JPH0136612B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for synthesizing sulfonyl chloride having a dye residue. Sulfonyl chlorides with dye residues are important as intermediates for the synthesis of dye-releasing compounds used in diffusion transfer color photography. Conventionally, phosphorus pentachloride [Helv.Chim.Acta 38 ,
1329 (1955)] and chlorsulfonic acid [U.S.
No. 3929760], but all of them emit smoke and are difficult to handle, making them unsuitable for industrial-scale synthesis. Also, thionyl chloride-N,N-dimethylformamide [Helv.Chim.Acta 42 , 1653 (1959)]
Although phosphorus oxychloride-N,N-dimethylformamide [US Pat. No. 4,013,633 (1977)] is known as a chromating agent, subsequent research has revealed that it has poor chemoselectivity. Phosphorus oxychloride-N,N-
Although chlorination using dimethylacetamide has been reported [JP-A-54-161332], further improvement in yield is desired. The first object of the present invention is to provide a method for synthesizing sulfonyl chloride with a high yield, and the second object is to provide a method for synthesizing sulfonyl chloride under mild conditions and with simple operations. The third object is to provide a functional group-selective method for synthesizing sulfonyl chloride. The present inventor has conducted intensive research in view of the above object, and as a result, has finally achieved the present invention that achieves the above object. That is, the present invention is characterized in that a sulfonic acid having a dye residue represented by the following general formula () is reacted with a compound represented by the general formula () in the presence of sulfolane. This is a method for synthesizing the sulfonyl chloride shown below. However, Dye represents a dye residue; R ¹ represents an alkyl group having 1 to 23 carbon atoms; R ² and R ³ may be the same or different and represent an alkyl group having 1 to 24 carbon atoms. R ¹ and R ² ; R ² and R ³ may be bonded to each other to form a ring. The above alkyl group may have a substituent, but preferably has no substituent. Y is an anion of an acid containing phosphorus or sulfur. Note that the compounds represented by [ ] also include corresponding salts (for example, alkali metal salts and salts of organic bases). Examples of dye residues represented by Dye are azo dye,
Examples include anthraquinone dyes, azomethine dyes, phthalocyanine dyes, and metal complex dyes. Above all, the special features of the method of the present invention are exhibited when the Dye is an azo dye residue. That is, in a preferred embodiment, the compounds represented by () and () are represented by the following formulas () and (), respectively. A-N=N-B-(L) _o ―SO ₃ H [] A-N=N-B-(L) _o ―SO ₂ Cl [] However, A represents an aromatic group or a heteroaromatic group. , B represents an aromatic group or a heteroaromatic group. L represents a divalent aromatic group or aliphatic group, and n is 0 or 1. Examples of the aromatic group represented by A or B include a phenyl group or a naphthalene group. These phenyl groups or naphthalene groups include hydroxyl groups, alkyl groups, phenyl groups, alkoxy groups, carbonamide groups, sulfonamide groups, carbamoyl groups, sulfamoyl groups,
It may be substituted with an amino group, a cyano group, a nitro group, an alkylsulfonyl group, an aromatic sulfonyl group, a halogen atom, a trifluoromethyl group, or the like. Examples of the heteroaromatic ring represented by A or B include a pyrazole group, a pyridine group, a quinoline group, and the like. These pyrazole groups, pyridine groups, quinoline groups, etc. are hydroxyl groups,
Alkyl group, phenyl group, alkoxy group, carbonamide group, sulfonamide group, carbomoyl group, sulfamoyl group, amino group, cyano group, nitro group, alkylsulfonyl group, aromatic sulfonyl group, halogen atom, trifluoromethyl group, etc. May be replaced. The divalent aromatic group represented by L includes a phenylene group. This phenylene group may be substituted with the substituents listed for the aromatic group represented by A above. The compound represented by the formula [] is a compound represented by the U.S. patent
3954476; 3932380; 3931144; 3942987;
4013635; 4013633; 4135929; 4076529; British patent 2026711A; 2027220A; 2029852A;
2010883A; West German patent application (OLS) 2630999;
2847371; Research Disclosure 17630 (1978);
Contains compounds described in 16475 (1977), etc. The alkyl group of R ¹ may be straight chain or branched,
It has 1 to 23 carbon atoms, preferably 1 to 17 carbon atoms, and more preferably 1 to 4 carbon atoms, and includes, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and the like. The alkyl group of R ² or R ³ may be linear or branched and has 1 to 24 carbon atoms, preferably 1 to 18 carbon atoms, and more preferably 1 to 4 carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, butyl group. Examples include bases. When R ¹ and R ² or R ² and R ³ are bonded to each other to form a ring, 1 to 2 heteroatoms (oxygen,
(nitrogen, sulfur). When R ¹ and R ² are combined, the amide bond forms part of the ring, so for example, morpholin-3-one, pyrrolidone,
A ring with an oxy group (=o) such as caprolactam, piperidone, and pyrrolidinone is formed. on the other hand
When R ₂ and R ₃ are combined, the amide nitrogen becomes a member of the ring, forming a ring such as morpholine, pyrrolidine, piperidine, etc. It is easy to obtain and easy to process after reaction.
When R ¹ , R ² and R ³ are all methyl groups; and when R ¹ and R ² combine to form a trimethylene group and
It is preferable that R ³ is a methyl group, and the former is particularly preferable. As Y, _OPOCl2 , OSOCl, etc. are preferable. The compound represented by formula () is preferably produced from an amide represented by formula () and an acid chloride represented by formula (). (However, the symbols R ¹ , R ² , and R ³ have the same meaning as in formula ().
Y ¹ is an acid residue containing phosphorus or sulfur. ) It should be added here that Y-H and Y ¹ -OH represent the same compound. Specific examples of the sulfonyl chloride synthesized in the present invention are as follows. Compound 1

[Formula] However

[Formula] Compound 2 In the formula of Compound 1

[Formula] Compound 3 In the formula of Compound 1

[Formula] Compound 4 In the formula of Compound 1

[Formula] Compound 5 In the formula of Compound 1

[Formula] Compound 6 In the formula of Compound 1

[Formula] Compound 7 In the formula of Compound 1

[Formula] Compound 8 In the formula of Compound 1

[Formula] Compound 9 In the formula of Compound 1

[Formula] Compound 10 In the formula of compound 1

[Formula] Compound 11 In the formula of compound 1

[Formula] Compound 12 In the formula of compound 1

[Formula] Compound 13 compound 14

【formula】 compound 15

[Formula] Compound 16 However, R ⁴ = CH ₃ , R ⁵ = H Compound 17 In the formula of compound 16 R ⁴ = -C ₂ H ₅ R ⁵ = H Compound 18 In the formula of compound 16 R ⁴ = -CH (CH ₃ ) ₂ R ⁵ = H Compound 19 In the formula of compound 16 R ⁴ = -C ₂ H ₅ R ⁵ = -C ₂ H ₅ Compound 20 In the formula of compound 16 R ⁴ = -C ₃ H ₇ -(n) R ⁵ = -C ₃ H ₇ -(n) Compound 21 In the formula of compound 16 R ⁴ , R ⁵ = -(CH ₂ ) ₄ - Compound 22 In the formula of compound 16 R ⁴ = -C ₆ H ₅ R ⁵ =H Compound 23 In the formula of compound 16 R ⁴ = CH ³ R ⁵ = CH ₃ Compound 24 In the formula of compound 16 R ⁴ = C ₄ H ₉ (n) R ₅ = C ₄ H ₉ (n) Compound 25 In the formula of compound 16 R ⁴ = C ₄ H ₉ (t) R ⁵ = H Compound 26 In the formula of compound 16 R ⁴ = R ⁵ = -CH(CH ₃ ) ₂ Compound 27 However, R ⁴ = CH ₃ , R ⁵ = H Compound 28 In the formula of compound 27 R ⁴ = C ₂ H ₅ , R ⁵ = H Compound 29 In the formula of compound 27 R ⁴ = CH(CH ₃ ) ₂ R ⁵ = H Compound 30 In the formula of compound 27, R ⁴ = R ⁵ = C ₂ H ₅ Compound 31 In the formula of compound 27, R ⁴ = C ₄ H ₉ (t) R ⁵ = H Compound 32 However, R ⁴ = CH ₃ , R ⁵ = H Compound 33 In the formula of Compound 32, R ⁴ = C ₂ H ₅ , R ⁵ = H Compound 34 In the formula of Compound 32, R ⁴ = CH(CH ₃ ) ₂ , R ⁵ =H Compound 35 In the formula of Compound 32, R ⁴ = R ⁵ = C ₂ H ₅ Compound 36 In the formula of Compound 32, R ⁴ = C ₄ H ₉ (t), R ⁵ = H Sulfonic acid()
is dissolved or suspended in sulfolane and reacted with the reactant (). Reactants () are amides () and acid chlorides ()
It is common to generate it in situ from
In this case, the dye sulfonic acid (), amide ()
and sulfolane (a solvent such as acetonitrile that does not affect the reaction may be added),
This can be achieved by a simple operation of dropping acid chloride () onto this. Further, the acid chloride (2) may be added dropwise after being diluted with a solvent that does not affect the reaction, or may be added dropwise as is (without dilution). The amount of amide () to be used in the present invention has no upper limit for the reasons mentioned above, and is basically a catalytic amount or more, more specifically about 0.001 mol or more per 1 mol of dye sulfonic acid (), preferably about 0.01 mol or more. Use in a molar or higher range. Particularly preferably, the amount is in the range of 0.1 mol to 5 mol. The amount of acid chloride () used in the present invention is:
Generally, about 1 mole of dye sulfonic acid ()
0.3 moles to about 20 moles, preferably about 1 mole to about 5 moles
Use in molar range. The sulfolane used in the present invention has a remarkable effect on improving the yield of the chlorination reaction of the present invention. Sulfolane is best used as a solvent, about 50ml to 50% per mole of dye sulfonic acid.
Preferably 100ml~10, more preferably 500ml~
Use within the range of 5. Since the reaction of the present invention described above proceeds rapidly, there is no particular limitation on the reaction temperature, but the reaction temperature is about 10°C to about 10°C.
The temperature is set at 200°C, preferably about 10°C to about 100°C, particularly preferably about 30°C to about 60°C. The reaction is usually carried out under normal pressure, but may also be carried out under low pressure or reduced pressure. The time for dropping phosphorus oxychloride can be appropriately determined based on the reaction temperature, the type of oxime used as a raw material, the scale of the reaction, etc., and can usually be set within a range of about 5 minutes to about 3 hours. After the dropwise addition of phosphorus oxychloride is completed, the above temperature may be maintained for an additional 30 minutes to 2 hours to complete the reaction. After the reaction is completed, it is usually left to cool and then poured into ice water to remove the precipitated crystals. If necessary, recrystallization is performed in a suitable solvent such as benzene, acetonitrile, etc. to obtain the desired sulfonyl chloride (2). In order to show more detailed synthetic operations, Examples and Comparative Examples are given below. Example 1 4.21 g of 3-cyano-4-(2-methoxy-5-sulfophenylhydrazone)-1-phenyl-5-pyrazolone sodium salt was suspended in a mixture of 10 ml of sulfolane and 10 ml of acetonitrile, and N,N
- 3.6 ml of dimethylacetamide was added. to this,
3.6 ml of phosphorus oxychloride was added at below 40°C. The reaction mixture was stirred at 50-55°C for 1.5 hours. After cooling,
It was poured into ice water and the precipitated crystals were collected. Yield of compound 8: 4.06 g (97%). mp.235-236℃ (decomposition). Comparative Example 1 Using the same compound as in Example 1, a reaction was carried out without sulfolane. 3-cyano-4-(2
-methoxy-5-sulfophenylhydrazono)-
1-phenyl-5-pyrazolone sodium salt 4.21
g was suspended in 40 ml of acetonitrile, followed by 3.6 ml of N,N-dimethylacetamide and then 3.6 ml of phosphorus oxychloride.
Added ml. After stirring at 50-55℃ for 1.5 hours,
When the same post-treatment as in Example 1 was carried out, Compound 8 was obtained in a yield of 3.40 g (81%). Comparing both experiments, it can be seen that the yield is significantly improved in the presence of sulfolane. Example 2 3-(N-methylsulfamoyl)-4-(2-
Methyl-4-sulfophenylhydrazono)-1-
Suspend 4.37 g of phenyl-5-pyrazolone sodium salt in a mixture of 20 ml of sulfolane and 30 ml of acetonitrile, and add N,N-dimethylacetamide.
3.6 ml was added followed by phosphorus oxychloride. The reaction mixture was stirred at 50-55°C for 1.5 hours. After cooling the reaction mixture, it was poured into ice water to collect the precipitated Compound 4. Yield 3.95g (91%). mp.217-218℃ (decomposition). Comparative Example 2 Using the same compound as in Example 2, a reaction was carried out without sulfolane. 4.37 g of 3-(N-methylsulfamoyl)-4-(2-methyl-4-sulfophenylhydrazono)-1-phenyl-5-pyrazolone sodium salt was suspended in 40 ml of acetonitrile, and N,N-dimethyl 3.6 ml of acetamide was added followed by phosphorus oxychloride. After stirring at 50 to 55°C for 1.5 hours, the same post-treatment as in Example 2 was performed to obtain Compound 4 in a yield of 3.04 g (70%). A comparison of Example 2 and Comparative Example 2 shows that the yield is significantly improved in the presence of sulfolane.

Claims (1)

[Scope of Claims] 1. A sulfonyl chloride represented by the following general formula (), which is characterized by reacting a dye compound represented by the following general formula () with a compound represented by the general formula () in the presence of sulfolane. synthesis method of However, Dye represents a dye residue; R ¹ represents an alkyl group having 1 to 23 carbon atoms; R ² and R ³ may be the same or different and represent an alkyl group having 1 to 24 carbon atoms. R ¹ and R ² ; R ² and R ³ may be bonded to each other to form a ring. Y is an anion of an acid containing phosphorus or sulfur.