CA1228066A - Process for the production of aromatic sulfonyl chloride having a quinonediazido group - Google Patents

Abstract

SO-1-36587C/YT/84.
ABSTRACT OF THE DISCLOSURE
A process for the production of an aromatic sulfonyl chloride having a quinonediazido group is described, comprising reacting a sulfonic acid or its salt represented by the formula (I), Ri-Ar-(SO3M)j, wherein all the symbols are as defined in the appended claims, with phosgene in the presence of a catalyst, whereupon an aromatic sulfonyl chloride having a quinone-diazido group of the formula (II), Ri-Ar-(SO2C?)j, is obtained. In accordance with the present invention, the desired sulfonyl chloride can be prepared by a simplified procedure and further in a high yield.

Description

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PROCESS FOR THE PRODU~TION OF AROMATIC
SULFONYL CHLORIDE HAVI~G A QUINONEDIAZIDO GROUP

FIELD OF THE INVF,NTION

The present invention relates to a process for the production o:E an aromatic sulfonyl chloride having a qui.nonediazido group. More particularly, it is concerned with a process for producing an aromatic sulfonyl chloride containing a quinonediazido group by reacting an aromatic sulfonic acid containing a quinonedia~ido group or its salt with phosgene in the presence of a catalyst r ~ ..

BACKGRO~ND OF THE INVENTION

It is well known that an aromatic sulfonyl chloride having a quinonediazido group (hereinafter referred to as "quinonediazide sulfonyl chloride") is useful as an intermediate for use in preparation of organic industrial chemicals such as those used in photography or pr~nting, dyes, or liquid crystals.
With recent marked advance of photography, printing, and electronics, the quinonediazide sulfonyl chloride has received an increasing attention particularly as an intermediate for light-sensitive agents utilizing its reactivity to light.
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1~2~3~)66 ~ Ieretofore, the quinonediazide sulfonyl chlo~ide has been prepared from quinonediazidesulfonic acid by techniques such as a method in which quinone-diazidesulfonic acid is reacted with a great excess of S chlorosulfonic acid, and a method in which quinone-diazidesulfonic acid is reacted with chlorine in the presence of chlorosulfonic acid or anhydrous sulfuric acid, for example (see West German Patents 246,573 and 246,574).
These known methods, however, suffer from several disadvantages. One is that since equilibrium exists between the starting quinonediazidesulfonic acid and the reaction product (quinonediazide sulfonyl chloride), if the yield of the product is intended to increase, it is necessary to add chlorosulfonic acid in a greatly excessive amount such as in a proportion of about 10 to 20 molar times the stoichiometric amount.
Even in such a case, the yield of the quinonediazide s~llfonyl chloride is at mos-t about 80~. Another disadvan-tage is that for removal of the unreacted startingmaterial, a complicated operation is required and, furthermore, a long operation time is undesirably needed.
In industrial practice, therefore, these known methods cannot be said to be advantageous.

In order to overcome t:he above defects and to establish a process for efficient production of the quinonediazide sulfonyl chloride, investigations have beer. made extensively on the reaction between quinone-diazidesulfonic acid or its salt and phosgene. As aresult, unexpectedly, it has been found that the quinone-diazide sulfonyl chloride can be produced in a simplified procedure in a high yield by reacting quinonediazide-sulfonic acid or its salt with phosgene in the presence of a catalyst.
SU~MARY OF THE INVENTION
-An object of the present invention is to provide a process for producing a sulfonyl chloride represented by the formula (II):

Ri-Ar-(S02CQ)j (II) by reacting a sulfonic acid or its salt represented by the formula (I):

Ri-Ar-(S03M)j (I) with phosgene in the presence of a catalyst and further in the presence or absence of a solvent.

0~6 In the above formulae (I) and (II), R, which mzy be the same or different, is a monovalent substit-uent selected from a halogen atom, a nitro group, and an alkyl group having from 1 to 5 carbon atoms; Ar is an organic group of the quinonediazide structure which is substituted by at least one oxy anion and at least one diazonium cation; M is a hydrogen atom, a mono-, di- or trivalent metal, or an organic amino cation; i is an integer of 0 to 5; and i is an integer of 1 to 5.
DETAILED DESCRIPTION OF THE INVENTION
Examples of the sulfonic acid or its salt of the formula (I) which can be used in the invention are aromatic sulfonic acids or their salts having a quinone-diazido group, represented by the following formulae (III), ~IV), and (V).

\ ~ ~N2 1 ~ (SO3~l)p (III) ~ R2 xc ~z~

( \3 )n ( 3 )m R1 l (IV) ~ ~N2 Xb x a ( 3 )n O

~ ~¢ ~ ¢ ~ ~X03M) P ~V) In the above formulae (III), (IV) and (V), R1 and R2, which may be the same or different, are each an aromatic fused ring residue represented by -C=C-C=C-, a monovalent substituent represented by -SO3M, or a monovalent substituent represented by -X, in which X, which may be the same or different, is a monovalent substituent selected from a hydrogen atom, a halogen atorn, a nitro group, and an alkyl group having from 1 to 3 carbon atoms; M is the same as deined above; and a, b, c, _, n and ~ are each 0 or a positive integer satisfying the relations that a+m=2, b~n=4, and c+p=4~
provided that at least one -SO~M group is contained in the formula.

~Z28066 Specific examples include benzoquinonediazide-monosulfonic acid, naphthoquinonediazidemonosulfonic acid, anthraquinonediazidesulfonic acid, phenanthrene-diazidemonosulfonic acid, pyridinequinonediazidemono-sulfonic acid, quinolenequinonediazidemonosulfonic acid,chrysenquinonediazidemonosulfonic acid, benzoquinone-diazidedisulfonic acid, naphthoquinonediazidedisulfonic acid, anthraquinonediazidedisulfonic acid, phenanthrene-quinonediazidedisulfonic acid, pyridinequinonediazide-disulfonic acid, quinolenequinonediazidedisulfonic acid,chrysenquinonediazidedisulfonic acid, benzoquinonedia2ide-trisulfonic acid,.naphthoquinonediazidetrisulfonic acid, anthraquinonediazidetrisulfonic acid, phenanthrene-quinonediazidetrisulfonic acid, pyridinequinonediazide-trisulfonic acid, quinolenequinonediazidetrisulfonicacid, chrysenquinonediazidetrisulfonic acid; their nitrG, c~oro, bromo or alkyl nucleus-substituted compounds; and their sodium, potassium, magnesium, calcium, barium, aluminum, trimethylammonium, triethylammonium, pyridinium, or N,N-dimethylanilinium salts.
In more detail, the following can be ~iven.
1,~-Benzoquinonediazide-2-sulfonic acid, 1,~-~enzoquincnediazide-3-sulfonic acid, 2-meth~
benzoquinonediazide-5-sulfonic acid, 2-methyl-1,~-benzoquinonediazide-6-sulfonic acid, 2-isopropyl-1,4-~ZX~3~36~

benzoquinonediazide-3-sulfonic acid, 2-chloro-1,4-benzoquinonediazide-5-sulfonic acid, 2-chloro-1,4-benzoquinonediazide-6-sulfonic acid, 2-bromo-1,4-benzoquinonediazide-5-sulfonic acid, 2-bromo-1,4-benzoquinonediazide-6-sulfonic acid, 2-nitro-1,4-benzoquinonediazide-5-sulfonic acid, 2,6-dimethyl-1,4-benzoquinonediazide-3-sulfonic acid, 2,6-dichloro-1,4-benzoquinonediazide-3-sulfonic acid, 2,6-dibromo-1,4-benzoquinonediazide-3-sulfonic acid, 2-chloro-6-nitro-1,4-benzoquinonediazide-3-sulfonic acid, 2-fluoro-1,4-benzoquinonediazide-5-sulfonic acid, 1,2-benzoquinone-diazide-3-sulfonic acid, 1,2-benzoquinonediazide-4-sulfonic acid, 1,2-benzoquinonediazide-5-sulonic acid, 1,2-benzoquinonediazide-6-sulfonic acid, 4-nitro-1,2-benzoquinonediazide-5-sulfonic acid, 4-chloro-1,2-benzoquinonediazide-5-sulfonic acid, 4-bromo-1,2-benzoquinonediazide-5-sulfonic acid, 6-chloro-1,2-benzoquinonediazide-4-sulfonic acid, 6-bromo-1,2-benzoquinonediazide-4-sulfonic acid, 6-chloro-1~2-benzoquinonediazide-5-sulfonic acid, 6-bromo-1,2-benzoquinonediazide-5-sulfonic acid, 6-nitro-1,2-benzoquinonediazide-5-sulfonic acid, 4-methyl-1,2-benzoquinonediazide-5-sulfonic acid, 5-methyl-1,2-benzoquinonediazide-4-sulfonic acid, 3,5-dichloro-1,2~
benzoquinonediazide-4-sulfonic acid~ 3,5,6-trichloro-1,2-~Z21~6~

benzoquinonediazide~4-sulfonic acid, 4-nitro-6-chloro-1,2-benzoquinonediazide-5-sulfonic ac:id, 1,2-benzoquinone-diazide-3,5-disulfonic acid, 1,2-naphthoquinonediazide-3-sulfonic acid, 1,2-naphthoquinonediazide-4-sulfonic acid, 1,2-naphthoquinonediazide-5-sulfonic acid, 1,2-naphthoquinonediazide-6-sulfonic acid, 1,2-naphtho-quinonediazide-7-sulfonic acid, 4-chloro-1,2-naphtho-quinonediazide-5-sulfonic acid, 3-bromo-1,2-naphtho-quinonediazide-5-sulfonic acid, 4-nitro-1,2-naphtho-quinonediazide-5-sulfonic acid, 6-nitro-1,2-naphtho-quinonediazide-4-sulfonic acid, 6-nitro-1,2-naphtho-quinonediazide-5-sulfonic acid, 1,2-naphthoquinone-diazide-3,6-disulfonic acid, 1,2-naphthoquinonediazide-4,6-disulfonic acid, 1,2-naphthoquinonediazide-4,6,8-trisulfonic acid, 2,1-naphthoquinonediazide-4-sulfonic acid, 2,1-naphthoquinonediazide-5-sulfonic acid, 2,1-naphthoquinonediazide-6-sulfonic acid, 2,1-naphtho-quinonediazide-7-sulfonic acid, 2,1-naphthoquinone-diazide-8-sulfonic acid, 3-chloro-2,1-naphthoquinone-diazide-5-sulfonic acid, 6-chloro-2,1-naphthoquinone-diazide-4-sulfonic acid, 8-chloro-2,1-naphthoquinone-diazide-4-sulfonic acid, 3-bromo-2,1-naphthoquinone-diazide-4-sulfonic acid, 7-bromo-2,1-naphthoquinone-diazide-4-sulfonic acid, 6,8-dichloro-2,1-naphthoquinone-diazide-4-sulfonic acid, 6-nitro-2,1-naphthoquinone-~22~ i6 diazide-4-sulfonic acid, 5-nitro-2,1-naphthoquinone-diazide-6-sulfonic acid, 2,1-naphthoquinonediazide-3,6-disulfonic acid, 2,1-naphthoquinonediazide-4,6-disulfonic acid, 1,4-naphthoquinonediazide-5-sulfonic acid, 1,9-naph-thoquinonediazide-6-sulfonic acid, 1,9-naphtho-quinonediazide-7-sulfonic acid, 7-chloro-1,4-naphtho-quinonediazide-7-sulfonic acid, 1,4-naphthoquinone-diazide-5,7-disulfonic acid, 1,8-naphthoquinonediazide-3-sulfonic acid, 1,8-naphthoquinonediazide-6-sulfonic acid, 1,8-naphthoquinonediazide-3,6-disulfonic acid, 1,7-naphthoquinonediazide 3-sulfonic acid, 1,7-naphtho-quinonediazide-3,6-disulfonic acid, 1,6-naphthoquinone-diazide-3-sulfonic acid, 2,6-naphthoquinonediazide~1,9-disulfonic acid, 2-nitro-1,4-naphthoquinonediazide-7-sulfonic acid, 9,10,2,1-anthraquinonediazide~4-sulfonic acid, 9,10,2,1-anthraquinonediazide-5-sulfonic acid, 9,10,1,9-anthraquinonediazide-5-sulfonic acid, 9,10,2,1-anthraquinonediazide-5,7-disulfonic acid, 2,1-phenanthrenequinonediazide-5-sulfonic acid, 2,1-phenanthrenequinonediazide-6-sulfonic acid, 9,10-phenanthrenequinonediazide-5-sulfonic acid, 9,10-phenanthrenequinonediazicle-5,7-disulfonic acid, 1-methyl-9-isopropyl-9,10-phenanthrenequinonediazide-6-sulfonic acid, 7-nitro-9,10-phenanthrenequinonedia~ide-5-s~-lfonic acid, 1-iodo-9,10--phenan~hrenequinonediazide-S-sulfonic ~2~ 66 acid, 2,3-pyridinequinonediazide-5-sulfonic acid, 4,3-pyridinequinonediazide-5-sulfonic acid, 2-methyl-4,3-pyridinequinonediazide-5-sulfonic acid, 4,3-quinoline-quinonediazide-6-sulfonic acid, 4,3-quinolinequinone-diazide-7-sulfonic acid, 6-chloro-4,3-quinolinequinone-diazide-8-sulfonic acid, 7,8-quinolinequinonediazide-5-sulfonic acid, 1,2-chrysenquinonediazide-6-sulfonic acid, 3,4-chrysenquinonediazide-6-sulfonic acid, 8-nitro-3,4-chrysenquinonediazide-6-sulfonic acid, and 8-bromo-10-nitro-3,4-chrysenquinonediazide-6-sulfonic acid; and their sodium, potassium, magnesium, calcium, barium, aluminum, trimethylammonium, triethylammonium, pyridinium, or N,N-dimethylanilinium salts.
In particular, 1,2-benzoquinonediazide-4-sulfonic acid, 1,2-benzoquinonediazide-5-sulfonic acid, 1,2-naphthoquinonediazide-4-sulfonic acid, 1,2-naphtho-quinonediazide-5-sulfonic acid, 1,2-naphthoquinone-diazide-6-sulfonic acid, 1,2-naphthoquinonediazide-7-sulronic acid, 2,1-naphthoquinonediazide-4-sulfonic acid, 20 2,1-naphthoquinonediazide-5-sulfonic acid, 2,1-naphtho-quinonediazide-6-sulfonic acid, and 2,1-naphthoquinone-diazide-7-sulfonic acid; and their sodium, potassium, calcium, or barium salts are preferably used. Especially preferred are 1,2-naphthoquinonediazide-5-sulfonic acid and 2,1-naphthoquinonediazide-4-sulfonic acid, and their sodium, potassium, calcium, or barium salts.

~2;28~6~

In accordance wlth the process of the present invention, the above starting material, quinonediazide-sulfonic acid or its salt is reacted with phosgene to prepare the corresponding sulfonyl chloride.
In practice of the process of the present invention, as the phossene, pure phosgene or industrial phosgene can be used.
The amount of phosgene used is usually at least 1 mole, preferably from about 1 to 2 moles, per equivalent of the sulfonic acid group present in the starting sulfonic acid or salt thereof. If the amount of phosgene used is less than 1 mole, the ,eaction is not completed and the starting material remains unreacted. On the other hand, if it is in excess of

2 moles, side reactions ascribable to the quinonediazide group occur, causing a reduction in yield.
Any catalysts can be used in the present invention as long as they are commonly used in sulfonyl chlorination of the sulfonic acid group In general, acid amides, particularly lower aliphatic amides such as N,N-dialkylcarboxyllc acid amides (e.g., N,N-dimethyl-formamide and N,N-diethylformamide), and polymers having these acid amides in the side chain are used. Among them, N,N-dimethylformamide and N,N-diethylformamide are preferably used, wi-th N,N-dimethylformamide beiny partic-ularly preferred.

~;~28~66 The amount of the catalyst used is generally at least 0.01 mole, preferably at least 0.05 mole, and particularly preferably at least 0.2 mole, per equi~alent of the sulfonic acid group present in the star-ting sulfonic acid or salt thereof. Since the catalyst used in the present invention can act also as a solvent, there is no special limitation with respect to the upper limit of the amount used.
The sulfonyl chlorination reaction is generally carried out in the presence of a solvent but can be performed even in the absence of a solvent. Examples Qf solvents which can be used include aromatic hydrocarbons such as benzene, toluene, xylene, monochlorobenzene, and or al~c~c~;~
dichlorobenzene; aliphatic hydrocarbons such as cyclo-hexane, hexane, n-heptane, n-octane, methylcyclohexane, 2-methylhexane, 2,3-dimethylpentane, ethylcyclohexane, cyclooctane, n-nonane, isooctane, n-decane, and n-dodecane; ethers such as diethyl ether and tetrahydro-furan; esters such as ethyl acetate and butyl acetate;
acid amides such as dimethylformamide and diethyl-formamide; halogenated hydrocarbons such as chloroform, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,2-trichloro-2-fluoroethane, 1,1,2-tribromoethane, 1,1,2-trichloropropane, 1,2-dichloropropane, and carbon tetra-chloride; nitriles such as acetonitrile and propionitrile;

8~:~6~

nitro compounds such as nitromethane, nitroethane, and nitrobenzene; and mineral acids such as chlorosuLfonic acid, sulfuric acid, and phosphoric acid. These solvents can be used s:ingly or in combina-tion with each other.
From viewpoints of solubility and yield of the formed sulfonyl chloride, it is preEerred that lower halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, and tetra-chloroethylene be used singly.
In order to increase the solubility of the reaction reagents in the solvent, it is preferred to add polar solvents such as acetonitrile, propionitrile, tetramethyl urea, dimethylformamide, diethylformamide, nitromethane, tetrahydrofuran, al~oxybenzenesulfonyl chlorides, benzenesulfonyl chloride, and phthalic chloride.
In the sulfonyl chlorination reaction, stability and reactivity vary to a certain extent depending on the type of the starting material. ~lso, the reactivity varies with the type and amount of the catalyst, the type of the solvent, and other reaction condi-tions. But the reaction temperature is usually from -30 to 100C, preferably from -20 to 60C.
If the reaction temperature exceeds 100C, decomposition of the catalyst and quinonediazido group occurs, undesirably resulting in a decrease in yield.

~2~ i6 On the other hand, if it is below -30C, the rate of reaction is undesirably low.
The reaction can be performed under either elevated pressure or reduced pressure. Usually it is performed under around atmospheric pressure. The sulfonyl chlorination reaction of the present invention can be performed continuously, semi-continuously, or batchwise.
In the case that the starting sulfonic acid or salt thereof contains water, it can be dehydrated in advance with phosgene in the presence of the catalyst, and such is rather desirable.
In the sulfonyl chlorination reaction of the present invention, it is important that phosgene be continuously supplied to a mixture prepared ~y mixing in advance the starting sulfonic acid or salt thereof and the catalyst and, if desired, the solvent at a rate suitable for the reactivity for sulfonyl chlorination of the starting sulfonic acid or salt thereof. If the rate of introduction of phosgene is too high as compared with the reactivity of the starting material, or if the catalyst is added in advance to a mixture of the starting sulonic acid or salt thereof and phosgene, side reac-tions are caused between the starting phosgene or an intermediate formed from the starting phosgene and the catalyst and the quinonediazido group, resulting in a ~2Z~ 6 decrease of yield. The reactivity for sulfonyl chlorina-tion varies with the type of the starting sulfonic acid or salt thereof, the type and amount of the catalyst, and other conditions such as the use of the solvent and reaction temperature. Thus, taking into consideration these conditions, the suitable phosgene introduction rate be chosen.
After the sulfonyl chlorination reaction is completed, if desired, unreacted phosgene and hydro-chloric acid formed as a by-product are separated from the reaction product by techniques such as a degassing treatment (e.g., an evacuation method, a method of pass-ing an inert gas such as nitrogen, and a combination thereof), or a water-washing treatment. The sulfonyl chlorination reaction product freed of the unreacted phosgene and by-product hydrychloric acid by the method as described above is subjected to a separation treatment such as dis-tillation or precipitation under reduced or atmospheric ~ressure, to thereby remove the solvent.
There is thus recovered the desired sulfonyl chloride from the sulfonyl chloride reaction product. The above precipitation treatment is achieved by introducing the reaction product into a solvent in which the sulfonyl chloride is sparingly soluble, such as ice water, benzene, and hexane. In general, there is employed a method in which solids resulting from so-called recryst~l-lization are filtered and separated The thus obtained sulfonyl chloride can be used directly or after a purification treatment such as recrystallization, in preparation of organic industrial chemicals such as those used as an intermediate for light-sensitive materials in photography or printing, dyes, or liquid crystals as well as an intermediate starting material for the preparation of photo-resists.
In accordance with the process of the presentinvention, a sulonyl chloride of the formula ~II), Ri-Ar-(SO2CQ)j can be prepared from a sulfonic acid or its salt of the formula (I), Ri-Ar-(SO3M)j and phosgene in a high yield. Further, since the reaction is completed using almost theoretical amounts of reaction reagents, it is not necessary to remove an e~cess of unreacted reaction reagent remaining after completicn of the reaction as in conventional methods, and the reaction operation is simplified. Thus the present invention can give rise to various advantages on an industrial scale.
The present invention is described in greater detail with reference to the following examples, although it is not intended to be limited thereby.

80~i6 EXAMPLE
Into a mixture of 98 parts by weight of sodium 1,2-naphthoquinonediazide-5-sulfonate, 1,428 parts by weight of 1,2-dichloroethane, and 111 parts by weight of N,N-dimethylformamide was blown 43 parts by weight ~1.2 times the reaction equivalent) of phosgene over 2 hours and 52 uminutes with stirring while maintaining the temperature of the mixture at 0 to 25C, to thereby achieve sulfonyl chlorination reaction. After the reaction was completed, the reaction mixture was washed four times wi-th 271 parts by weight of ice water. The solvent, 1,2-dichloroethane, was distilled away under reduced pressure at room temperature. The residue was dried under reduced pressure at room temperature, where-15 upon 90 parts by weight of 1,2-naphthoquinonediazide-5-sulfonyl chloride tpurity, 98.8~) was obtained. The percent yield in relation to the reaction reagent, sodium 1,2-naphthoquinonediazide-5-sulfonate, was 92%.
E~AMPL~S 2 TO 20 The same procedure as in Example 1 was repeated except that the type and amount of the reaction reagent sulfonic acid or salt thereof, the solvent, and the catalyst were changed as shown in Table 1. The results are also shown in Table 1.

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O I I N
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t~ ~ I N^ N , ,~ o~ I o g C~ I N -- N
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C -- ~ ~ ~ ~ t_l 0 N I ,1~ J J ~ ~J
o ~ C ~~ O
E ~ ~ g ~u ~ O O ~n O O
1 ~ -~ C ~ C) C ~ . _I I N I N :~ ,I C ~1 ~1 "J r~ ~ ~ r1 ~ ~ C~l ~a ~ L' ~n ~a ~,1 ~ v O ~ O ^~ O ~l cn ~ ~n ~ V~n U~ n P~ n ~ .
E o n ~o 1~ ~o cr~ O
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-- 20 ~

~ZZ~3~6~

-The same procedure as :in Example 1 was repeated except that the type and amount of the sulfonic acid or salt thereof, the amount of phosgene blown, the type and amount of the solvent, and the reaction temperature were changed as shown in Table 2. The results are also shown in Table 2.

8~)66 1 ~0 ~ O O O O ~ ~ O
~ . r~
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E ~ :~
0 r ~ s r r r~ r. ~ ~
c~ ~ ~ ~ r E ~ .. u ?~ E r~E rl E r~ E r~E rlV E . r~E rlE r~
r~ E1 E r~ E ri Er~ Eu ~r~ Er~ E rl a EI ~ a t a Ea E~ ?~ a E I e z ~z ~ z 1~ Z ~Z ~z r. z ~ z ~ z ^ o^ o - o ^ o^ o^ ~ ^ o ^ o ^ c~
Z wz ~u Z 4~ Z 4~Z ~Z a~Z ~ Z ~ Z 0 . r ~ c) o o ~ o o o o o L c~ .1 o o o ~ o o o o o~
l . r~ S~J O C~
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a ~ ,. c CJ C ~
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~r~ O ~ O --v a -- ~ O ~, Nr~ I V
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rv~
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V ~ 0 r r 0cr c c e I
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C c~. ~P~ ~1~L '~ ~ '_ C~ .r~ CJ ~ ~ ~ ~I ~1 O 0 r~ 0 r-l 0 r-~ O ~1 r. r-~
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c~ v u~ v~ ~cr 0 u~ V V~

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C ~ 0 0 0 co 0 0 0 a~ 0 ~ C) E ~
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COMPARATIVE EXA2`1PLE
A mixture of 98 parts by weight of sodium 1,2-naphthoquinonediazide-5-sulfonate and 1,263 parts by weight of chlorosulfonic acid was stirred at a tempera-ture of 65 to 67C for 4 hours to achieve sulfonylchlorination. After ~he reaction was completed, the reaction mixture was cooled to 20C and poured into 8,400 parts bir weight of îce water with stirring.
Precipitate formed was filtered off, washed many times 10 with water in a total amount of 12,000 parts by weight, and then dried under reduced pressure at room tempera-ture. Thus, there was obtained 83.1 parts by weight of 1,2-naphthoquinonediazide-5-sulfonyl chloride (purity, 91.2%~. The percent yield in relation to the reaction reagent, sodium 1,2-naphthoquinonediazide-5-sulfonate, was 78~.

98 parts by weight of sodium 2,1-naphtho-quinonediazide-4-sulfona-te was mixed with 128 parts by weight of 70~ fuming sulfuric acid at a temperature not more than 20C. The mixture was heated to 50C, and 45 parts by weight of chlorine was blown thereinto for

4 hours while stirring to achieve sulfonyl chlorination.
Af ter the reaction was completed, the reaction mixture 25 was cooled to 20C and then poured into 1,000 parts by ~22~30~i6 weight of ice water while stirring. Precipitate formed was riltered off, washed many times with water in a total amount of 5,000 parts by weight, and then dried under reduced pressure at room temperature. Thus, there was obtained 85 parts by weight of sodium 2,1-naphtho-quinonediazide-4-sulfonate (purity, 85.8~). The percent yield in relation to the reaction reagent, sodium 2,1-naphthoquinonedi.azide~4-sulfonate, was 75~.
While the invention has been descr.ibed in detail and with reference to specific embodimen~s thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Claims (12)

WHAT IS CLAIMED IS:

1. A process for producing an aromatic sulfonyl chloride having a quinonediazido group, repre-sented by the formula (II):
Ri-Ar-(SO2C?)j (II) wherein R, which may be the same or different, is a monovalent substituent selected from a halogen atom, a nitro group, and an alkyl group having from 1 to 5 carbon atoms; Ar is an aromatic organic group of the quinone-diazide structure which is substituted by at least one oxy anion and at least one diazonium cation; i is an integer of from 0 to 5; and i is an integer of from 1 to which comprises reacting a sulfonic acid or a salt thereof represented by the formula (I):
Ri-Ar-(SO3M)j (I) wherein R, Ar, i and j are the same as defined above;
and M is a hydrogen atom, a mono-, di- or trivalent metal, or an organic amino cation, with phosgene in the presence of a catalyst and further in the presence or absence of a solvent.

2. A process as claimed in Claim 1, wherein said sulfonic acid or salt thereof of the formula (I) is an aromatic sulfonic acid or a salt thereof repre-sented by the formula (III), (IV), or (V):
(III) (IV) (V) wherein R1 and R2, which may be the same or different, are each an aromatic fused ring residue represented by , a monovalent substituent represented by -SO3M, or a monovalent substituent represented by -X, in which X, which may be the same or different, is a monovalent substituent selected from a hydrogen atom, a halogen atom, a nitro group, and an alkyl group having from 1 to 3 carbon atoms; and M is a hydrogen atom, a mono-, di-or trivalent metal, or an organic amino cation; and a, b, c, m, n and p are each 0 or a positive integer satisfying the relations that a+m=2, b+n=4, and c+p=4, provided that at least one -SO3M group is contained in the formula.

3. A process as claimed in Claim 2, wherein the aromatic ring of said aromatic sulfonic acid or salt thereof of the formula (III), (IV), or (V) is a benzene ring or a naphthalene ring.

4. A process as claimed in Claim 1, 2, or 3, wherein in the formulae (I), (III), (IV), and (V), M is a hydrogen atom, a sodium atom, a potassium atom, a magnesium atom, a calcium atom, a barium atom, an aluminum atom, a trimethylammonium group, a triethyl-ammonium group, a pyridinium group, or an N,N-dimethyl-anilinium group.

5. A process as claimed in Claim 1 or 2, wherein said sulfonic acid or salt thereof is 1,2-benzoquinonediazidemonosulfonic acid, 1,2-naphthoquinone-diazidemonosulfonic acid, or 2,1-naphthoquinonediazide-monosulfonic acid, or sodium, potassium, calcium, or barium salts thereof.

6. A process as claimed in Claim 1 or 2, wherein said sulfonic acid or salt thereof is one selected from the group consisting of 1,1-naphthoquinone-diazide-5-sulfonic acid and 2,1-naphthoquinonediazide-4-sulfonic acid, and sodium, potassium, calcium, and barium salts thereof.

7. A process as claimed in Claim 1, wherein the amount of phosgene used is from about 1 to 2 moles per mole of the sulfonic acid group in said sulfonic acid or salt thereof.

8. A process as claimed in Claim 1, wherein said catalyst is an acid amide.

9. A process as claimed in Claim 8, wherein said acid amide is N,N-dimethylformamide.

10. A process as claimed in Claim 1, 8, or 9, wherein the amount of said catalyst used is at least 0.01 mole per mole of the sulfonic acid group in said sulfonic acid or salt thereof.

11. A process as claimed in Claim 1, wherein said solvent contains methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, or tetrachloro-ethylene.

12. A process as claimed in Claim 1, wherein the reaction temperature is from -30°C to 100°C.