JPS61246190A - Tert-butyldimethylsilyl-p-vinylphenyl sulfide and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I. USE:A raw material for synthesizing a poly-p-mercaptostyrene useful as an oxidation-reauction polymer and a metallic ion adsorbing polymer. PREPARATION:A p-halogenothiophenol shown by the formula II (X is halogen) is reacted with tert-butyldimethylsilyl chloride shown by the formula C4H9(CH3)2 SiCl usually in an aprotic solvent such as methylene chloride, etc., in the presence of a base such as triethylamine, etc. preferably at 20-30 deg.C for 0.5-2hr to give a tert-butyldimethylsilyl-p-halogenophenyl sulfide shown by the formula III. Then, this compound is reacted with metallic Mg to give a 4-(tert- butyldimethylsilylmercapto)phenyl magnesium halide shown by the formula IV, which is reacted with a vinyl halide in the presence of a catalyst.

Description

[Detailed Description of the Invention] [Object of the Invention] The present invention provides a novel compound represented by the following structural formula:
Specifically, the object of the present invention is to provide tert-butyldimethylsilyl-P-vinylphenyl sulfide and a method for producing the same.

(Industrial Application) LerL-buty which is a compound of the present invention! Resimethylsilyl-P-vinylphenyl sulfide is useful as a raw material for the synthesis of poly-P-mercaptostyrene, which is known as a redox polymer and a metal ion adsorption polymer.

That is, LerL-butyldimethylsilyl- of the present invention
P-vinylphenyl sulfide is a useful substance as a raw material for polymers capable of radical and ionic polymerization.
This is a novel compound that has not been described in any conventional literature.

(Prior Art) The beet-butyl-P-vinylphenyl sulfide proposed in the terk-phthyl-P-vinylphenyl sulfide and its production method filed by the present inventors on March 20, 1985, after radical and ionic polymerization, Thiol groups could not be reproduced without cleavage with a strong acid such as 70% perchloric acid or anhydrous hydrogen fluoride, or reduction with sodium ammonia or the like.

(Problems to be Solved by the Invention) Since the above-mentioned strong acids and sodium-ammonia are difficult to contain and handle, it is not easy to reproduce thiol groups. For this reason, it is necessary to use an easy-to-handle reagent and a protecting group that is easily removed.

[Structure of the invention]

These shortcomings of the conventional technology can be improved and polyP-
In order to produce mercaptostyrene (as a precursor monomer for poly-P-mercaptostyrene), the present inventors have developed a novel compound in which the thiol group is protected at °C by a T-chain compound. L8re-butyldimethylsilyl-P-vinylphenyl sulfide can be subjected to radical polymerization and ionic polymerization, and it is possible to easily reproduce the thiol group by polymerization, pickling or alkali 1-C. The present invention has been achieved by discovering the following.

(Means for Solving the Problems) The gist of the present invention is expressed by the formula tL4 Lert-butyldimethylsilyl-P
-Vinyl phenyl sulfide and two methods for producing it.

The production method of i4t is P-halogenothiophenol and Ler
t-Butyldimethylsilyl chloride in the presence of a base (
This reaction gave tert-butyldimethylsilyl-P-halogenophenyl sulfide, which was then reacted with metallic magnesium to form 4-(term-butyldimethylsilylmerkabut)phenyl sulfide. A method of reacting gnesium halide with vinyl halide in the presence of a catalyst,
The second method is to react P-(β-halogenoethyl)thiophenol and Lert-butyldimethylsilyl chloride in the presence of a base to form cerm-butyldimethylsilyl-P-β-halogenoethyl phenyl sulfide. This is a method of dehydrohalogenation in the presence of hydrogen.

The feature of the production method of the present invention is that after protecting the thiol group using tert-butyldimethylsilyl chloride, the aromatic ring can be directly vinylated or dehydrohalogenated to easily form term -butyldimethylsilyl- A method for producing P-vinylphenyl sulfide, comprising: b
Ru.

Reaction formula-1 (4) +1) (in the formula or halogen atom) The compound (ri) is placed in an aprotic solvent, specifically, methylene chloride, N,N-dimethylformamide, needle, etc., or a solvent is used. Without the presence of a base (specifically, an amine such as triethylamine, pyridine, or imidazole), the thiol is silylated using tert-butyldimethylsilyl chloride to form the compound (8).
). During this reaction, 4-(n,N
-dimethylamino)pyridine is preferably used.

(e"(-The amount of butyldimethylsilyl chloride used may be about 1 to 1.2 times the mole of compound (2). The amount of the base to be used is about 1 to 5 times the mole of C based on compound (2). In particular, when a solvent is used, it may be used in an amount of 1 to 2 times the mole.4-(N,N-dimethylaminonepyridine may be used in an amount of 0.5 to 0.01 times the mole of the compound (2).

The reaction temperature at this time is 10 to 50°C, preferably 20 to 8°C.
The reaction time was 0.5 to 15 hours.
Preferably it takes about 0.5 to 2 hours.

After the reaction, either filter the salt, distill off the solvent, etc., and directly distill it, or after the reaction, add water to the reaction solution, separate the organic phase, remove the solvent, and distill it to obtain compound (8). It's also good to do.

Next, under nitrogen Fg atmosphere or reduced pressure at 100-170℃.
The Grignard reagent of compound (4) is synthesized by reacting the activated metallic magnesium and compound (21) in anhydrous trihydrofuran by stirring for 2 to 20 hours, preferably 6 to 12 hours.

During this reaction, iodine or a halogenated hydrocarbon such as methyl iodide, ethyl bromide, dibromoethane, etc. is used as a reaction activator, and a compound (
It is preferable to add a small amount of 8) before (or at the same time) dropping.The halogen atom of compound (8) is C:
Chlorine, chlorine or bromine atoms are preferred. As the metallic magnesium, commercially available shaved 2b or tope metallic magnesium may be used, and the suitable usage state is about 1 to 5 times the molar amount of C to compound (3).

When compound (8) is added dropwise to magnesium metal which has reached its lowest level of activity, the reaction temperature is 20'C to the solvent reflux temperature, and the reaction time is about 15 minutes to 1 hour. After dripping,
72-100'' CICC Stirred for 2-5 hours Vinyl nylide, such as vinyl chloride, vinyl chloride, etc., is reacted in a solvent, such as anhydrous tetrahydrofuran, in an anhydrous needle in the presence of a catalyst to obtain C1, the compound of the present invention@(1).

In this reaction, the Grignard reagent is diluted with anhydrous hydrogen ash such as anhydrous benzene, filtered, and C is used.

The catalyst C is preferably a nickel complex, such as dichloro[1,2-bis(diphenylphosphino)ethane]nickel, dichloro(1,1-bis(diphenylphosphino)propane nickel, dichloro(1,2-bis(diphenylphosphino)propane)nickel, It is preferable to use a dihalodiphosphine nickel complex such as (dimethylphosphino)ethane]nickel, dichloro[his(triphenylphosphine:/))nickel, etc. The layer of the nickel complex is rixto'
~lXl0'' times the mole, preferably 5X10'~2
It is sufficient to use about X10'' times the molar amount.

The amount of vinyl halide used is C1 per compound (8).
It is sufficient to use about 15 to 15 times the mole, preferably 1.5 to 5 times the mole.

At this time, the reaction temperature is -10 to 34°C, preferably 10
The reaction time is about 1 to 8 hours.

Reaction formula-2 (In the formula, X is a halogen atom) are synthesized.

For example, if X is salt≠atom, use thionyl chloride and C1
Further, when X is a bromine element F, halogenation can be carried out using hydrogen bromide.

Compound (5) is reacted with tert-butyldimethylsilyl chloride in an aprotic solvent or without using a solvent in the presence of a base to synthesize Compound C (6).

The solvent, base, and catalyst are the compounds of reaction formula-1 (in the case of silylation of The range described in the silylation of (8) is preferable.

Next, compound (6) was prepared in εert-butyl alcohol with potassium tar-butoxide or in benzene with 1,5-diazabicyclo(4,1,0)-5-nonene, 1,8-diazabicyclo(5,4 The compound (1) of the present invention is produced by dehydrohalogenation using a bulky base such as ,0)-7-undecene.

The amount of base to be used is 1 to 8 moles of C per 1 mole of compound (6);
Preferably, it is sufficient to use about 1.2 to 1.5 times the mole amount.

It is preferable to add a small amount of a polymerization inhibitor such as hydroquinone or Lert-butyl caracol to this reaction system.

At this time, the reaction temperature was about 10 to 40'C, and the reaction time was 1
Do this for about 0 minutes to 1 hour.

(Function) In general, it is known that the 8-8i bond undergoes hydrolysis very easily, and in particular, compounds in which a thiol is protected with a trimethylsilyl group are easily hydrolyzed by C water at room temperature.

However, according to the present invention, a compound in which a thiol is protected with a tert~butyldimethylsilyl group is also stable in the synthesis of Grignard reagents, cross-coupling reactions, and decomposition reactions.C is also stable in hydrogenation reactions.

This is because the acid attacks the sulfur of the 8-8i bond, and the basic force 8-
This is thought to be because the Lert-butyldimethylsilyl group, in which one methyl group of the trimethylsilyl group is protected with a bulky terc-butyl group, is vulnerable to attack by acids and bases in order to attack silicon in the 8i bond. .

Hitherto, there have been few known examples of protecting thiol groups with silicon compounds in synthetic reactions. The present invention is based on Lert
This is the first example showing that the -butyldimethylsilyl group is useful as a protecting group for thiols in synthetic reactions.

(e) (-The elimination of the butyldimethylsilyl group can be easily carried out in an aqueous or alcoholic solution of a base such as sodium hydroxide or potassium hydroxide, or with a carboxylic acid such as acetic acid, hydrochloric acid, or sulfuric acid.

(Example) The present invention will now be described in more detail with reference to Examples.

Example 1 49.8 f (0.4 B moles) of cert-butyldimethylsilyl chloride, 36.8 f (0.4 B moles) of triethylamine in 80 wt of methylene chloride. :M (0.36 mol) and 4-(N,
N-')l chill 7 E/)pi')shin8.11 (
0,025 mol) was added to room temperature, and a solution of P-chlorothiophenol 4 f3.51 (0.8 mol) in 30 ml of methylene chloride was added to room temperature (over 50 minutes). The mixture was further stirred for 1 hour.

Add 100 w of water to this reaction solution, branch it, add anhydrous magnesium sulfate to the methylene chloride phase, dry it, distill off the methylene chloride, and perform distillation under pressure to obtain tert-butyldimethylsilyl-P-chloro. 54.71 phenyl sulfide was obtained. The purity was 99°496 and the yield was 7.
It was 0.0%. Boiling point 99-100”C/0.1
It was 5 fl Hf.

In the next step, commercially available shaved metal magnesium 14°61
(0,6 mol) 'e4KIHI (160'' at Da pressure
The mixture was heated to C and stirred for 8 hours to activate C. Under nitrogen atmosphere, in 85xl of anhydrous tetrahydrofuran (Ler.
t-Butyldimethylsilyl-P-chlorophenylsulfide 88.8y (0.15 mol) and dibromoethane 2
．． The solution prepared by adding 4 ml of C was added to the activated magnesium metal over a period of 85 minutes at room temperature. Thereafter, it was heated and stirred at 72-100'C for 2.5 hours, and after cooling C1, a portion of the reaction solution was collected and hydrolyzed with C1 water, and analyzed by gas chromatography.
It was confirmed that only 1% of rt-butyldimethylsilyl-P-chlorophenylsulfide remained.

75 ml of anhydrous benzene was added to the reaction solution, and the mixture was filtered under a nitrogen atmosphere to remove metallic magnesium.

Next, dichloro[1°3-bis(diphenylphosphino)pro/(n)nickel 77η (L4×10' mol) was added to 200 ytl of anhydrous vinyl chloride.
The Grignard reagent prepared above was added to the reaction solution into which 4.4 IC 0.8 T mol) was blown at 4 to 13°C over a period of 45 minutes, and the mixture was further stirred at room temperature with a trowel for 2 hours.

Add 200% water to the reaction solution. Add wJ and separate the ether phase to 1
It was washed with 0% aqueous sodium hydrogen carbonate solution and dried over anhydrous magnesium sulfate. 2.5-dijerk-butylhydroquinone 5 da was added to this, the ether was distilled off, and the mixture was distilled under reduced pressure to obtain 18.4N of tert-butyldimethylsilyl-P-vinylphenyl sulfide. The purity was 97.4% and the yield was 47.7%. The boiling point was 103-105"C (0.15 mHy).

Example 2 In a methylene chloride bowl, tert-butyldimethylsilyl chloride 45.9F (0.31 mol), triethylamine 33.7N (0.88 mol) and 4-(N) were added.

N-dimethylamino)pyridine 2.7 f (0,02
mol) was added to room temperature, and to this was added a solution of P-(β-bromoethyl)thiophenol 60F (0.28 mol) in methylene chloride Bogl at room temperature over 45 minutes, and the mixture was further heated to room temperature. The mixture was stirred for 1 hour.

This reaction solution was filtered under a nitrogen atmosphere, and methylene chloride was distilled off to obtain a crude solution. l! 85.21 of Cert-butyldimethylsilyl-P-(β-bromoethylphenyl) sulfide was obtained.

Next, 13.51 g of potassium tert-butoxide was dissolved in 123 g of tert-butyl alcohol, 20.31 g of the above crude butyldimethylsilyl-P-(β-bromoethylphenyl) sulfite was added at room temperature, and Stirred to room temperature for 0.15 minutes. Filter under nitrogen atmosphere, add 5q of 2,5-di-term-butylhydroquinone, distill off eert-butyl alcohol, add 100 ml of methylene chloride and 50 ml of water, separate the layers, and wash the methylene chloride phase with concentrated hydrochloric acid. The mixture was dried over anhydrous magnesium sulfate, the methylene chloride was distilled off, and the mixture was distilled under reduced pressure.
7.41 of t-butyldimethylsilyl-P-vinylphenyl sulfide was obtained. The pure IJj was 99.0%, and the yield was 43.9%. The boiling point is 132-138°C (1
111Hg).

The analytical values and physical properties of eert-butyldimethylsilyl-P-vinylphenyl sulfide, which was obtained by repurifying the obtained product, were as follows.

(1) Colorless liquid, boiling point 104-105°C (0.15°C)
mHp ) (2) Elemental analysis value Ct4H2z88i C calculated value C: 67 U4 H: 8.85 S: 1
2.80 Si: 11.21 Actual value C: s'n
H: 8.87 S: 12.78 st: o, 24
(31NMEL spectrum (90M±, CDC15, internal standard TMS) δ(PP
m): 0.18 (6L8) 0.97 (9H
,S) 5.22 (IH, dd, Jl-10,8Hz, J2
-1.1Hz)5.70 (ILdd, Jl-17,
6Hz, J2=1.1)h)6.67 (LH,dd,
Jt -17,6)tz-J2-10.8Hz)7.
82 (4f1.d) (4) Infrared absorption spectrum (・KB t) max C1g 2956, 2932.2860.1492.1472.
1B94.1250゜1090, 908.838.82
2.802.774.458 [Effects of the Invention] By using the novel substance of the present invention, polyP-mercaptostyrene having a thiol group and copolymers thereof can be easily obtained.

Applicant: Steel Chemical Industry Co., Ltd. Representative Hiroshi Sasaki

Claims (8)

[Claims] (1) Tert-butyldimethylsilyl-P-vinylphenyl sulfide represented by the following formula ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼. (2) Reacting P-halogenothiophenol and tert-butyldimethylsilyl chloride in the presence of a base,
After forming tert-butyldimethylsilyl-P-halogenophenyl sulfide, it was reacted with metallic magnesium.
-(tert-butyldimethylsilylmercapto)phenylmagnesium halide, which is reacted with vinyl halide in the presence of a catalyst.
A method for producing butyldimethylsilyl-P-vinylphenyl sulfide. (3) The method according to claim (2), wherein the P-halogenothiophenol is P-chlorothiophenol. (4) The method according to claim (2), wherein the vinyl halide is vinyl chloride. (5) The method according to claim (2), wherein a nickel complex is used as a catalyst for the reaction of 4-(tett-butyldimethylsilylmercapto)phenylmagnesium halide and vinyl halide. (6) P-(β-halogenoethyl)thiophenol and t
tert-butyldimethylsilyl chloride is reacted in the presence of a base to form tert-butyldimethylsilyl-P-
After converting into (β-halogenoethylphenyl) sulfide,
t characterized by dehydrohalogenation in the presence of a base.
Method for producing ert-butyldimethylsilyl-P-vinylphenyl sulfide. (7) P-(β-halogenoethyl)thiophenol is P
-(β-bromoethyl)thiophenol. The method according to claim (6). (8) The method according to claim (6), wherein the base is potassium tert-butoxide.