WO1992017443A1 - Procede de preparation de chlorures d'acide 2-alkylthio-benzolsulfonique - Google Patents

Procede de preparation de chlorures d'acide 2-alkylthio-benzolsulfonique Download PDF

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Publication number
WO1992017443A1
WO1992017443A1 PCT/EP1992/000678 EP9200678W WO9217443A1 WO 1992017443 A1 WO1992017443 A1 WO 1992017443A1 EP 9200678 W EP9200678 W EP 9200678W WO 9217443 A1 WO9217443 A1 WO 9217443A1
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WO
WIPO (PCT)
Prior art keywords
alkylthio
acid chlorides
temperatures
copper
chloride
Prior art date
Application number
PCT/EP1992/000678
Other languages
German (de)
English (en)
Inventor
Hans-Jochem Riebel
Original Assignee
Bayer Aktiengesellschaft
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 Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Publication of WO1992017443A1 publication Critical patent/WO1992017443A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups

Definitions

  • the invention relates to a new process for the preparation of 2-alkyl thio-benzenesulfonic acid chlorides which can be used as intermediates for the preparation of herbicides.
  • 2-alkylthio-benzenesulfonic acid chlorides such as 2-methylthio-benzenesulfonic acid chloride
  • 2-alkylthio-anilines such as 2-methylthio-aniline
  • sodium nitrite in mixtures of hydrochloric acid and acetic acid
  • sulfur dioxide in the presence of copper chloride
  • R represents straight-chain or branched alkyl, obtained in very good yields and in high purity, if 2-alkylthio-anilines of the general formula (II)
  • R has the meaning given above, with aqueous solutions of alkali metal nitrites in the presence of concentrated aqueous hydrochloric acid (without the addition of acetic acid) at temperatures between -10 ° C. and + 10 ° C. and then, if appropriate after addition there would be an organic solvent, reacted with sulfur dioxide in the presence of a copper catalyst at temperatures between -10 ° C and + 50 ° C.
  • the 2-alkylthio-benzenesulfonic acid chlorides of the formula (I) can be obtained in higher yields and in better quality than according to known methods by the process according to the invention, in which, in contrast to the prior art, the use of acetic acid as a solvent is dispensed with. Disposing of acetic acid as a solvent reduces the disposal problems; the method according to the invention is therefore very well suited for use on an industrial scale.
  • the process according to the invention preferably relates to the preparation of 2-alkyl thio-benzenesulfonic acid chlorides of the formula (I) »in which
  • R represents straight-chain or branched alkyl having 1 to 6 carbon atoms.
  • the process according to the invention relates to the preparation of compounds of the formula (I) in which R represents ethyl, propyl, isopropyl, butyl, isobutyl or sec-butyl.
  • Formula (II) provides a general definition of the 2-alkylthio-ani line to be used as starting materials in the process according to the invention.
  • R preferably or in particular has the meaning which has been given above or in connection with the description of the compounds of the formula (I) to be prepared according to the invention as preferred or as particularly preferred for R.
  • the starting materials of the formula (II) are known and / or can be prepared by processes known per se (cf. Synthesis 1990, 911-914; DE-OS 3528033).
  • the process according to the invention is carried out using alkali metal nitrites.
  • Sodium nitrite or potassium nitrite, in particular sodium nitrite, is preferably used.
  • the process according to the invention is carried out in the second stage in the presence of a copper catalyst.
  • Copper (I) chloride and / or copper (II) chloride is preferably used.
  • the process according to the invention is preferably carried out in the second stage in the presence of an organic solvent.
  • preference is given to aliphatic and aromatic, optionally halogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane, petroleum ether, gasoline, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform or carbon tetrachloride.
  • reaction temperatures can be varied over a wide range in the process according to the invention.
  • the first stage of the process is used
  • Subsequent stage (implementation with S0 2 ) between -10 ° C and + 50 ° C, preferably between -5 ° C and + 30 ° C.
  • the process according to the invention is generally carried out at normal pressure. However, it is also possible to work under elevated or reduced pressure, generally between 100 mbar and 10 bar.
  • 1 mol of 2-alkyl thio-ani 1 in the formula (II) is generally between 0.9 and 1.2 mol, preferably between 1.0 and 1.1 mol of alkali metal nitrite, between 100 ml and 1000 ml, preferably between 200 ml and 500 ml, of concentrated aqueous hydrochloric acid, between 1 and 10 mol, preferably between 2 and 5 mol, sulfur dioxide, and between 0.001 and 0.1 mol, preferably between 0.005 and 0.05 mol, one Copper catalyst.
  • the 2-alkylthio-ani lin of the formula (II) and the concentrated aqueous hydrochloric acid are first mixed with cooling. With further cooling and stirring, the aqueous solution of an alkali metal nitrite is then slowly metered in and stirring is continued until implementation of the first stage has been completed. Then a copper catalyst and optionally an organic solvent are added to the reaction mixture and the sulfur dioxide is slowly metered in. The mixture is stirred until the reaction has ended.
  • the workup can be carried out in the usual way.
  • the reaction mixture is optionally diluted with water and / or with an organic solvent which is practically immiscible with water and shaken thoroughly.
  • the organic phase is separated off, washed with water, dried and filtered. After the organic solvent has been carefully distilled off under reduced pressure, the product of the formula (I) is obtained as an oily residue which can be reacted further without further purification.
  • the 2-alkylthio-benzenesulfonic acid chlorides to be prepared by the process according to the invention can be used as intermediates for the preparation of herbicides (cf. EP-A 173319). Manufacturing examples:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Afin de produire avec un très bon rendement des chlorures (I) très purs d'acide 2-alkylthio-benzolsulfonique (utiles comme produits intermédiaires pour la synthèse de substances actives herbicides), on fait réagir selon le schéma (A) des 2-alkylthio-anilines (II) avec des solutions aqueuses de nitrites de métaux alcalins en présence d'acide chlorhydrique aqueux concentré (sans adjonction d'acide acétique) à des températures comprises entre -10 °C et +10 °C, puis on les fait réagir, le cas échéant après avoir ajouté un solvant organique, avec de l'anhydre sulfureux en présence d'un catalyseur de cuivre à des températures comprises entre -10 °C et +50 °C.
PCT/EP1992/000678 1991-04-05 1992-03-26 Procede de preparation de chlorures d'acide 2-alkylthio-benzolsulfonique WO1992017443A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19914110963 DE4110963A1 (de) 1991-04-05 1991-04-05 Verfahren zur herstellung von 2-alkylthio-benzolsulfonsaeurechloriden
DEP4110963.5 1991-04-05

Publications (1)

Publication Number Publication Date
WO1992017443A1 true WO1992017443A1 (fr) 1992-10-15

Family

ID=6428845

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1992/000678 WO1992017443A1 (fr) 1991-04-05 1992-03-26 Procede de preparation de chlorures d'acide 2-alkylthio-benzolsulfonique

Country Status (4)

Country Link
AU (1) AU1444192A (fr)
DE (1) DE4110963A1 (fr)
PL (1) PL294103A1 (fr)
WO (1) WO1992017443A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0059241A1 (fr) * 1981-02-28 1982-09-08 BASF Aktiengesellschaft Procédé de préparation des halogénures aromatiques de sulfonyle
EP0173319A1 (fr) * 1984-08-30 1986-03-05 Bayer Ag Arylsulfonylguanidines substituées

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0059241A1 (fr) * 1981-02-28 1982-09-08 BASF Aktiengesellschaft Procédé de préparation des halogénures aromatiques de sulfonyle
EP0173319A1 (fr) * 1984-08-30 1986-03-05 Bayer Ag Arylsulfonylguanidines substituées

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMISCHE BERICHTE Bd. 90, Nr. 6, 1957, WEINHEIM, DE Seiten 841 - 852; H. MEERWEIN ET AL.: 'VERFAHREN ZUR HERSTELLUNG AROMATISCHER SULFONS[URECHLORIDE, EINE NEUE MODIFIKATION DER SANDMEYERSCHEN REAKTION' *
RECEUIL DES TRAVAUX CHIMIQUES DES PAYS-BAS Bd. 84, Nr. 1, Januar 1965, DEN HAAG Seiten 24 - 30; A.J. PRINSEN ET AL: 'THE SYNTHESIS OF ARYLSULFONYLHALIDES' *

Also Published As

Publication number Publication date
DE4110963A1 (de) 1992-10-08
AU1444192A (en) 1992-11-02
PL294103A1 (en) 1992-12-14

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