JPS603428B2 - Method for producing reactive xanthene dyes - Google Patents

Description

[Detailed description of the invention]

The subject of Patent No. 687986 is the following general formula [where R and R' are hydrogen atom, halogen atom, hydroxyl, lower alkoxy, carboxyl or sulfonic acid group, R,
and R2 is a hydrogen atom or optionally a hydroxyl, carboxyl, sulfonic acid, or phenyl group or -O
S03 represents an alkyl group substituted by a group, R and R2 together with the nitrogen atom can be members of an alkyleneimine ring optionally containing a heteroatom, R3 is a hydrogen atom or an alkyl group, A is mononuclear 3 or 2
Nuclear aromatic residues, such as phenylene or naphthylene groups or diphenyl, diphenylamine, diphenylsulfide, diphenylsulfone or azobenzole residues, which contain halogen atoms, Can be substituted with a lower alkital group, a lower alkoxy group, a carboxyl group or a nitro group,
W is a divalent crosslinking factor, such as 1C Koichi, 1CH21C&
Y represents a group of formula, where Z represents an inorganic or organic residue that can be eliminated under alkalinity, R4 represents a hydrogen atom or an alkyl group, m, n and q represent 0 or 1. , p means 1 or 2. This method is a method for producing a reactive xanthene dye having the following general formula One mole of the compound is converted into an amino compound of the following general formula (wherein R3, W, A, R4, m, n, p and q have the above-mentioned meanings) or an amino compound of the following formula (wherein R and R2 have the above-mentioned meanings). ) in a pure aqueous, aqueous-based or organic medium at a temperature of about 0 to about 120°C, preferably about 20°C.
The resulting monocondensation product is then reacted at a temperature between 80° C. and about 80° C., optionally in the presence of an acid binder, and the resulting monocondensation product is then converted to
R, R2 amine or at least 1 mol of the above-mentioned 8-hydroxyethylsulfonyl group-containing amino compound and pure water;
from about 70°C to about 200°C in an aqueous monoorganic or organic medium;
Preferably, the reaction is carried out at about 9000 to about 160°C in the presence of an acid binder, resulting in the following general formula [wherein R,, R2
, R, R, R3, R4, W, A, m, n, q and p have the meanings given above. ) as a sulfating agent, phosphorylating agent,
By treatment with a halogenating agent, an alkyl- or arylsulfonic acid halide or -carboxylic acid halide or -carboxylic acid anhydride, in the above formula Z is a group 1○-S03day, 1○-P032day2, 1halogen or -
o-Acyl meaning xanthylium dyes, optionally by treating the dyes thus obtained with an alkaline agent, such as an alkali hydroxide or alkali carbonate, such as sodium hydroxide or sodium carbonate. by reacting (adding) the dye thus obtained optionally with a thiosulphate, a dialkylamine or a phenol, in which Z is a residue -S-S03, -N This is carried out by leading to the corresponding dyes meaning (alkyl)2 or 1. However, this known process requires an intermediate isolation of the reaction product obtained during the condensation in an intermediate stage before further processing. The inventors have found that when operating in pure organic media using specific solvents, the above-mentioned drawbacks in this method of operation,
Thus, it has been found that the process itself can be improved both in terms of general operating technology and economically by eliminating the additional operational step of intermediate isolation of the reaction product. That is, the present invention relates to the following general formula {1) (wherein R and R are hydrogen atoms, halogen atoms, such as fluoro-, chloro-, or bromine atoms, or hydroxyl,
represents an alkyl group, an alkoxy group, a hydroxy group, and R and R2 are a hydrogen atom, a cyclohexyl group, or optionally a halogen atom or a hydroxy group;
Carboxy, sulfonic acid- or phenyl group or one OS
It can be an alkyl group substituted by a QH group or an N-acyl group, or a member of an alkyleneimine ring optionally containing a heteroatom together with the nitrogen atom, such as a piveridine or morpholine ring. , R3 is a hydrogen atom or an alkyl group, A is a mononuclear or divalent aromatic group, such as a phenylene or naphthylene residue, or diphenyl, diphenyl ether, diphenylamine.
, diphenyl sulfide, diphenyl sulfone, or azobenzole residue, and these are halogen atoms, lower alkyl groups, lower alkoxy groups,
It may be substituted with a hydroxy-, carboxy-, sulfo- or nitro group, Y represents a group of the following formula, where Z is a halogen atom, a sulfato group (OS
03H), phosphato group (1OP03 day 2) or -○-
Acyl group, R4 represents a hydrogen atom or an alkyl group, m
and n means 0, 1 or 2, q means 0 or 1, and p means 1 or 2. ), which describes a new method for preparing reactive xanthene dyes of the following general formula without isolating any intermediates:

[3' (in the formula, B represents a chloro or bromine atom, R and R have the above-mentioned meanings, and R5 is the following general formula'
4'iro* or a residue represented by the following general formula (5), where R,, R2, R3, R4, A, m'n
, p and q have the meanings given above. ) of the monohalogen xanthylium compound represented by the following general formula '61 (where R3, A, R4, m, n, p and q
has the meaning given above. ) or an amine of the following formula [7} (wherein R and R2 have the meanings given above) and at least 1 mole of an amine of the following formula [7] (wherein R and R2 have the meanings given above) and a pure organic soot, preferably a solvent containing carbonamide groups, especially from about 70 to about 200 oo, preferably in acid amides or N-alkylated acid amides of closed or cycloaliphatic carboxylic acids or in acid amides of inorganic acids or N-alkyl derivatives thereof optionally containing organic residues. The following general formula
In the formula R,, R2, R, R', R3, R4, A, m, n,
q and p have the meanings given above. ) without intermediate isolation of the xanthylium compound.
esterification by treatment with a sulfating agent, a phosphorylating agent, a halogenating agent, an alkyl- or aryl-carboxylic acid halide or a z-carboxylic acid anhydride,
1 in which Z represents a radical, OP03, 2, -halogen or -0-acyl, leading to a xanthene dye. 2 residues R, R', R,
, R2, R3 and R4 include in particular those containing 1 to 5 C atoms in the alkyl residue. Halogen atoms and acylamino groups contained in the residues R and R2 are in particular chloro- and bromine atoms or di- or lower alkanes- or alkenecarbonylaminos or aromatic, for example phenyl- or penzoyl- or chloro-, methyl- in the nucleus. , ethyl, nitro, cyanogen, sulfo, hydroxy, methoxy, ethoxy, hydroxyl, phenylsulfonylamino or pennzylamine substituted by a sulfonamido or sulfonamido group.
-○-Acyl residues represented by Z are in particular lower alkylcarbonyloxy, alkylsulfonyloxy, aromatic carbonyloxy or sulfonyloxy residues such as penzoyloxy, phenylsulfonyloxy or phenyl substituted by a chloro, methyl or sulfo group. It is a sulfonyl or penzoyloxy residue. Among the compounds produced by this new method, those in which the substituents and residues in the general formula [1'' are defined as below can be cited as preferred. R and R are the same or different and mean a hydrogen atom, a fluoro, chloro, bromo, hydroxy, hydroxy, sulfonic acid, lower alkyl or lower alkoxy group, especially a methoxy or ethoxy group. R and R2 are the same or different and are a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, which can be substituted by a phenyl residue or a hydroxyl, carboxylic, sulfonic or sulfato group; Alternatively, it refers to a cyclohexyl residue, or R, and R2 together with the N atom form a piperidine or morpholine ring. R3 represents a hydrogen atom or a lower alkyl group, particularly a methyl or ethyl group. R4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. A means phenylene or naphthylene or a naphthylene residue or a diphenyl, diphenyl ether, diphenylamine, diphenyl sulfide, diphenyl sulfone or azobenzole residue, in which case A is an aromatic It can be substituted in the nucleus by halogen, hydroxyl, lower alkyl, lower alkoxy, carboxy, sulfonic acid mono- or nitro groups. Z is a hydroxy group, a lower alkyl or alkylphenyl or acyloxy residue of a phenylsulfonic acid or -carboxylic acid, such as a p-tolylsulfonyloxy or acetoxy residue, a lower dialkylamino residue such as a dimethyl or jetylamino group, phenoxy, It means a phosphato, sulfato or thiosulfato residue or a halogen atom, such as chloro or bromo. The expression "r-lower" refers to alkyl residues having 1 to 4 carbon atoms. In the method improved by the present invention, during the condensation of a monohalogen xanthylium compound of formula {31 with an amine of formula {7} and subsequently the resulting xanthylium compound of formula {Among the organic solvents used as reaction medium in leading to the compounds of 11, acid amides such as formamide, N-methyl- and N-ethylformamide, N-methyl and N-ethylacetamide,
-dimethyl- and N.N-diethylformamide, N.
N-dimethyl- and N・N-jethylacetamide, N
Particular preference is given to methylpyrrolidone, tetramethylurea and also hexamethylphosphoric triamide, in particular N-methylpyrrolidone being mentioned. The following may be mentioned in particular as starting compounds for the reaction carried out according to the process according to the invention: for monohalogen xanthylium compounds of the formula DT-
Mention may be made of those listed in German Patent Specification No. 915128 and Japanese Patent No. 7-6, as well as the substances which can be prepared according to the description therein. Amines of formula {61 that are suitable for this method include, for example: 4-aminophenyl-B-hydroxy-ethylsulfone, 4-aminobenzyl-8-hydroxy-ethylsulfone, 4-aminophenethyl-8-hydroxy-ethylsulfone, 4-(aminomethyl)-phenyl-8-hydroxy-ethylsulfone , 4-(Yamaichi aminoethyl)
-Phenyl-6-hydroxy-ethyl sulfone, 3-hydroxy-4-aminophenyl-8-hydroxy-ethyl sulfone, 3,6-dimethoxy-4-aminophenyl-8-hydroxy-ethyl sulfone, 3-methoxy-
4-amino-6-methyl-phenyl-8-hydroxy-ethylsulfone, 3-aminophenyl-8-hydroxy-ethylsulfone, 3-aminobenzyl-8-hydroxy-ethylsulfone, 3-amino-6-methoxyphenyl-8- Hydroxy-ethyl sulfone, 3-amino-4-methoxyphenyl-3-hydroxy-ethyl sulfone, 3-amino-4-hydroxy-phenyl-8-hydroxy-ethyl sulfone, 3-amino-4-carpoxyphenyl-8-hydroxy-ethyl Sulfone, 3-
Amino-4-methoxybenzyl-8-hydroxy-ethylsulfone, 2-methyl-5-amino'-penzyl-8-hydroxy-ethylsulfone, 5-amino-2-methyl-m-xylylyl-QI. Q3-bisulfonylethanol, 4-aminobiphenyl-41-(3-hydroxyethylsulfone),
5-aminonaphthyl-4-methylylene-8-hydroxy-ethylsulfone, 5-aminonaphthyl-1-3-
Hydroxyethylsulfone, 6-aminonaphthyl-1
-(8-hydroxy-ethylsulfone), 4-amino-2'-nitrodiphenylamino-4'-(8-hydroxyterethylsulfone), 2-methyl-4-amino-azobenzole-4'-( 3-hydroxyethylsulfone), 2,4-dimethyl-3-aminophenyl-8-hydroxy-ethylsulfone, 3,5-dimethyl-4-aminophenyl-3-hydroxy)ethylsulfone, 2
-Methyl-5-t-butyl-3-aminophenyl-3-hydroxyethylsulfone, 3-chloro and 3-bromo-4-aminophenyl-G-hydroxyethylsulfone, 4-chloro and 4-from-3-aminophenyl-
8;-Hydroxyethylsulfone, 3-sulfo-4-aminophenyl- and 4-sulfo-3-7minophenyl-3-hydroxyethylsulfone. Certain amines of the formula HNR,R2 which are suitable for this process are in particular n-propylamine, diethylamine, cyclo'hexylamine, piverizine,
Morpholine, benzylamine, phenethylamine, 8-aminoethanol, aminoacetic acid, imidiacetic acid, taurine or N-methyltaurine. The acid binder for condensation is preferably an inorganic compound,
For example, caustic soda solution, sodium bicarbonate or sodium carbonate and the corresponding potassium compounds, especially in powdered form, are used. Suitable sulfating agents are, for example, concentrated sulfuric acid, oleum at various concentrations, CK-free sulfuric acid, chlorosulfonic acid, amidolsulfonic acid or other hydrothermal sulfuric acid-donating compounds. Suitable phosphorylating agents are, for example, concentrated phosphoric acid, pyro-, meta- or polyphosphoric acids, polyphosphoric acid alkyl esters or phosphoric acid and phosphorus(V) oxide.
It is a mixture of Examples of halogenating agents include thionylc. Lido or thionyl bromide can be used. Examples of acylating agents used include acetic anhydride or acetyl chloride. Isolation of the xanthene dyes of the general formula '1' obtained according to the above method can be carried out by neutralizing the reaction mixture with an alkaline agent, such as caustic soda solution, sodium carbonate, sodium bicarbonate, sodium acetate or the corresponding potassium compound. After that, precipitation is performed using another solvent. As precipitants it is possible to use, for example, carbon tetrachloride, chloroform, methylene chloride, acetone, methanol, ethanol, butanol and benzol. Compared to the process of Patent No. 7965, this new process offers the following advantages: In the new process of the invention, the condensation as well as the subsequent esterification reaction or residues leading to the corresponding dye of formula '1} The subsequent reaction in Y is also carried out without intermediate isolation, so that the separation and drying of the xanthylium compound of formula {81 is omitted. This represents significant time savings. Furthermore, by using an organic solvent in the pure organic reaction soot, the dye of formula ■ can be converted to the formula {
The amount of esterifying agents, such as sulfuric acid, phosphorylating, halogenating, and acylating agents required to lead to the dye No. 11 is significantly reduced. Large amounts of sulfates, phosphates, chlorides, bromides and acetates are therefore no longer formed during the work-up. A further advantage is that in the new process it is possible to operate with significantly smaller reaction volumes and thus space-time yields can be considerably increased. Furthermore, in the method of the present invention, the reaction soot or the solvent used as a precipitant, of which the furnace liquor consists mainly or almost without exception, can be recovered in good yield by distillation, thereby achieving the above-mentioned purpose. It can be reused. Compared to the method described in Japanese Patent No. 7986, in which the compound of formula [8} is isolated by salt folding, wastewater with a high salt content is produced, in this new method, such wastewater is
Since the above-mentioned inorganic salts are not produced, the normally required measures for environmental protection are not required. Furthermore, the new method provides improved yields compared to known methods. Example 1 50 parts by weight of a monohalogen xanthylium compound of the following formula prepared according to the description in German Patent No. 915128 are mixed with 5.3 parts by weight of soda in 16 parts by weight of N-methylpyrrolidone or N.N-dimethylformamide. N in the presence of parts by weight
- Methyl taurine - 1 with 16.1 parts by weight of sodium
Rope for 3 hours at 10℃. Subsequent esterification with 3 parts by weight of chlorosulfonic acid at 45 qo for 2 hours, cooling and isolation of the dye formed by dilution with methanol and neutralization with methanolic caustic soda and caustic potash. The free acid form of the dye precipitated as a sodium or potassium salt corresponds to the following formula. This is taken out of the oven, washed with methanol, and dried. The dye, produced as a reddish-purple powder, dissolves in water to a bluish-red color and in the presence of sodium bicarbonate gives a bluish-red, intense, very brilliant dyeing and print** on cotton. Example 2 61.4 parts by weight of a monohalogen xanthylium compound of the following formula prepared according to the description in German Patent No. 915128 were mixed with 5.0 parts by weight of soda in 20 parts by weight of N-methylacetamide. React for 3 hours at 115oo with 16.1 parts by weight of N-methyl taurine sodium in the presence of 3 parts by weight.
The resulting condensation product was mixed with 22 parts by weight of anhydrous sulfuric acid and esterified at 4,500 ml.
Neutralize at 0 parts by weight. The precipitated dye corresponds to the following formula as a free warm acid. This is taken out of the furnace and washed with methanol. After drying, a purple-purple powder is obtained, which dissolves in water to a purple color and gives a red-purple print on cotton fabrics with high brightness and good washing fastness. Example 3 A monohalogen xanthylium compound of the following formula 59. Parts by weight of the base were mixed with 5 parts by weight of soda in 17 parts by weight of N.N-dimethylacetamide. The fins were incubated with 16.1 parts by weight of sodium N-methyltaurate in the presence of 16.1 parts by weight of sodium N-methyltaurate at 11T◯ for 3 hours*, and then reacted with 2 parts by weight of chlorsulfonic acid at 50°C for 2 hours. Then, while cooling, dilute with ethyl alcohol and neutralize with potassium acetate. The free acid form of the precipitated potassium salt of the dye corresponds to the following formula. This is collected in a furnace and washed with ethanol. After drying, a red powder is obtained which dissolves in water to a bluish-red color with a yellowish glow and gives a bluish-red dyeing with a high brilliance on cotton. Example 4 5 parts by weight of the sodium salt of the monohalogen xanthylium compound of the following formula were added to 4-aminophenyl-8-hydroxyethylsulfone in 19 parts by weight of hexamethyl-phosphoric acid triamide in the presence of 5.5 parts by weight of soda. It is condensed with 20.1 parts by weight at 140° C. for 3 hours. This is followed by esterification and work-up as described in Example 1. The monochromatic dye corresponds to the following formula in its free acid form and is produced as a reddish-purple powder and has similar properties to the dye described in Example 1. Example 5 The 8-sulfatoethylsulfonyl dye described in Example 1 was prepared in the manner described in Example 1, with the exception that the reaction mixture was neutralized with soda after the end of the esterification and then 6 parts by weight of soda were added; Hold the temperature at 55o0 for 30 minutes*]. Next, excess soda is neutralized with acetic acid, precipitated with acetone, filtered, washed with acetone and dried. A dye whose free acid form corresponds to the following formula is formed as a reddish-purple powder. It dissolves in water to a bluish-red color and gives very bright print patterns on cotton fabrics with good washfastness.
*Mount 6 Parts by weight of the following monochloroxanthylium transferor 6 prepared according to the description in German Patent No. 915128 are reacted with sodium N-methyltaurine under the reaction conditions of the procedure described in Example 1. let Next, 44 parts by weight of acetic anhydride was added to the reaction mixture, and the mixture was heated to 10,500 ml. The dye formed corresponds in free acid form to the following formula, is produced as a purple powder, dissolves purple in water, and gives a bluish-red dyeing with good wash fastness and high brightness on cotton. . Example 7 Product 5 of the formula described in German Patent No. 915128
9. The weight part of red chloride was condensed with N-methyl taurine-sodium as described in Example 1, followed by thionyl chloride 34
React with parts by weight at 50 qo. The resulting dye has a free acid form equivalent to the following formula, is produced as a red powder, dissolves in water to a bluish-red color with a yellow crab glow, and has a high brightness on cotton with good washing fastness. Gives a bluish-red print. The dyes listed in the table below can be produced in the same manner as described in the examples above.

Claims (1)

[Claims] 1 The following general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, R and R' are hydrogen atoms, halogen atoms, hydroxy, alkyl, alkoxy, carboxy, or sulfonic acid groups, R_1 and R_2 are hydrogen atoms, cyclohexyl groups, or optionally halogen atoms or hydroxy-
, carboxy-, sulfonic acid- or phenyl group or -O
SO_3 is an alkyl group substituted by a H- or -NH-acyl- group, or together with the nitrogen atom is a member of an alkyleneimine ring optionally containing a heteroatom, R_3 is a hydrogen atom or an alkyl group, A is a mononuclear or dinuclear aromatic residue, which is substituted in the aromatic nucleus by a halogen atom, lower alkyl group, lower alkoxy group, hydroxy-, carboxy-, sulfo- or nitro group. is formed, and Y represents a group with the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc.
2) or -O-acyl group, R_4 represents a hydrogen atom or an alkyl group, m and n are 0, 1 or 2, q is 0 or 1
, P means 1 or 2. ] When producing a reactive xanthene dye in a pure organic medium, the following general formula (3) ▲ can be produced without isolating the intermediate.
There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, B represents a chloro or bromine atom, and R and R
' has the above meaning, R_5 represents the residue of the following general formula (4) ▲ Numerical formula, chemical formula, table, etc. ▼, where R_3, R_4, A, m, n, p and q are the above has the meaning of ] One mole of the monohalogen xanthylium compound is expressed by the following formula (7). There are mathematical formulas, chemical formulas, tables, etc.
and R_2 have the above meanings. ) with at least 1 mole of an amine in the presence of an acid binder in a solvent containing a carbonamide group at about 70°C to about 200°C to obtain the following general formula (8) ▲ Numerical formula, chemical formula, table etc.▼(In the formula, R_1, R_2, R, R',
R_3, R_4, A, m, n, q and p have the meanings given above. ) is esterified by treatment with a sulfating agent, phosphorylating agent, halogenating agent, alkyl- or aryl-carboxylic acid halide or -carboxylic acid anhydride without intermediate isolation, and In, Z is a group -OSO_3H, -OPO_3H_2, -
A process characterized in that it leads to xanthene dyes meaning halogen or -O-acyl. 2 General formula below ▲ Numerical formula, chemical formula, table, etc. are available ▼ [In the formula, R and R' are hydrogen atoms, halogen atoms, hydroxy, alkyl, alkoxy, carboxy, or sulfonic acid groups, and R_1 and R_2 are hydrogen atoms , cyclohexyl group or optionally halogen atom or hydroxy-,
Carboxy-, sulfonic acid- or phenyl group or -OS
O_3 is an alkyl group substituted by a H- or -HN-acyl- group, or together with the nitrogen atom is a member of an alkyleneimine ring optionally containing a heteroatom, R_3 is a hydrogen atom or an alkyl group, A is mononuclear or 2
A nuclear aromatic residue, which can be substituted in the aromatic nucleus by a halogen atom, lower alkyl group, lower alkoxy group, hydroxy-, carboxy-, sulfo- or nitro group, where Y is represented by the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ represents a group, where Z is a halogen atom, a sulfato group (OSO_3H), a phosphato group (-
OPO_3H_2) or -O-acyl group, R_4 represents a hydrogen atom or an alkyl group, m and n are 0, 1 or 2
, q means 0 or 1, P means 1 or 2. ] When producing a reactive xanthene dye in a pure organic medium, the following general formula (3) ▲ can be produced without isolating the intermediate.
There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, B represents a chloro or bromine atom, and R and R
' has the above meaning, R_5 represents the residue of the following general formula (4) ▲ Numerical formula, chemical formula, table, etc. ▼, where R_3, R_4, A, m, n, p and q are the above has the meaning of ] 1 mole of monohalogen xanthylium compound ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 and R_2
has the meaning given above. ) with at least 1 mole of amine in hexamethylphosphoric acid triamide in the presence of an acid binder at about 70°C to about 200°C to obtain the following general formula (8) ▲ Numerical formula, chemical formula, table, etc. There is ▼ (in the formula R_1, R_2, R, R'
, R_3, R_4, A, m, n, q and p have the meanings given above. ) is esterified by treatment with a sulfating agent, phosphorylating agent, halogenating agent, alkyl- or aryl-carboxylic acid halide or -carboxylic acid anhydride without intermediate isolation, and In, Z is a group -OSO_3H, -OPO_3H_2, -
A process characterized in that it leads to xanthene dyes meaning halogen or -O-acyl. 3 General formula below ▲ Numerical formula, chemical formula, table, etc. are available ▼ [In the formula, R and R' are hydrogen atoms, halogen atoms, hydroxy, alkyl, alkoxy, carboxy, or sulfonic acid groups, R_1 and R_2 are hydrogen atoms , cyclohexyl group or optionally halogen atom or hydroxy-,
Carboxy-, sulfonic acid- or phenyl group or -OS
an alkyl group substituted by an O_3H- or -HN-acyl- group, or, together with the nitrogen atom, a member of an alkyleneimine ring optionally containing a heteroatom;
R_3 is a hydrogen atom or an alkyl group, and A is a mononuclear or dinuclear aromatic residue. or can be substituted with a nitro group, and Y represents a group of the following formula ▲ There are numerical formulas, chemical formulas, tables, etc. ▼, where Z is a halogen atom, a sulfato group (OSO_3H), a phosphate group (-
OPO_3H_2) or -O-acyl group, R_4 represents a hydrogen atom or an alkyl group, m and n are 0, 1 or 2
, 9 means 0 or 1, P means 1 or 2. ] When producing a reactive xanthene dye in a pure organic medium, the following general formula (3) ▲ can be produced without isolating the intermediate.
There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, B represents a chloro or bromine atom, and R and R
' has the above-mentioned meaning, and R_5 represents a residue of the following general formula (5) ▲ Numerical formula, chemical formula, table, etc. ▼, where R_1 and R_2 have the above-mentioned meaning. ] 1 mole of a monohalogen xanthylium compound represented by the following general formula (6) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (wherein R_3, A, R_4, m, n, p and q have the above meanings. ) in the presence of an acid binder in a solvent containing a carbonamide group at about 70°C to about 20°C.
The following general formula (8) was obtained by reacting at 0℃ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1, R_2, R, R', R_3, R_4, A
, m, n, q and p have the meanings given above. ) is esterified by treatment with a sulfating agent, phosphorylating agent, halogenating agent, alkyl- or aryl-carboxylic acid halide or -carboxylic acid anhydride without intermediate isolation, and In, Z is a group -OSO_3H, -OPO_3H_2, -
A process characterized in that it leads to xanthene dyes meaning halogen or -O-acyl. 4 General formula below ▲ Numerical formula, chemical formula, table, etc. are available ▼ [In the formula, R and R' are hydrogen atoms, halogen atoms, hydroxy, alkyl, alkoxy, carboxy, or sulfonic acid groups, R_1 and R_2 are hydrogen atoms , cyclohexyl group or optionally halogen atom or hydroxy-,
Carboxy-, sulfonic acid- or phenyl group or -OS
an alkyl group substituted by an O_3H- or -NH-acyl group, or, together with the nitrogen atom, a member of an alkyleneimine ring optionally containing a heteroatom;
R_3 is a hydrogen atom or an alkyl group, and A is a mononuclear or dinuclear aromatic residue. or can be substituted with a nitro group, and Y represents a group of the following formula ▲ There are numerical formulas, chemical formulas, tables, etc. ▼, where Z is a halogen atom, a sulfato group (OSO_3H), a phosphate group (-
OPO_3H_2) or -O-acyl group, R_4 represents a hydrogen atom or an alkyl group, m and n are 0, 1 or 2
, q means 0 or 1, P means 1 or 2. ] When producing a reactive xanthene dye in a pure organic medium, the following general formula (3) ▲ can be produced without isolating the intermediate.
There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, B represents a chloro or bromine atom, and R and R
' has the above-mentioned meaning, and R_5 represents a residue of the following general formula (5) ▲ Numerical formula, chemical formula, table, etc. ▼, where R_1 and R_2 have the above-mentioned meaning. ] 1 mole of a monohalogen xanthylium compound represented by the following general formula (6) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (wherein R_3, A, R_4, m, n, p and q have the above meanings. ) in the presence of at least 1 mole of an amino compound consisting of
The following general formula (8) was obtained by reacting at 0℃ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1, R_2, R, R', R_3, R_4, A
, m, n, q and p have the meanings given above. ) is esterified by treatment with a sulfating agent, phosphorylating agent, halogenating agent, alkyl- or aryl-carboxylic acid halide or -carboxylic acid anhydride without intermediate isolation, and In, Z is a group -OSO_3H, -OPO_3H_2, -
A process characterized in that it leads to xanthene dyes meaning halogen or -O-acyl.