Note: Descriptions are shown in the official language in which they were submitted.
3L22~30~
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.
~!
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.
8066
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)
N2
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.
- 5
~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-
-- 8
~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.
10 --
~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.
- 11 -
~;~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;
- 12 -
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.
- 13 -
~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
- 14 -
~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
- 15 -
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.
- 16 -
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.
-o ..
a~
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O ~ ~ 6~ o o ~ r~
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S :~ ~' a~
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L ~ o r- ~;r o co L
~ ?~ 3 c
v~ ~
. ~ O~
5 ~o V ~ o ~ o o O
O ~ CO ~ 1~ 0 ~D
~ 3 ~
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v
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v a~ S Q~ S c~ I E v a~ ~ ~ s a~
t~ c a) ~ a~ ~o ~ Q) ~ CJ ~ ~ ~
E~ E'E e'E s ~ ~E E'E e'E
z E z F~ ~ s z ~ z E æ E
^ o - o I v
v v ~ O O O O O O O O ~
C ~ v o o o ~ o o o a:) v
~ O o rd - - - - O
<~ v ~ 3 ~ ~ ~ ~ U
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r ~ O ~ ~ I J
O c) I ~ S v
C ~ '`~ S C ~ rD ~ v U ~1
~, ~ ~ ~a c o a cr~ ~ ro ~d ~1 0
r ~ L- d v r~J S ._~ v v S v
~ ~ E~ ~D ¢ . rJ E~ ~ 'd E~ ~D
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v vc ~ v r~ r~ ~ 00 a~ ~o
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-- 18
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æ ~- æ ~ z ~ z ~ z ~ z ~ z ~
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-- 20 ~
~ZZ~3~6~
EXAMPLES 21 TO 29
-
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.
- 21 -
8~)66
1 ~0 ~ O O O O ~ ~ O
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r-~ I ~ I I I ~:)
0 r~ rJ r Ir~
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c~ ~ ~ ~ r E ~ .. u
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r~ E1 E r~ E ri Er~ Eu ~r~ Er~ E rl
a EI ~ a t a Ea E~ ?~ a E I e
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-- 22 --
~2X8
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C ~ 0 0 0 co 0 0 0 a~ 0
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-- 23 --
6G
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~.
COMPARATIVE EXAMPLE 2
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
- 24 -
~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.
