CN1063868A - The preparation method of sulfonyl halide - Google Patents
The preparation method of sulfonyl halide Download PDFInfo
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- CN1063868A CN1063868A CN92100864A CN92100864A CN1063868A CN 1063868 A CN1063868 A CN 1063868A CN 92100864 A CN92100864 A CN 92100864A CN 92100864 A CN92100864 A CN 92100864A CN 1063868 A CN1063868 A CN 1063868A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C313/00—Sulfinic acids; Sulfenic acids; Halides, esters or anhydrides thereof; Amides of sulfinic or sulfenic acids, i.e. compounds having singly-bound oxygen atoms of sulfinic or sulfenic groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C313/08—Sulfenic acids; Derivatives thereof
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of preparation structural formula: RCY (Z) SO
2The method of the sulfonyl halide of X, wherein X, Y and Z are halogens, and R is alkyl, halogen, halogenated alkyl or aryl, this method is to be that the sulfuration phenyl halogenide of RCY (Z) SX is finished by the oxidation structure formula.Sulfonyl halide is the useful intermediates of sterilant.
Description
The present invention relates to the preparation method of sulfonyl halide.Previously, the all halogenated hydrocarbons sulfonyl halide is by all halogenated hydrocarbons and V-Brite B reaction, carry out then that the halogenation of sulfonic acid intermediate prepares, this method is documented in " chemical journal ", and 1986,44(1) 45-50(Chemical Abstracts, 105,171793b) page or leaf and " chemical journal ", 1984,42
*10,1114-1115(Chemical Abstracts, 102,78313g) page or leaf, the author of two pieces of articles is people such as W.Huang.This method relates to uses for example tetracol phenixin and 1,1 of high-volatile all halogenated hydrocarbons, the 1-Refrigerant R 113, and for avoiding it to enter the rational approach that atmosphere is taked.
The present invention relates to a kind of preparation halogenated alkane sulfonyl halide, comprise the method for all halogenated hydrocarbons sulfonyl halide, it avoids using these volatile matter.
Therefore, the invention provides a kind of method for preparing the sulfonyl halide of structural formula I, this method comprises corresponding thio-phenyl halogenide and the oxidant reaction that makes the structural formula II.X in the structural formula I, Y and Z are independently selected from halogen, preferred chlorine, fluorine or bromine; R is halogen, alkyl or haloalkyl, or can be by any aryl that replaces of halogen.
Suitable oxygenant comprises that for example, superoxide and peracid are as hydrogen peroxide, peracetic acid and peroxybenzoic acid.
Preferred oxygenant is the mixture of hydrogen peroxide and Glacial acetic acid.If desired, this method can at high temperature be carried out.
The compound of the structural formula I by method of the present invention preparation comprises, for example:
Three chloro methane sulfuryl chlorides;
Three bromo methane sulfonyl bromines;
Three fluoro methane sulfonyl bromines;
1.1-two chloro-2,2,2-Halothane sulfuryl chloride, and
1,1-two chloro-1-(4-chloro-phenyl-s) the methane sulfuryl chloride.
The compound oxidation of structural formula II can be become the compound of structural formula I by method of the present invention, the example of structural formula II compound comprises:
Trichloromethane thio-phenyl muriate;
Methenyl bromide thio-phenyl bromide;
Trifluoromethane thio-phenyl bromide;
1,1-two chloro-2,2,2-Halothane thio-phenyl muriate; With
1,1-two chloro-1-(4-chloro-phenyl-s) methane thio-phenyl muriate.
The thio-phenyl halogenide of structural formula II can obtain by the halogenation decomposition of appropriate precursors, the thioether of the disulphide of the example of these precursors such as structural formula III and structural formula IV, wherein the halogenation with the methylene radical of R group is to decompose the thio-phenyl halogenide and the benzyl halogenide that produce the structural formula II by the halogenation of sulphur-benzyl key to finish.
The sulfonyl halide of structural formula I can be used as valuable chemical intermediate in chemosynthesis.A kind of useful especially method (for example comprises the sulfonyl halide of structural formula I and unsaturated ester, 3,3-dimethyl-penten-obtusilic acid methyl esters) reaction prepares the compound of structural formula V, and the compound of structural formula V is the valuable intermediate that is used for pyrethroid insecticides.These reactions are delivered and intactly are documented in the unexamined patent that we apply on the same day, and the exercise question of this patent is " method for preparing halogenated compound ".
The compound that reaction by sulfonyl halide can prepare comprises:
3,3-dimethyl-4,6,6,6-tetrachloro methyl caproate;
3,3-dimethyl-4,6,6,6-tetrabromo methyl caproate;
3,3-dimethyl-4,6,6,6-tetrachloro ethyl hexanoate;
3,3-dimethyl-4-bromo-6,6,6-trifluoro methyl caproate;
4,4-dimethyl-1,5,7,7,7-pentachloro-heptan-2-ketone;
4,4-dimethyl-1,5,7,7-tetrachloro-7-(4-chloro-phenyl-)-heptan-2-ketone;
3,3-dimethyl-4,6,6,6-tetrachloro caproic acid;
3,3-dimethyl-4,6,6-three chloro-7,7,7-trifluoro Methylheptanoate;
3,3-dimethyl-4,6,6-three chloro-7,7,7-trifluoro oil of cognac;
3,3-dimethyl-4,6,6-three chloro-6-(4-chloro-phenyl-s)-methyl caproate;
3,3-dimethyl-4,6,6-three chloro-7,7,7-trifluoro acid benzyl ester in heptan;
3,3-dimethyl-4,6,6-three chloro-7,7,7-trifluoro enanthic acid-2,6-benzyl dichloride ester;
3,3-dimethyl-4,6,6-three chloro-7,7,7-trifluoro enanthic acid-4-methyl-2,3,5,6-ptfe benzyl;
3,3-dimethyl-4,6,6,6-tetrachloro caproic acid five fluoro-methylbenzyl esters;
3,3-dimethyl-4,6,6,6-tetrachloro caproic acid-2,3,5,6-ptfe benzyl;
3,3-dimethyl-4,6,6-three chloro-7,7,7-trifluoro enanthic acid-2-methyl-3-phenyl benzyl ester;
3,3-dimethyl-4,6,6,6-tetrachloro caproic acid-3-phenoxy group benzyl ester;
3,3-dimethyl-4,6,6,6-tetrachloro caproic acid-alpha-cyano-3-phenoxy group benzyl ester;
3,3-dimethyl-4,6,6,6-tetrabromo caproic acid-alpha-cyano-3-phenoxy group benzyl ester;
3,3-dimethyl-4,6,6,6-tetrachloro caproic acid-alpha-cyano-4-fluoro-3-phenoxy group benzyl ester;
3,3-dimethyl-4,6,6-three chloro-7,7,7-trifluoro enanthic acid-alpha-cyano-3-phenoxy group benzyl ester; And
3,3-dimethyl-4,6,6-three chloro-7,7,7-trifluoro enanthic acid-alpha-cyano-4-fluoro-3-phenoxy group benzyl ester.
These compounds can be used to prepare pyrethroid insecticides by the technology that for example English Patent No.1520443 describes.
The further details of the inventive method is set forth in the following example.
Embodiment 1
This embodiment describes the preparation of two-(2,2, the 2-trifluoromethyl) disulphide.
Under nitrogen atmosphere, with 2,2, the mixture of 2-trifluoroethyl bromine (9.8g), sodium sulphite 9 hydrates (14.4g), sulphur (1.9g), bromination hexadecyl tributyl phosphorus (1.0g) and water (18.0g) is added in the Carius pipe, and with the seal of tube.To manage heating 8 hours under 70 ℃, cooling, content with vapor distillation obtain buttery two-(2,2, the 2-trifluoroethyl) disulphide, productive rate 67%.Product is identified with the GC-mass spectrum.
Embodiment 2
This embodiment describes 1,1-two chloro-2,2, the muriatic preparation of 2-Halothane thio-phenyl.
Under room temperature and dry nitrogen atmosphere, with the thio-phenyl muriate (4,46g) be added drop-wise to two-(2,2, the 2-Halothane) disulphide (1.0g) at methylene dichloride (5.0cm
3) solution in, use the gas liquid chromatography analysis after 3 hours, the productive rate of required product is 60%.This product is identical with following embodiment 4 resulting products.
Embodiment 3
This embodiment describes 2,2, the preparation of 2-trifluoroethyl sulfo-toluene.
Under nitrogen atmosphere, with 1-chloro-2,2,2-Halothane (20g), benzyl mercaptan (12.4g, 99% concentration), the mixture of sodium hydroxide (22% aqueous solution 22.0g) and bromination hexadecyl tributyl phosphorus (0.51g) is added in the Carius pipe that reseals 70 ℃ of following heating 10 hours.Pipe is cooled to 0 ℃ then, Kaifeng, content is divided into two-layer.Organic layer below collecting washes with water, obtains 2,2 by the short-path distillation purifying, 2-trifluoroethyl sulfo-toluene, b.p.60-70 ℃/10mmHg, 17.4g(productive rate 84%, concentration 99%).With look-matter spectrum and nucleus magnetic resonance and by with people such as C.Bunyagidj at J.Org.Chem., the data that provide in 1981,46,3335 compare to determine product.
Embodiment 4
This embodiment describes 1,1-two chloro-2,2, the muriatic preparation of 2-Halothane thio-phenyl.
With 2,2,2-trifluoroethyl sulfo-toluene (20.0g, concentration 99% is from the method acquisition of the foregoing description 3) is at sym.-tetrachloroethane (26.4cm
3) in solution be cooled to 0 ℃, under this temperature to about 3 hours of the logical chlorine of solution.The orange-yellow solution purging with nitrogen gas that obtains like this, and carry out rectifying, obtain 1,1-two chloro-2,2,2-Halothane thio-phenyl muriate, deep yellow oily thing, b.p.63-65 ℃/200mbar(17.4g, concentration 73%, molar yield 60%), this product pollutes by the tetrachloroethane of remnants with less than 1% Benzyl Chloride.With look-matter spectrum, and by with people such as H.Fritz at Chem.Ber., the data that provide on 1989,122,1757 compare to determine product.
Embodiment 5
This embodiment describes 1,1-two chloro-2,2, the preparation of 2-trichloroethane sulfuryl chloride.
At 10 ℃, with 1,1-two chloro-2,2,2-trichloroethane thio-phenyl muriate (6.3g is from the method acquisition of embodiment 4) is dissolved in the Glacial acetic acid (16.0g), and this solution is cooled to 5 ℃.In 30 minutes, (30% solution 16.8g in water) is added drop-wise in the muriatic solution of thio-phenyl with hydrogen peroxide, solution is heated to 60 ℃ then, until yellow completely dissolve (about 2 hours).Mixture is chilled to room temperature, and excessive hydrogen peroxide is handled with the aqueous solution (10%w/w) of Sodium Pyrosulfite and made its decomposition.Mixture is divided into two-phase, and the organic phase below collecting is also used look-matter spectrometer analysis.It is needed 1 that this organic phase contains 75%w/w, 1-two chloro-2,2, and 2-Halothane sulfuryl chloride, molar yield is 57%.Compare by material and to confirm product with people's such as H.Wei-Yuan method (Acta Chim.Sinica, 1986,44,45(Chemical Abstracts 105,171793b)) preparation.
Embodiment 6
This embodiment describes 3,3-dimethyl-4,6,6, the preparation of 6-tetrachloro methyl caproate.
Dichloro three-(triphenylphosphine oxide group) ruthenium (II) (0.2g) in the presence of, (22.5g) is added to 3 with the trichloromethane sulfuryl chloride, in toluene (8.67g) solution of 3-dimethyl-penten-obtusilic acid methyl esters (8.26g), under the nitrogen atmosphere this mixture was heated 40 hours at reflux temperature (about 111 ℃).Use gas-liquid chromatograph (glc) to determine the composition of reaction mixture then, the amount of required product is with 3 of adding, 3-dimethyl-penten-obtusilic acid methyl esters is 76% for the basic calculation productive rate, and with 3 of consumption, 3-dimethyl-penten-obtusilic acid methyl esters is 90% for the basic calculation productive rate.Product by look-matter spectrum and from English Patent No.1520443 institute described method obtain 3,3-dimethyl-4,6,6,6-tetrachloro capronate is confirmed.
Embodiment 7
This embodiment describes 3,3-dimethyl-4,6,6, the preparation of 6-tetrachloro methyl caproate.
(44.5g) is added to 3 with the trichloromethane sulfuryl chloride, and in the mixture of 3-dimethyl-penten-obtusilic acid methyl esters (16.52g), toluene (17.34g) and benzoyl peroxide (0.563g), this mixture was 90 ℃ of heating 3.5 hours.Composition with the definite reaction mixture of gas-liquid chromatograph shows that with 3 of adding, 3-dimethyl-penten-obtusilic acid methyl esters is a basic calculation, and required product obtains with 92% productive rate.
Embodiment 8
This embodiment describes 3,3-dimethyl-4,6,6-three chloro-7,7, the preparation of 7-trifluoro Methylheptanoate.
With 1,1-two chloro-2,2,2-trichloroethane sulfuryl chloride (1.5g) and 3, the mixture of 3-dimethyl-penten-obtusilic acid methyl esters (2.0g) were 110 ℃ of heating 40 minutes, and composition is analyzed by glc and determined that the productive rate that shows required product is 79%.
Embodiment 9
This embodiment describes 3,3-dimethyl-4,6,6-three fluoro-7,7, the preparation of 7-trifluoro Methylheptanoate.
With 1,1-two chloro-2,2,2,2-Tetrafluoroethane sulfuryl chloride (0.2g) is added to 3, and in the mixture of 3-dimethyl-penten-obtusilic acid methyl esters (0.18g), toluene (0.13g) and dibenzoyl peroxide (0.015g), this mixture heated 2 hours down at reflux temperature (about 111 ℃).To gained reaction mixture composition determine show that the productive rate of required product is 82%, and do not have sulfuryl chloride to exist.
Chemical structural formula in the specification sheets
R-CH
2-S-CH
2C
6H
5（Ⅳ）
Claims (5)
1, a kind of preparation structural formula is:
The method of sulfonyl halide, wherein X, Y and Z are independently selected from halogen, and R is halogen, alkyl, halogenated alkenyl or the aryl that can be replaced arbitrarily by halogen, this method comprises makes structural formula be:
Corresponding thio-phenyl halogenide and oxidant reaction.
2, the process of claim 1 wherein that oxygenant is selected from superoxide and peracid.
3, the method for claim 2, wherein oxygenant is selected from hydrogen peroxide, peracetic acid and peroxybenzoic acid.
4, the method for claim 3, wherein oxygenant is the mixture that peroxide is crossed hydrogen and Glacial acetic acid.
5, the process of claim 1 wherein that thio-phenyl halogenide by halogenation decomposition texture formula is:
Disulphide or structural formula be:
R-CH
2-S-CH
2C
6H
5
Thioether and obtain.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9100655.1 | 1991-01-11 | ||
| GB919100655A GB9100655D0 (en) | 1991-01-11 | 1991-01-11 | Preparation of sulphonyl halides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1063868A true CN1063868A (en) | 1992-08-26 |
Family
ID=10688326
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92100864A Pending CN1063868A (en) | 1991-01-11 | 1992-01-11 | The preparation method of sulfonyl halide |
Country Status (6)
| Country | Link |
|---|---|
| CN (1) | CN1063868A (en) |
| AU (1) | AU1160992A (en) |
| GB (2) | GB9100655D0 (en) |
| PT (1) | PT100005A (en) |
| TW (1) | TW215432B (en) |
| WO (1) | WO1992012125A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111004155A (en) * | 2019-09-11 | 2020-04-14 | 浙江埃森化学有限公司 | Preparation method of trifluoromethyl sulfuryl halide |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111116363B (en) * | 2019-12-27 | 2023-04-14 | 山东潍坊润丰化工股份有限公司 | Preparation method of carboxylic ester compound |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2664443A (en) * | 1952-01-08 | 1953-12-29 | Olin Mathieson | Process of producing trichloromethane sulfonyl chloride |
| NL299822A (en) * | 1962-10-29 | |||
| FR2599366B1 (en) * | 1986-05-28 | 1988-08-26 | Rhone Poulenc Spec Chim | PROCESS FOR THE PREPARATION OF BENZYL SULFIDE AND TRIFLUOROMETHYL |
| DE3741309A1 (en) * | 1987-12-05 | 1989-06-15 | Bayer Ag | METHOD FOR PRODUCING TRIFLUORMETHANESULPHONIC ACID CHLORIDE |
-
1991
- 1991-01-11 GB GB919100655A patent/GB9100655D0/en active Pending
-
1992
- 1992-01-08 AU AU11609/92A patent/AU1160992A/en not_active Abandoned
- 1992-01-08 WO PCT/GB1992/000038 patent/WO1992012125A1/en active Application Filing
- 1992-01-08 GB GB9200266A patent/GB2251619A/en not_active Withdrawn
- 1992-01-09 TW TW081100125A patent/TW215432B/zh active
- 1992-01-10 PT PT100005A patent/PT100005A/en not_active Application Discontinuation
- 1992-01-11 CN CN92100864A patent/CN1063868A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111004155A (en) * | 2019-09-11 | 2020-04-14 | 浙江埃森化学有限公司 | Preparation method of trifluoromethyl sulfuryl halide |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2251619A (en) | 1992-07-15 |
| GB9100655D0 (en) | 1991-02-27 |
| GB9200266D0 (en) | 1992-02-26 |
| AU1160992A (en) | 1992-08-17 |
| WO1992012125A1 (en) | 1992-07-23 |
| PT100005A (en) | 1993-01-29 |
| TW215432B (en) | 1993-11-01 |
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| Date | Code | Title | Description |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |