triethylamine and 10 g of phthalic anhydride were added. The mixture was stirred at room temperature for 1 hour. Thereafter the mixture was diluted with ethylacetate and washed with a 1N hydrogen chloride solution, water and a saturated sodium chloride solution. The mixture was concentrated by evaporation and thereafter purified by column chromatography using dichloromethane as eluent. 5.4 g of dye II.132 were obtained.
EXAMPLE 30
Synthesis of dye III.8
3 g of malononitrile dimer and 20 ml of methanol were stirred at 0.degree.-5.degree. C. 5.3 g of p-diethylaminophenyl diazonium tetrafluorobromide salt dissolved in 20 ml of methanol was added dropwise. Thereafter 40 g of ice were added and a solution of 6 g of sodium acetate and 1 g of sodium hydroxide in 100 ml of water was added dropwise. The mixture was stirred for 1 h. The precipitate was filtered, washed with water and dried at 50.degree. C. 5.8 g of dye III.8 were obtained.
EXAMPLE 31
Synthesis of dye IV.1
6 g of malononitrile dimer, 20 g of the below identified compound and 400 ml of methanol were added together while stirring. ##STR509##
16 g of sodium carbonate dissolved in 100 ml of water was added dropwise and thereafter a solution of 9.4 g iodine in 120 ml of methanol was added dropwise. The mixture was stirred for 30 minutes. The precipitate was filtered, washed with water and dried at 50.degree. C. After crystallization from ethanol 8.7 g of dye IV.1 were obtained.
EXAMPLE 32
Synthesis of dye IV.2
2 g of dye IV.1, together with 80 ml of toluene and 40 ml of dichloromethane were stirred at room temperature. 0.8 g of triethylamine and 4.25 g of succinic anhydride were added. The mixture was left over weekend and then a further amount of 6 ml of triethylamine was added. The mixture was stirred overnight and was thereafter diluted with dichloromethane. The reaction product was washed with 1N hydrogen chloride, with water, with saturated sodium hydrogen carbonate and with saturated sodium chloride. Then the reaction product was dried over sodium sulfate and concentrated by evaporation. After crystallization from ethanol 1.6 g of dye IV.2 were obtained.
EXAMPLE 33
Synthesis of dye IV.7
2 g of dye IV.1 were dissolved in 50 ml of dichloromethane and the solution was stirred at 0.degree. C. After adding 4.3 ml of pyridine, 5.76 g of ethylchloroformate was added dropwise. After stirring for 30 minutes a further amount of 2.88 g of ethylchloroformate was added. Thereafter the mixture was diluted with dichloromethane, washed twice with 1N hydrogen chloride, once with saturated sodium chloride, with saturated sodium hydrogen carbonate and with saturated sodium chloride. The reaction product was dried over magnesium sulfate and concentrated by evaporation. After crystallization from ethanol 1.6 g of dye IV.7 were obtained.
EXAMPLE 34
Synthesis of dye IV.15
2.65 g of malononitrile dimer, 10 g of the below identified compound and 175 ml of methanol were added together at room temperature while stirring. ##STR510##
7 g of sodium carbonate dissolved in 45 ml of water was added dropwise while stirring and thereafter a solution of 4.25 g iodine in 55 ml of methanol was added dropwise. The mixture was stirred for 1 h. The precipitate was filtered, washed with methanol and water and dried at 50.degree. C. After crystallization from acetone 4 g of dye IV.15 were obtained.
EXAMPLE 35
Synthesis of dye IV.21
3 g of dye IV.15, 30 ml of dichloromethane and 9.5 ml of pyridine were added together and stirred on an ice bath. 178 ml of ethylchloroformate was added dropwise. After stirring and check for completion of the reaction by thin layer chromatography (dichloromethane/methanol 98:2) the mixture was diluted with dichloromethane, washed with a 1N hydrogen chloride solution, with a saturated sodium chloride solution, dried over magnesium sulfate and concentrated by evaporation. After recrystallization from ethanol (80 ml) 2.4 g of dye IV.21 were obtained.
EXAMPLE 36
Synthesis of dye IV.63
4 g of dye IV.57 (synthesized analogous to dye IV.15), 40 ml of dichloromethane and 17 ml of pyridine were added together and stirred on an ice bath. 15.2 ml of ethylchloroformate was added dropwise. After stirring for 1 hour and check for completion of the reaction by thin layer chromatography (dichloromethane/methanol 98:2) the mixture was diluted with ethyl acetate, washed with a 1N hydrogen chloride solution, with water, dried over magnesium sulfate and concentrated by evaporation. After recrystallization from ethanol (60 ml) 1.0 g of dye IV.63 were obtained.
EXAMPLE 37
Synthesis of dye V.15
13 g of malononitrile dimer, 27 g of the below identified compound and 400 ml methanol were stirred. ##STR511##
32 g of sodium carbonate dissolved in 200 ml of water was added dropwise and thereafter a solution of 38.5 g iodine in 430 ml of methanol was added dropwise. The mixture was stirred for 1 h. The precipitate was filtered, washed with methanol and water and dried. 19.2 g of dye V.15 were obtained.
EXAMPLE 38
The absorption maxima (.lambda..sub.max) and molar extinction coefficients (.epsilon.) of the dyes identified below were determined in methanol. The results are listed in table 6.
TABLE 6______________________________________dye .lambda..sub.max (nm) .epsilon. (mol.sup.-1 cm.sup.-1 1)______________________________________I.6 638 82852I.8 611 67292I.13 534 55393I.16 620 74730I.19 610 52681I.20 625 68243I.22 638 57000I.25 537 43390I.26 526 47360I.28 638 86415I.31 533 43119I.35 604 48120I.36 638 83324I.37 653 83006I.42 526 38747I.46 537 34182I.49 521 28876I.51 515 39010I.52 655 76020I.61 523 46370I.62 538 45847I.64 419 34033I.65 614 67805I.70 525 30294I.76 624 66000I.77 614 63934I.82 505 28930I.85 527 47078I.91 628 64428I.92 637 82295I.93 638 80823I.94 638 89608I.95 638 89591I.96 638 91145I.97 552 42137I.103 584 34034I.106 602 60817I.107 638 85481I.108 535 54167I.109 620 75652I.111 638 80665I.114 591 46578I.115 629 25435I.116 515 43006I.117 639 106020I.121 515 42733I.122 531 56105I.124 623 62536I.125 610 81994I.126 626 67818I.127 617 31915I.128 635 57250I.134 638 91311I.136 642 65027I.138 638 63883I.140 527 47533I.141 534 57416I.142 638 94156II.4 388 28905II.5 551 68237II.6 434 36557II.7 431 27981II.9 484 40842II.11 644 31974II.13 457 28893II.15 451 34780II.17 340 18857II.22 453 28999II.23 573 70563II.24 340 23529II.26 547 73658II.27 452 27983II.30 405 36428II.34 525 18874II.35 643 23423II.39 500 46197II.45 548 56461II.51 620 34074II.52 525 10506II.59 523 39797II.61 529 38191II.63 345 18782II.65 541 51855II.67 463 34925II.70 509 22013II.71 396 28132II.75 361 18818II.77 328 17010II.87 435 26971II.90 408 23311II.91 503 23117II.92 577 63729II.93 407 21138II.100 606 62890II.103 337 22699Il.108 394 22645II.110 385II.111 362 21082II.112 451 42453II.113 419 34033II.115 452 29855II.116 453 31041II.117 421 19565II.118 454 30400II.123 457 27925II.124 484 32813Il.127 569 26224II.128 458 23755II.129 443 30749Il.130 460 33180II.131 477 35528II.132 549 52926II.13 551 48816III.8 250 43096III.9 247 33100IV.1 470 35187IV.2 543 55170IV.7 541 56566IV.21 513 32357IV.30 533 62454IV.63 579 55434V.1 437 2506______________________________________
EXAMPLE 39
A dye-donor element for use according to thermal dye sublimation transfer was prepared as follows:
A solution of dye as identified in Table 7 and binder in 10 ml of solvent was prepared (the nature of the binder and the solvent is identified below). From this solution a layer having a wet thickness of 100 .mu.m was coated on 6 .mu.pm thick polyethylene terephthalate film. The resulting layer was dried by evaporation of the solvent.
A commercially available Hitachi material type VY S100A was used as receiving element.
The dye-donor element was printed in combination with the receiving element in a Hitachi color video printer VY-1OOA.
The receiver sheet was separated from the dye-donor element and the maximum color density of the recorded dye image on the receiving sheet (D.sub.max) was measured by means of a Macbeth densitometer RD919 in Status A mode.
The stability to light of the dyes was tested as follows. The receiver sheet carrying transferred dye was divided into 3 strips. The first strip was exposed for 5 hours, the second for 15 hours and the third for 30 hours to white light and ultraviolet radiation in a Xenotest (trade name) type 50 apparatus of Hanau Quartzlampen GmbH, Hanau, W. Germany. The density was measured again and the loss of density in percent was derived.
These experiments were repeated for each of the dye/binder combinations identified in table 7.
In table 7 B1 stands for co-vinylbutyral-vinylacetal-vinyl alcohol, B2 for nitrocellulose with a nitrogen content between 6.75% and 14% by weight, B3 for cellulose acetate butyrate having an acetyl content of 29.5% and a butyryl content of 17%, B4 for co-styrene-acrylonitrile, S1 for methyl ethyl ketone, S2 for tetrahydrofuran, S3 for dichloromethane.
TABLE 7______________________________________ mg dye/ % density lossdye binder mg binder solvent D.sub.max 5 h 15 h 30 h______________________________________I.6 B3 50/50 S1 .sup. 230.sup.(a) 3 10 16I.6 B2 50/20 S1 264 1 1 6I.8 B3 50/50 S1 133 15 42 73I.8 B2 50/20 S1 169 21 49 80I.13 B3 40/50 S1 198 86I.13 B2 50/20 S1 219 89I.16 B3 50/50 S1 263 9 22 61I.16 B3 50/50 S1 263 9 22 61I.16 B2 50/20 S1 262 2 8 23I.19 B3 50/50 S1 143 9 31 77I.19 B2 50/20 S1 173 5 31 76I.20 B3 50/50 S1 175 21 61I.20 B2 50/20 S1 204 11 59I.25 B3 50/50 S1 202 83I.25 B2 50/20 S1 239 86I.26 B3 50/50 S1 261 4 54 85I.26 B2 50/20 S1 239I.26 B2 50/20 S1 239 4 54 85I.28 B2 50/50 S1 264 9 13 27I.28 B2 50/20 S1 234I.28 B2 30/20 S1 258 3 9 24I.35 B3 50/50 S1 182 13 57I.35 B2 50/20 S1 205 9 50I.36 B3 50/50 S1 139 3 16 26I.36 B2 50/20 S1 241 38 25 37I.37 B3 50/50 S1 201 36 85I.37 B2 50/20 S1 212 54 87I.42 B2 50/50 S2 214 33 77I.42 B2 50/20 S1 242 14 60I.42 B2 50/20 S1 242 14 60I.42 B2 50/50 S2 214 33 77I.46 B3 50/50 S1 240 86I.46 B2 50/20 S1 249 88I.52 B3 50/50 S1 140 48I.52 B2 50/20 S1 151 50I.61 B4 50/50 S1 211 21 80 89I.62 B3 50/50 S1 223 90I.62 B2 50/20 S1 251 90I.65 B3 50/50 S1 205 41 63I.65 B2 50/20 S1 239 54I.70 B2 50/20 S1 222 3 62 92I.70 B3 50/50 S1 237 13 80 92I.76 B3 50/50 S1 257 6 9I.76 B3 50/50 S1 257 2 7 12I.76 B2 50/20 S1 256 2 7 12I.76 B3 50/50 S1 198I.76 B2 50/20 S1 190I.77 B3 50/50 S1 203 2 3 51I.77 B2 50/20 S1 253 12 19 32I.85 B2 25/20 S1 269 18 79I.85 B2 50/20 S1 262 8 53I.85 B2 50/50 S1 275 10 70I.91 B3 50/50 S1 211 17 52I.91 B2 50/20 S1 213 14 63I.92 B3 50/50 S1 237 8 23 60I.92 B2 50/20 S1 248 2 9 19I.93 B3 50/50 S1 197 8 19 68I.93 B2 50/20 S1 234 1 3 66I.94 B3 50/50 S1 225 4 5 13I.94 B2 50/20 S1 229 1 0 2I.95 B3 50/50 S1 233 4 9 17I.95 B2 50/20 S1 256 5 5 8I.96 B3 50/50 S1 229 9 28 58I.96 B2 50/20 S1 251 3 4 19I.106 B3 50/50 S1 225 74 90I.106 B2 50/20 S1 244 68 91I.106 B2 30/20 S1 189 70 89I.107 B3 50/50 S1 177 1 2 24I.107 B2 50/20 S1 212 1 7 19I.108 B3 50/50 S1 223 17 56I.108 B2 50/20 S1 229 16 54I.109 B3 50/50 S1 227 14 94 78I.109 B2 50/20 S1 247 2 62 78I.111 B3 50/50 S1 181 2 3 12I.111 B2 50/20 S1 192 2 2 1I.115 B3 50/50 S1 196 30 81I.115 B2 50/20 S1 222 54I.116 B3 50/50 S1 236 30 22 55I.116 B2 50/20 S1 240 2 18 53I.117 B3 50/50 S1 208 5 12 25I.117 B2 50/20 S1 235 3 8 16I.121 B3 50/50 S1 261 15 47 71I.121 B2 50/20 S1 274 12 47 78I.121 B2 50/20 S1 274 12 47 78I.122 B2 50/20 S2 158 4 82I.122 B2 50/20 S2 158 4I.123 B4 40/50 S1 269 25 69I.124 B3 50/50 S1 233 3 20 60I.124 B2 50/20 S1 .sup. 198.sup.(a) 10 23 61I.124 B3 50/50 S1 233 3 20 60I.125 B3 50/50 S1 199 10 33 64I.125 B2 50/20 S1 203 10 5 67I.126 B3 50/50 S1 254 7 35 68I.126 B2 50/20 S1 258 10 42 71I.127 B3 50/50 S1 151 26 61I.127 B2 50/20 S1 176 23 61I.128 B3 50/50 S1 270 2 9 45I.128 B2 50/20 S1 260 0 0 1I.134 B3 50/50 S1 260 2 5 10I.134 B2 50/20 S1 264 7 8 11I.136 B3 50/50 S1 189 12 14 47I.136 B2 50/20 S1 180 12 26 51I.138 B3 50/50 S1 208 6 19 26I.138 B2 50/20 S1 191 8 19 35I.140 B3 50/50 S1 198 89I.140 B2 50/20 S1 203 89I.141 B3 50/50 S1 150 57I.141 B2 50/20 S1 192 28I.142 B3 50/50 S1 182 0 1 23I.142 B2 50/20 S1 190 1 0 5II.5 B3 50/50 S1 177II.5 B2 50/20 S1 270 72II.7 B4 50/50 S1 238 57 87II.7 B4 99/50 S1 248II.7 B4 99/50 S1 196II.9 B4 50/50 S1 235 90II.13 B3 50/50 S1 188 7 12 19II.13 B2 50/20 S1 199 5 10 17II.15 B3 50/50 S1 205 5 10 14II.15 B2 50/20 S1 117 3 6 11II.22 B3 50/20 S1 144 3 4 10II.22 B2 50/20 S1 168 2 0 2II.22 B3 50/50 S1 15S 0 2 7II.23 B3 50/50 S2 196 28 40 82II.23 B2 50/20 S2 239 23 64 S5II.26 B3 50/50 S1 138 4II.26 B2 50/20 S1 218 68II.27 B2 50/20 S1 169 10 10 14II.27 B3 50/50 S1 125II.34 B3 50/50 S1 145 93II.34 B2 50/20 S1 166 94II.35 B3 50/50 S1 136II.35 B2 50/20 S1 1S7 83II.45 B3 50/50 S1 236 8SII.45 B2 50/20 S1 227 76II.51 B3 50/50 S1 171 81II.51 B2 50/20 S1 207 90II.52 B3 50/50 S1 146 79II.59 B3 50/50 S1 199 95II.59 B2 50/20 S1 228 96II.61 B3 50/50 S1 204 96II.61 B2 50/20 S1 237 96II.63 B3 50/50 S1 261 4II.65 B2 50/20 S1 244II.70 B2 50/20 S1 156 95II.70 B3 50/50 S1 133 94II.87 B3 50/50 S1 177 SSII.87 B2 50/20 S1 192 S4II.91 B3 50/50 S1 133 93II.91 B2 50/20 S1 157 94II.92 B3 50/50 S1 139 83II.92 B2 50/20 S1 157 88II.100 B3 50/50 S1 148 78II.100 B2 50/200 S1 172 S0II.110 B2 100/20 S1 110 22 41 6II.110 B2 99/20 S1 110 22 41 6II.112 B2 50/20 S1 207 51 88II.112 B2 50/20 S1 207 51 88II.112 B4 50/50 S1 188II.113 B3 50/50 S1 155 53 85II.113 B3 50/50 S1 155 53 83II.113 B2 50/20 S1 161 88II.115 B3 50/50 S1 179 1 4 7II.115 B2 50/20 S1 196 3 2 5II.116 B2 50/20 S1 184 0 2 5II.116 B3 50/50 S1 165 2 7 11II.118 B3 50/50 S1 148 5 9 16II.118 B2 50/20 S1 148 2 5 12II.123 B3 50/50 S1 174 4 9 17II.123 B2 50/20 S1 194 13 14 21II.124 B2 50/20 S1 115 7 17 30II.127 B3 50/50 S1 115 86II.127 B2 50/20 S1 132 87II.128 B2 50/20 S1 117 82II.129 B3 50/20 S1 131 82II.129 B2 50/20 S1 151 8II.130 B3 50/20 S1 125 8II.130 B2 50/20 S1 134 84II.131 B3 50/50 S1 133 91II.131 B2 50/20 S1 159 92II.132 B3 50/20 S1 200 79II.132 B2 50/20 S1 209 79II.133 B3 50/50 S1 232 62II.133 B2 50/20 S1 239 62III.9 B2 200/40 S1 134 13 10 20IV.1 B3 50/50 S2 141 30 74IV.1 B2 50/20 S2 117 29 69IV.2 B3 50/50 S2 115 23 69IV.7 B3 50/50 S1 184 21 65 92IV.7 B2 50/20 S1 218 17 60 93IV.21 B2 50/50 S1 142 33 79IV.21 B2 50/20 S1 230 23 76V.15 B2/B3 50/50 S1 152______________________________________ .sup.(a) transmission density

	Number	Date	Country
Parent	709821	Jun 1991
Parent	524461	May 1990

Dyes and dye-donor elements for use in thermal dye sublimation transfer

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Regaila et al, Egyptian Journal of Pharmaceutical Sciences, vol. 30(1-4), 1989, pp. 159-170.
Regaila et al, Chemical Abstracts, vol. 112 (1989) 157949v.
VanAllan et al, Chemical Abstracts, vol. 74 (1970) 53594f.