WO1992012125A1 - Preparation of sulphonyl halides - Google Patents

Preparation of sulphonyl halides Download PDF

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Publication number
WO1992012125A1
WO1992012125A1 PCT/GB1992/000038 GB9200038W WO9212125A1 WO 1992012125 A1 WO1992012125 A1 WO 1992012125A1 GB 9200038 W GB9200038 W GB 9200038W WO 9212125 A1 WO9212125 A1 WO 9212125A1
Authority
WO
WIPO (PCT)
Prior art keywords
dimethyl
formula
sulphonyl
methyl
preparation
Prior art date
Application number
PCT/GB1992/000038
Other languages
English (en)
French (fr)
Inventor
Gary Neil Sheldrake
Original Assignee
Zeneca Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zeneca Limited filed Critical Zeneca Limited
Publication of WO1992012125A1 publication Critical patent/WO1992012125A1/en

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Classifications

    • 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
    • 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

Definitions

  • This invention relates to the preparation of sulphonyl halides.
  • Perhaloalkanesulphonyl halides have previously been prepared by reaction of perhaloalkanes with sodium dithionite followed by halogenation of the intermediate sulphonic acids as described by W. Huang et al, Huaxue Xuebao, 1986, 44(1), 45-50 (Chemical Abstracts, 105, 171793b) and W. Huang et al, Huaxue Xuebao, 1984, 42 *10), 1114-1115 (Chemical Abstracts, 102, 78313g).
  • Such methods involve the use of highly volatile perhaloalkanes, such as carbon tetrochloride and 1,1,1,-trichlorotrifluoroethane, and this requires considerable precautions to avoid escape of such volatile materials to the atmosphere.
  • the present invention relates to a process for preparing haloalkane sulphonyl halides, including perhaloalkane sulphonyl halides which avoids the use of these volatile materials.
  • the present invention provides a process for the
  • X, Y and Z are each selected from halo, preferably chloro, fluoro or bromo, and R is halo, alkyl or haloalkyl, or aryl which may optionally be substituted with halo, which comprises reacting the corresponding sulphenyl halide of formula II:
  • Suitable oxidising agents include, for example, peroxides and
  • peracids such as hydrogen peroxide, peracetic acid and perbenzoic acid.
  • a preferred oxidising agent is a mixture of hydrogen peroxide and glacial acetic acid.
  • the process can be conducted at elevated temperatures if desired.
  • the compounds for formula II which may be oxidised to obtain the compounds of formula I by the process of the invention, include for example:
  • halogenolysis of suitable precursors such as a disulphide of formula III: or a thioether of formula IV:
  • halogenation of the methylene group bearing the R group is accompanied by halogenolysis of the sulphur-benzyl bond giving rise to the sulphenyl halide of formula II and benzyl halide.
  • the sulphonyl halides of formula I are valuable chemical intermediates which may be used in chemical synthesis.
  • One particularly useful process involves reaction of the sulphonyl halides of formula I with unsaturated esters, such as for example, methyl 3,3-dimethylpent-4-enoate, to prepare compounds of formula V:
  • Such compounds can be used to make pyrethroid insecticides by, for example, the techniques described in UK Patent No. 1520443.
  • This Example illustrates the preparation of bis-(2,2,2-trifluoromethyl) disulphide.
  • This Example illustrates the preparation of 1,1-dichloro-2,2,2-trifluoroethane sulphenyl chloride.
  • This Example illustrates the preparation of 2,2,2-trifluoroethylthiomethylbenzene.
  • This Example illustrates the preparation of 1,1- dichloro-2,2,2-trifluoroethane sulphenyl chloride.
  • 1,1,2, 2-tetrachloroethane (26.4cm 3 ) was cooled to 0°C and chlorine gas passed into the solution for ca 3 hours at this temperature.
  • the orange solution thus obtained was sparged with nitrogen and subjected to
  • This Example illustrates the preparation of 1,1-dichloro-2,2,2-trichloroethane sulphonyl chloride.
  • 1,1-Dichloro-2,2,2-trichloroethane sulphenyl chloride (6.3g) obtained by the method of Example 4) was dissolved in glacial acetic acid (16.0g) at 10°C and the solution cooled to 5°C.
  • Hydrogen perodide (16.8g of a 30% solution in water) was added dropwise to the solution of the sulphenyl chloride over 30 minutes after which the solution was heated to 60°C until the yellow colour had been completely discharged (ca 2 hours). The mixture was cooled to the ambient temperature and the excess hydrogen peroxide decomposed by treatment with an aqueous solution (10% w/w) of sodium metabisulphite.
  • Trichloromethane sulphonyl chloride (22.5g) is added to a solution of methyl 3,3-dimethylpent-4-enoate (8.26g) in toluene (8.67g) in the presence of tris-(triphenylphosphinyl)ruthenium(II) dichloride (0.2g) and the mixture heated under an nitrogen atmosphere at the reflux temperature (ca. 111°C) for 40 hours. The composition of the reaction mixture was then determined by gas liquid chromatography (glc). The desired product was present in an amount indicating a yield of 76% by weight based on methyl 3,3-dimethylpent-4-enoate charged, and 90% based on methyl
  • Trichloromethane sulphonyl chloride (44.5g) was added to a mixture of methyl 3,3-dimethylpene-4-enoate (16.52g), toluene (17.34g) and benzoyl peroxide (0.563g) and the mixture heated at 90oC for 3.5 hours.
  • 1,1-Dichloro-2,2,2,2-trifluoroethane sulphonyl chloride (0.2g) was added to a mixture of methyl 3,3-dimethylpent-4-enoate (0.18g), toluene (0.13g) and dibenzoyl peroxide (0.015g) and the mixture heated at the reflux temperature (ca. 111°C) for 2 hours. Determination of the resultant reaction mixture composition showed that the desired product had been produced to a yield of 82%, and that no sulphonylchloride remained.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
PCT/GB1992/000038 1991-01-11 1992-01-08 Preparation of sulphonyl halides WO1992012125A1 (en)

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
WO1992012125A1 true WO1992012125A1 (en) 1992-07-23

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PCT/GB1992/000038 WO1992012125A1 (en) 1991-01-11 1992-01-08 Preparation of sulphonyl halides

Country Status (6)

Country Link
CN (1) CN1063868A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
AU (1) AU1160992A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
GB (2) GB9100655D0 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
PT (1) PT100005A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
TW (1) TW215432B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
WO (1) WO1992012125A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111116363A (zh) * 2019-12-27 2020-05-08 山东潍坊润丰化工股份有限公司 一种羧酸酯类化合物的制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111004155A (zh) * 2019-09-11 2020-04-14 浙江埃森化学有限公司 一种三氟甲基亚磺酰卤的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2664443A (en) * 1952-01-08 1953-12-29 Olin Mathieson Process of producing trichloromethane sulfonyl chloride
EP0247953A1 (fr) * 1986-05-28 1987-12-02 Rhone-Poulenc Chimie Procéde de préparation du sulfure de benzyle et de trifluorométhyle
EP0319767A2 (de) * 1987-12-05 1989-06-14 Bayer Ag Verfahren zur Herstellung von Trifluormethansulfonsäurechlorid

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL299822A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) * 1962-10-29

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2664443A (en) * 1952-01-08 1953-12-29 Olin Mathieson Process of producing trichloromethane sulfonyl chloride
EP0247953A1 (fr) * 1986-05-28 1987-12-02 Rhone-Poulenc Chimie Procéde de préparation du sulfure de benzyle et de trifluorométhyle
EP0319767A2 (de) * 1987-12-05 1989-06-14 Bayer Ag Verfahren zur Herstellung von Trifluormethansulfonsäurechlorid

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 72, no. 7, 16 February 1970, Columbus, Ohio, US; abstract no. 31156W, E. DYKMAN ET AL.: 'IMPROVED SYNTHESIS OF TRICHLOROMETHANESULFONYL CHLORIDE' page 258 ;column 2 ; *
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY vol. 63, no. 6, June 1941, pages 1764 - 1765; M.S. SCHECHTER ET AL.: 'THE PREPARATION OF TRICHLOROMETHANESULFONYL CHLORIDE' *
JOURNAL OF THE CHEMICAL SOCIETY (C) 1966, pages 1171 - 1179; R.E. BAMKS ET AL.: 'PERFLUOROALKYL DERIVATIVES OF SULPHUR. PART VIII. SYNTHESIS AND REACTIONS OF PERFLUOROETHYLENESULPHONYL FLUORIDE.' *
JOURNAL OF THE CHEMICAL SOCIETY 1955, pages 2901 - 2910; R.N.HAZELDINE ET AL.: 'PERFLUOROALKYL DERIVATIVES OF SULFUR. PART II. TRIFLUOROMETHANESULPHONIC, -SULPHINIC, AND -SULPHENIC ACID AND THE INFRARED SPECTRA OF COMPOUNDS CONTAINING -SO2- AND S=O GROUPS.' *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111116363A (zh) * 2019-12-27 2020-05-08 山东潍坊润丰化工股份有限公司 一种羧酸酯类化合物的制备方法

Also Published As

Publication number Publication date
TW215432B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1993-11-01
GB9200266D0 (en) 1992-02-26
GB2251619A (en) 1992-07-15
CN1063868A (zh) 1992-08-26
GB9100655D0 (en) 1991-02-27
PT100005A (pt) 1993-01-29
AU1160992A (en) 1992-08-17

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