JP2001261585A - Synthetic method of vinyl halide compounds - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a vinyl halide in high selectivity in a high yield. SOLUTION: This method for synthesizing the vinyl halide compound of general formula (3) is characterized by reacting an aromatic ketone of general formula (1) with an acid halide of general formula (2), QCOX.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel method for producing vinyl halide using ketones and acid halides as raw materials.

[0002]

2. Description of the Related Art A vinyl chloride derivative can be produced by reacting a corresponding ketone with phosphorus pentachloride.
It has been known for a long time. However, this reaction method has a problem that various substances are produced as by-products and the selectivity is low, and various developments of reagents replacing phosphorus pentachloride have been conventionally studied. The way has not yet been found.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a new method for producing vinyl halide with high selectivity and high yield.

[0004]

Means for Solving the Problems The present invention provides the following general formula (1)

Embedded image (Wherein, R ^{1 to} R ⁵ are hydrogen, halogen, an alkyl group,
Alkoxy group, allyl group, aralkyl group, aryl group,
Amino group, alkylamino group, hydroxyl group, carboxyl group, formyl group, nitro group, cyano group, carboxylate group and sulfonate group, each independently selected from the group consisting of May form a condensed ring, and the group may be bonded to the condensed ring, and A is selected from hydrogen, halogen, an alkyl group, an alkoxy group, an aryl group, an amino group, an alkylamino group and a hydroxyl group. Group selected from the group
And an aromatic ketone represented by the following general formula (2)

Embedded image Wherein Q is an aliphatic group which may have a substituent or an aromatic group which may have a substituent, and X is a halogen. The following general formula (3)

Embedded image (Wherein, R ^{1 to} R ⁵ are hydrogen, halogen, an alkyl group,
Alkoxy group, allyl group, aralkyl group, aryl group,
An amino group, an alkylamino group, a hydroxyl group, a carboxyl group, a formyl group, a nitro group, a cyano group, an ester group and a sulfonyl ester group, each independently selected from the group consisting of May be bonded to the condensed ring thereof, and A is selected from the group consisting of hydrogen, halogen, an alkyl group, an alkoxy group, an aryl group, an amino group, an alkylamino group, and a hydroxyl group. Selected groups, and X is a halogen).

The reaction is carried out in a Lewis acid, in particular, for example, Z
The yield can be increased by using a weak Lewis acid such as nX ₂ , FeX ₃ or SnX ₂ (X is a halogen). Examples of Lewis acids include ZnCl ₂ , ZnBr ₂ ,
ZnF ₂ , ZnI ₂ , FeCl ₃ , FeBr ₃ , SnC
l ₂ , SnBr _{2 and the} like.

The Lewis acid is preferably supported on a carrier and used as a solid catalyst. The carrier is not limited, and examples of the carrier include silica, alumina, and molecular sieve. In particular, a catalyst in which ZnCl ₂ is supported on silica has a high yield and is preferable.

[0007] The reaction of the present invention can usually be carried out in the atmosphere, and can also be carried out in an atmosphere of an inert gas such as nitrogen or argon. The reaction temperature is 0 to 200.
° C, preferably 10 to 80 ° C, more preferably 20 to
40 ° C. The solvent is not particularly limited as long as it is inert to the reaction system.For example, as in a halogen compound such as dichloroethylene, an aliphatic hydrocarbon such as hexane, and an aromatic hydrocarbon such as benzene, Those which are not compatible with water and are not very strong are preferred.

The alkyl group for R ^{1 to} R ⁵ in the compound represented by the general formula (1), which is one of the raw materials of the present invention, includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, T-butyl and the like can be mentioned, and usually those having about 1 to 20 carbon atoms are preferable. Examples of the alkoxy group include an alkoxy group corresponding to the above-described alkyl group.

As the allyl group, a linear or branched one having usually about 1 to 6 carbon atoms, such as a propenyl group (allyl group), a butenyl group or a pentenyl group can be used.

Examples of the aryl group include a phenyl group and a phenyl group having a substituent. Examples of the aralkyl group include a benzyl group which may have a substituent. [0008]
The alkyl group mentioned in

Allyl groups described in [0009] can be mentioned.

The alkylamino group includes an alkylamino group having an alkyl moiety corresponding to the alkyl group.

Examples of the carboxylate group include formate, acetate, propionate, nicotinate, thiophenecarboxylate, and furancarboxylate. The ester portion usually has 1 to 20 carbon atoms. May be a linear or branched alkyl group or an aryl group, and the aryl group may be a single ring or 2 to 6 condensed rings.

Examples of the sulfonic acid ester group include methanesulfonic acid ester, ethanesulfonic acid ester, and propanesulfonic acid ester. The ester portion is the same as in the case of the carboxylic acid ester.

As the condensed ring formed by the adjacent groups of R ^{1 to} R ⁵ together, the aromatic moiety in the compound of the general formula (1) may be a group represented by the following formula.

[0015]

Embedded image Z is O, S, NH, NR (R is an alkyl, alkoxy, aryl, aralkyl group), CR ²⁰ (R ²⁰ is
Hydrogen, C _1-12 alkyl, aryl)

Representative examples of the compound represented by the general formula (1) include alkyl aryl ketones such as acetophenone, propiophenone and butyrophenone, aralkyl aryl ketones such as benzyl phenyl ketone, and phenyl picolyl ketone. And heteroaryl aryl ketones such as tons.

In the compound represented by the general formula (2), when Q is an aliphatic group, examples thereof include acetyl chloride, propionic acid chloride and butanoic acid chloride. Examples of such a case include benzoic acid chloride and naphthoic acid chloride, and examples of a heterocyclic group include picolinic acid chloride, and examples of an aralkyl group include phenylacetic acid chloride.

Examples of the compound of the general formula (3) which is the target compound of the present invention include α-chlorostyrene, α-chlorostilbene, α-chlorostilbazole and the like.

The proportion of the aromatic ketone represented by the general formula (1) and the acid halide represented by the general formula (2) is preferably such that the acid halide is used in an excess mole. A preferred use ratio is 1.1 equivalent to 20 equivalents,
It is particularly preferable to use about 8 equivalents of the acid halide with respect to the aromatic ketone.

[0020]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited thereby.

Example 1 Part 1: Zinc chloride supported on silica gel (ZnCl ₂ / SiO _2)
2 ) Production 10 g of zinc chloride is dissolved in 100 ml of water, and 40 g of silica gel (Wakogel C-200) is added thereto. Three
After stirring for 0 minutes, water was distilled off with an evaporator and dried under reduced pressure (150 ° C./14 mmHg) for 10 hours to obtain a silica gel-supported zinc chloride (ZnCl ₂ / SiO ₂ ) catalyst. 1 g of zinc chloride supported on silica gel contains 1.467 mmol of zinc chloride.

Part 2: Synthesis of 1-chloro-1,2-diphenylethene (α-chlorostilbene) In a 50 ml eggplant-shaped flask, benzylphenyl ketone (0.196 g, 1 mmol) and acetyl chloride (0.6
28 g, 8 mmol), ZnCl ₂ / SiO ₂ catalyst (0.136 g, corresponding to ZnCl ₂ : 0.2 mmol)
, And the solvent 1,2-dichloroethane (10 ml) was added, followed by stirring at 30 ° C. for 4 hours. The reaction mixture is filtered and Z
Wash the nCl ₂ / SiO ₂ catalyst with dichloroethane.
The combined filtrate and washings are washed with saturated aqueous sodium bicarbonate to remove excess acetyl chloride. Further wash with saturated saline. After the organic layer is dried over anhydrous sodium sulfate, the solvent is distilled off using an evaporator and concentrated. Flash column chromatography (silica gel, hexane)
To isolate the product, 1-chloro-1,2-diphenylethene (also referred to as α-chlorostilbene) from the residue. Yield 0.194 g (90%). White crystals (recrystallized from methanol), mp 53-4 ° C. FIG. 1 is a chart showing the range of 0 to 10 ppm in H-NMR, and FIG. 2 is an enlarged view of the range of 7 to 8 ppm.
FIG. 3 shows a full-range chart of C ¹³ -NMR of this product, and FIG.
The IR chart is shown in FIG. 5, and the mass spectrometry chart is shown in FIG.

Similarly, 0.2 mmol of AlC
l ₃ , FeCl ₃ , SnCl ₂ , ZnCl ₂ , SiO ₂
Was used to obtain the results shown in Table 1. The reaction formula is as follows.

[0024]

Embedded image

[0025]

[Table 1]

The use of weak Lewis acids such as ferric chloride, zinc chloride and stannous chloride produces the desired product in considerable yields. The yield is good when ferric chloride is used, but the reaction solution is colored dark brown. On the other hand, when stannous chloride was supported on the silica gel carrier, the reaction solution was not colored at all, and a high yield was obtained.

Example 2 (Synthesis of 1-chloro-1-phenylbutene) In a 50 ml eggplant-shaped flask, n-butyrophenone (0.
151 g, 1 mmol), acetyl chloride (0.628
g, 8 mmol), ZnCl ₂ / SiO ₂ (0.136
g, ZnCl ₂ : 0.2 mmol), and the solvent 1,2-dichloroethane (10 ml) was added, followed by stirring at 30 ° C. for 4 hours. The reaction mixture is filtered and ZnCl ₂ / S
Wash the iO ₂ catalyst with dichloroethane. The combined filtrate and washings are washed with saturated aqueous sodium bicarbonate to remove excess acetyl chloride. Further wash with saturated saline. After the organic layer is dried over anhydrous sodium sulfate, the solvent is distilled off using an evaporator and concentrated. The product, 1-chloro-1-phenylbutene, was isolated from the residue by flash chromatography (silica gel, hexane) (colorless oil). Yield 0.13 g (77%). The reaction formula is as follows.

[0028]

Embedded image

[0029]

(1) According to the present invention, a novel method for synthesizing a vinyl halide compound can be provided. (2) According to the present invention, a vinyl halide compound can be obtained with a high selectivity and a high yield.

[Brief description of the drawings]

FIG. 1. H- of 1-chloro-1,2-diphenylethene
1 shows a chart in the range of 0 to 10 ppm in NMR.

FIG. 2 shows an enlarged H-NMR chart in the range of 7 to 8 ppm in FIG.

FIG. 3. C of 1-chloro-1,2-diphenylethene
¹ shows an entire chart of ^13- NMR.

4 is an enlarged C ¹³ around 125 to 140 ppm in FIG.
3 shows an NMR chart.

FIG. 5. IR of 1-chloro-1,2-diphenylethene
The chart is shown.

FIG. 6 shows a mass spectrometry chart of 1-chloro-1,2-diphenylethene.

FIG. 7: H-NMR of 1-chloro-1-phenylbutene
2 shows a chart in the range of 0 to 10 ppm in the above.

FIG. 8 shows an IR chart of 1-chloro-1-phenylbutene.

FIG. 9 shows a mass spectrometry chart of 1-chloro-1-phenylbutene.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 22/04 C07C 22/04 37/00 37/00 39/19 39/19 41/22 41/22 43 / 225 43/225 B 45/63 45/63 47/55 47/55 51/363 51/363 63/04 63/04 67/307 67/307 69/76 69/76 Z 201/12 201/12 205 / 06 205/06 209/74 209/74 211/44 211/44 253/30 253/30 255/50 255/50 303/30 303/30 309/39 309/39 // C07B 61/00 300 300 C07B 61 / 00 300 (72) Inventor Takashi Takeda 1-3-3 Higashikawasaki-cho, Chuo-ku, Kobe-shi, Hyogo F-term (reference) in Chemipro Kasei Co., Ltd. 4H006 AA02 AC13 AC30 BA07 BA11 BA19 BA37 BA67 BJ50 BM10 BN30 BP30 BQ30 BS30 BU26 BU46 4H039 CA21 CA50 CB40

Claims (6)

[Claims] (1) The following general formula (1): (Wherein, R ^{1 to} R ⁵ are hydrogen, halogen, an alkyl group,
Alkoxy group, allyl group, aralkyl group, aryl group,
Amino group, alkylamino group, hydroxyl group, carboxyl group, formyl group, nitro group, cyano group, carboxylate group and sulfonate group, each independently selected from the group consisting of May form a condensed ring, and the group may be bonded to the condensed ring, and A is selected from hydrogen, halogen, an alkyl group, an alkoxy group, an aryl group, an amino group, an alkylamino group and a hydroxyl group. Group selected from the group
And an aromatic ketone represented by the following general formula (2): Wherein Q is an aliphatic group which may have a substituent or an aromatic group which may have a substituent, and X is a halogen. The following general formula (3) (Wherein, R ^{1 to} R ⁵ are hydrogen, halogen, an alkyl group,
Alkoxy group, allyl group, aralkyl group, aryl group,
An amino group, an alkylamino group, a hydroxyl group, a carboxyl group, a formyl group, a nitro group, a cyano group, an ester group and a sulfonyl ester group, each independently selected from the group consisting of May be bonded to the condensed ring thereof, and A is selected from the group consisting of hydrogen, halogen, an alkyl group, an alkoxy group, an aryl group, an amino group, an alkylamino group, and a hydroxyl group. X is a selected group, and X is a halogen). 2. The method according to claim 1, wherein the reaction is performed in the presence of a Lewis acid. 3. The method for synthesizing a vinyl halide compound according to claim 2, wherein the Lewis acid is carried on a carrier. 4. The vinyl halide according to claim ₃ , wherein the Lewis acid is selected from the group consisting of ZnX ₂ , FeX ₃ and SnX ₂ (where X is a halogen). Method for synthesizing compounds. 5. The carrier is silica gel and the Lewis acid is ZnX.
_{2. The} method for synthesizing a vinyl halide compound according to claim 1, wherein X is a halogen. 6. The synthesis of the vinyl halide compound according to claim 1, wherein the acid halide represented by the general formula (2) is used in an excess mole relative to the aromatic ketone represented by the general formula (1). Law.