JPH0473428B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing an aromatic sulfonium salt having an organic hydroxy compound residue in its aromatic ring.

[Conventional technology and its problems]

Aromatic sulfonium salts, especially PF ₆ , AsF ₆ ,
Aromatic sulfonium salts with non-nucleophilic anions such as SbF ₆ are photosensitive and generate strong acids when irradiated with light, so they have attracted attention and are used as initiators for photo-cationic polymerization.

For the synthesis method of aromatic sulfonium salts, please refer to
“The chemistry of the sulfonium group”:
Edited by CJMStiring, published by John Wiley & Sons, 1981
(2011), but little is known about methods that contain alcohol residues.

Among them, the method that attracts attention as a general synthesis method is described in the Bulletin of the Chemical Society of Japan.
Society of Japan: S.Oae and YHKhim, 42
There is a method of replacing chlorophenyl diphenyl sulfonium halide with ethanol in the presence of a basic compound, as described in Vol., p. 1622). However, since this reaction requires heating and side reactions occur, it is difficult to employ it as a general method.

An object of the present invention is to provide a method for producing aromatic sulfonium salts having various organic hydroxy compound residues in their aromatic rings in good yield under mild conditions.

[Means for solving problems]

The present inventors extensively studied methods for synthesizing aromatic sulfonium salts having an organic hydroxyl residue in the aromatic ring, and found that aromatic sulfonium salts having fluorine in the aromatic ring were synthesized under mild conditions with various organic sulfonium salts. It was discovered that the substitution reaction with a hydroxy compound proceeds with good yield, and the present invention was achieved.

The manufacturing method of the present invention is based on the following formulas (a) to (i) (However, X is Cl ^- , Br ^- , PF ₆ ^- , BF ₄ ^- , AsF ₆ ^- ,
A fluorine-substituted aromatic sulfonium salt represented by (with a counter anion selected from SbF ₆ ^- ) is reacted with a first aliphatic alcohol and/or its alkali metal derivative to convert the first aliphatic alcohol residue into The present invention is characterized by obtaining an aromatic sulfonium salt having a fluorine atom of at least one benzene nucleus at the bonded position of the substituted aromatic sulfonium salt.

The above-mentioned fluorine-substituted aromatic sulfonium salt has at least one benzene nucleus directly bonded to the sulfur atom forming the sulfonium and at least one of the ortho- or para-positions of the benzene nucleus. It is necessary that a fluorine atom is bonded to the benzene nucleus, and substituents such as halogens other than hydrogen atoms, nitro groups, alkoxy groups, aliphatic groups, An aromatic group or the like may be bonded. Such fluorine-substituted aromatic sulfonium salts include can be mentioned.

The primary aliphatic alcohol used in the present invention may have substituents that are stable under the reaction conditions, such as hydroxyl groups, alkyl groups, aryl groups,
Includes groups such as nitro groups and halogens. Suitable aliphatic alcohols include ethanol, methanol, ethylene glycol, 2-methoxyethanol, 2
Examples include -n-butoxyethanol, 2-phenoxyethanol, benzyl alcohol, polyethylene glycol, and cellosolve. The phenols may be substituted phenols, but those with low electron-withdrawing properties are preferred. Such substituents include alkyl groups, alkoxy groups, halogens, and the like.

As the derivative of the primary aliphatic alcohol used in the present invention, an alkali metal derivative represented by the formula () can be used.

ROM () [However, R is the above organic hydroxy compound residue, M is
Metal selected from Li, Na, K] When a primary aliphatic alcohol is used in the practice of the present invention, a basic compound must be present. Preferred basic compounds are organic amines or alkali or alkaline earth metal hydroxides. Furthermore, when using a water-soluble basic compound, it is also good to use ammonium salt, Klein ether, etc. as an interlayer transfer catalyst. The basic compound is preferably used in an amount equivalent to or more than the amount of the aromatic sulfonium salt. When using the alkali metal derivative of the organic hydroxy compound represented by the formula (), the above basic compound may be used in combination, but it is not necessary to use it in particular.

The reaction uses an equivalent or more amount of the first aliphatic alcohol or its derivative relative to the fluorine-substituted aromatic sulfonium salt. The reaction solvent is the first
The aliphatic alcohol itself often serves as
Although not particularly required, when the first aliphatic alcohol is expensive, a common organic solvent can be used. Further, depending on the case, there may be no problem even if water is present in the reaction solvent. It is also preferable to use an aprotic polar solvent for the purpose of increasing the reaction rate. Substitution reactions with primary aliphatic alcohols usually proceed quickly around room temperature;
For example, it is also preferable to perform gentle heating at 100°C or less. After the reaction is completed, the product can be recovered by pouring into water (which may contain acid), filtering the organic layer, or performing solvent extraction.

〔Effect of the invention〕

According to the method of the present invention, one or more primary aliphatic alcohol residues are introduced into at least one of the sites to which a fluorine atom of the benzene nucleus of the fluorine-substituted aromatic sulfonium is bonded. Aromatic sulfonium salts can be obtained in high yield without decomposition of aromatic sulfonium salts. The aromatic sulfonium salt obtained by the method of the present invention is useful as a photosensitive sulfonium salt.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention does not exceed the gist thereof.
The present invention is not limited to the following examples.

Example 1 4,4'-bis-[bis(p-fluorophenyl)
Sulfonio]phenyl sulfide bishexafluoro-phosphate was stirred in excess ethylene glycol (10 eq.) in the presence of sodium hydroxide (2 eq.) at room temperature for 1 day. It was then poured into water to obtain a pale yellow oil. After repeated washing with water several times, a white solid was isolated with a yield of 70% by silica gel column chromatography. This compound is ¹³ C-NMR
(DMSO- _d6 was used as solvent for TMS internal standard; 163.3, 140.3, 133.3, 132.4, 131.3, 126,
0, 117.3, 114.6, 70.5, 59.2ppm), ^1H -NMR,
It was confirmed by IR to be 4,4'-bis[bis(p-2-hydroxyethoxyphenyl)sulfonio]phenyl sulfide bishexafluorophosphate.

Example 2 When the same reaction and purification as in Example 1 were carried out using p-fluorophenyl diphenylsulfonium hexafluorophosphate and ethanol, a white solid was isolated with a yield of 77%. This compound was analyzed by ^13C -NMR (DMSO- _d6 as TMS internal standard).
used as solvent; 164.0, 134.8, 134.5, 131.8,
131.6, 126.7, 124.3, 118.0, 60.0, 15.1ppm), ^1H
-NMR [DMSO- _d6 was used as the solvent for TMS internal standard; 7.0-7.8 (14H), 3.90 (2H), 1.32
(3H)], IR and elemental analysis confirmed that it was p-ethoxyphenyldiphenylsulfonium hexafluorophosphate.

Example 3 1-bis(p-fluorophenylsulfonio)
Example 1 using -4-phenylthiobenzene hexafluorophosphate and ethylene glycol
When the same reaction and purification was carried out, a white solid was isolated with a yield of 74%. This compound is ¹³ C−
NMR [TMS internal standard, in DMSO-d ₆ (ppm);
163.1, 148.9, 145.0, 134.2, 131.1, 130.7,
130.1, 129.7, 128.6, 128.0, 123.6, 118.3, 70.5,
59.2], ¹ H-NMR [DMSO- as TMS internal standard
Using d ₆ as solvent; 7.8 (17H), 4.8 (2H), 4.2
(4H), 3.8(4H)], IR and elemental analysis confirmed that it was 1-bis(p-2-hydroxyethoxyphenylsulfonio)-4-phenylthiobenzenehexafluorophosphate.

Example 4 When the same reaction and purification as in Example 1 was carried out using p-fluorophenyl diphenylsulfonium hexafluorophosphate and ethylene glycol, a white solid was isolated with a yield of 75%. This compound was analyzed by ¹³ C-NMR (TMS internal standard).
Using DMSO− _d6 as solvent; 164.0, 117.0,
112.2, 110.1, 70.5, 59.2, 28.1ppm), ^1H −NMR
[DMSO-d ₆ was used as the solvent for TMS internal standard; 8.04 (2H), 7.61 (2H), 4.80 (2H), 4.2
(2H), 3.81 (2H), 3.25 (6H)], and was confirmed to be p-2-hydroxyethoxyphenyldimethylsulfonium hexafluorophosphate by IR and elemental analysis.

Claims (1)

[Claims] 1 The following formulas (a) to (i) (However, X is Cl ^- , Br ^- , PF ₆ ^- , BF ₄ ^- , AsF ₆ ^- ,
A fluorine-substituted aromatic sulfonium salt represented by (with a counter anion selected from SbF ₆ ^- ) is reacted with a first aliphatic alcohol and/or its alkali metal derivative to convert the first aliphatic alcohol residue into A method for producing an aromatic sulfonium salt having a primary aliphatic alcohol residue, which comprises obtaining an aromatic sulfonium salt having a fluorine atom of at least one benzene nucleus at the bonded position of the substituted aromatic sulfonium salt. .