Patent GB-903268-A (GB)
Title: Polymerizable heterocyclic dye-forming intermediates and their production and uses
IPC: C07D277/64
Filed: 1960-03-07
Abstract: Dye intermediates of the formula: <FORM:0903268/IV(a)/1> wherein n is 0 or 1, W is an alkyl group or a hydrocarbon mercapto group, R1 is an alkyl or substituted alkyl group (e.g. a phenyl, halogen or carboxyl substituted alkyl group), X is an anion (e.g. halide, arylsulphonate or alkylsulphate) and Z completes with the atoms indicated in the formula the residue of a 5-membered or 6-membered heterocyclic nucleus (e.g. thiazole, oxazole, selenazole, iminazole, indolenine, pyridine, benzthiazole, naphthathiazole quinoline or benzoquinoline), said nucleus containing a fused or substituent benzene ring containing as a substituent a radical of the formula: <FORM:0903268/IV(a)/2> where R2 is a hydrogen atom, a C1-4 alkyl group, an aryl group, an aralkyl group or a halogen atom, may be addition-polymerized in the presence of an addition polymerization initiator activatable by actinic light and thermally inactive below 80 DEG C. (e.g. benzoin, benzoin methyl ethers, anthraquinone and others disclosed in Specifications 741,294 and 741,441). Conversion to methine dyes may be carried out prior to or after polymerization has taken place.  The polymerization may also be conducted in the presence of vinyl or vinylidene compounds as disclosed in Specifications 741,294 and 741,441.  A large number of specified adjurvants may also be present during the polymerization. Specifications 746,804, 749,225, 765,893, 786,344 and 788,343 also are referred to.ALSO:The invention comprises dye intermediates of the formula:-<FORM:0903268/IV (b)/1> wherein n is O or 1, W is an alkyl group or a hydrocarbon mercapto group, R1 is an alkyl or substituted alkyl group (e.g. a phenyl, halogen or carboxyl substituted alkyl group), X is an anion (e.g. halide, arylsulphonate or alkylsulphate) and Z completes with the atoms indicated in the formula the residue of a 5-membered or 6-membered heterocyclic nucleus (e.g. thiazole, oxazole, selenazole, iminazole, indolenine, pyridine, benzthiazole, naphthathiazole quinoline or benzoquinoline), said nucleus containing a fused or substituent benzene ring containing as a substituent a radical of the formula:- <FORM:0903268/IV (b)/2> where R2 is a hydrogen atom, a C1-4 alkyl group, an aryl group, an aralkyl group or a halogen atom.  The above compounds may be prepared by reacting the corresponding compounds in which the group <FORM:0903268/IV (b)/3> is replaced by an amino group with an appropriate halide or other amide forming derivative of an acid of the formula CH2=C(R2)-COOH. 6-nitroquinaldine is prepared by reacting para-nitroaniline with paraldehyde and hydrochloric acid.  Reduction with stannous chloride acid and hydrochloric acid yields the corresponding 6-aminoquinaldine, used as a starting material. 2,21,4,41-Tetranitrodiphenyldisulphide is prepared from 2,4-dinitrochlorobenzene and sodium polysulphide.  Further reaction with zinc and acetic anhydride, followed by hydrolysis with hydrochloric acid, yields 2-methyl-5-aminobenzthiazole hydrochloride, used as a starting material.  Specifications 741,294, 741,441, 746,804, 749,225, 765,893, 786,344 and 788,343 are referred to.ALSO:Various methine dyes are prepared by reacting, optionally before or after addition polymerization, dye intermediates of the formula:- <FORM:0903268/IV (b)/1> wherein n is 0 or 1, W is an alkyl group or a hydrocarbon mercapto group, R1 is an alkyl or substituted alkyl group (e.g. a phenyl, halogen or carboxyl substituted alkyl group), X is an anion (e.g. halide, arylsulphonate or alkylsulphate) and Z completes with the atoms indicated in the formula the residue of a 5-membered or 6-membered heterocyclic nucleus (e.g. thiazole, oxazole, selenazole, iminazole, indolenine, pyridine, benzthiazole, naphthathiazole quinoline or benzoquinoline), said nucleus containing a fused or substituent benzene ring containing as a substituent a radical of the formula:- <FORM:0903268/IV (b)/2> where R2 is a hydrogen atom, a C1-4 alkyl group, an aryl group, an aralkyl group or a halogen atom, with, for example, a heterocyclic quaternary ammonium salt and an ortho ester in the presence of an acid binding agent to form a carbocyanine dye; with, for example, a diarylformamidine or a C-alkyl diaryl formamidine in the presence of acetic anhydride, followed by reaction with a heterocyclic quaternary ammonium salt, also to form a carbocyanine dye; with, for example, a dialkylaminobenzaldehyde or para-dialkylamino cinnamic aldehyde in the presence of a basic condensing agent to form a styryl dye; with, for example, another quaternary ammonium salt of the type used in preparing cyanine dyes in the presence of anilido-acrolein and an organic base to form a dicarbocyanine dye, or in the presence of glutaconic aldehyde dianilide and an organic base to form a tricarbocyanine; or with, for example, active ketomethylene compounds, to form a merocyanine dye.  6-nitroquinaldine is prepared by reacting para-nitroaniline with paraldehyde and hydrochloric acid. Reduction with stannous chloride acid and hydrochloric acid yields the corresponding 6-aminoquinaldine, used as a starting material. 2,21,4,41-Tetranitrodiphenyldisulphide is prepared from 2,4-dinitrochlorobenzene and sodium polysulphide.  Further reaction with zinc and acetic anhydride, followed by hydrolysis with hydrochloric acid, yields 2-methyl-5-aminobenzthiazole hydrochloride, used as a starting materials.  Specifications 741,294, 741,441, 746,804, 794,225, 765,893, 786,344 and 788,343 are referred to.