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WO2025074365A1 - Procédé de préparation de chlorure de thiophène 3-sulfonyle substitué - Google Patents

Procédé de préparation de chlorure de thiophène 3-sulfonyle substitué Download PDF

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Publication number
WO2025074365A1
WO2025074365A1 PCT/IL2024/050974 IL2024050974W WO2025074365A1 WO 2025074365 A1 WO2025074365 A1 WO 2025074365A1 IL 2024050974 W IL2024050974 W IL 2024050974W WO 2025074365 A1 WO2025074365 A1 WO 2025074365A1
Authority
WO
WIPO (PCT)
Prior art keywords
formula
compound
nitrite
chloride
salt
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
PCT/IL2024/050974
Other languages
English (en)
Inventor
Michael Grabarnick
Wenjun Wang
Shaoxiang WU
Wei Liu
Rui Gao
Jinping Zhang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Adama Agan Ltd
Original Assignee
Adama Agan Ltd
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 Adama Agan Ltd filed Critical Adama Agan Ltd
Publication of WO2025074365A1 publication Critical patent/WO2025074365A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the invention relates to a process for preparing substituted 4-alkoxy carbonyl thiophene 3- sulphonyl chloride of formula (I), which are known as intermediates for active ingredients in agriculture, especially used for the preparation of herbicidal active compound of formula (X).
  • the present invention provides that the acidic medium comprises of aqueous solution of hydrochloric acid, wherein the strength of hydrochloric acid in the range from 10 to 35%.
  • the present invention provides that the diazotising agent is nitrite salt or organic nitrite.
  • the nitrite salt or organic nitrite is selected from the group comprising ammonium nitrite, butyl nitrite, amyl nitrite, dicyclohexyl ammonium nitrite, ethyl nitrite, isoamyl nitrite, lithium nitrite, sodium nitrite, potassium nitrite, zinc nitrite and mixtures thereof.
  • the molar ratio of diazotising agent and compound of formula (II) is 1 : 1 to 2: 1.
  • the present invention provides that the phase transfer catalyst is selected from the group comprising quaternary ammonium salt, quaternary phosphonium salt and mixtures thereof. Further, the phase transfer catalyst is selected from the group comprising tetrabutylammonium bromide (TBAB), tetrabutylammonium chloride (TBAC), dodecyltrimethylammonium bromide (DOTAB), dodecyltrimethylammonium chloride (DTAC), dodecyldimethylammonium chloride (DDAC), benzyltriethylammonium chloride (TEBAC), tetraethylammonium bromide (TEAB), methyl tricapryl ammonium chloride, methyl tributyl ammonium chloride (MTBAC), methyl trioctyl ammonium chloride, hexadecyltributylphosphonium bromide and mixtures thereof.
  • the present invention provides that the molar ratio of chlorine gas and compound of formula (II) is 1 : 1.5 to 1 : 5.
  • the present invention provides that the compound of formula (I), formula (II) and formula (III), wherein Ri is selected from the group comprising methoxy, ethoxy, propoxy, butoxy and R2 is selected from the group comprising methyl, ethyl, n-propyl, isopropyl or butyl.
  • the compound of formula (I) is 4-methoxycarbonyl 2-methyl-thiophene-3- sulphonyl chloride.
  • phase-transfer catalyst refers to a catalyst that facilitates the transition of reactant from one phase to another phase where reaction occurs.
  • step (i) the diazotising agent is dropped into the reaction mixture of compound of formula (II) in an acidic medium at a temperature in the range of 0 to 10°C, preferably 0 to 5°C.
  • the reaction progress was monitored by HPLC to obtain compound of formula (III).
  • step (ii) and step (iii) carried out at a temperature in the range of 20 to 40°C.
  • the organic solvent may comprise one or more of a polar aprotic water immiscible solvent, in which solubility of sulphur dioxide is high enough to carry out the reaction, like the solvent of 1,2-di chloroethane, di chloromethane and mixture thereof.
  • the metal catalyst and the phase transfer catalyst were added to the solution of sulphur dioxide in the organic solvent.
  • the metal catalyst is selected from the group comprising salt of copper (I), salt of copper (II) and mixtures thereof.
  • copper (I) chloride or copper (II) chloride is used as metal catalyst, preferably copper (II) chloride is used as a metal catalyst.
  • the molar ratio of metal catalyst and compound of formula (II) is 1 : 10 to 1 : 100. In particular, the molar ratio of metal catalyst and compound of formula (II) is 1 : 10 to 1 : 50.
  • the chlorine gas is the cheapest reagent, easily available and producing minimum waste in chlorination processes.
  • the only by-product of the reaction of the present invention is hydrogen chloride.
  • the amount of the chlorine gas needed for production with maximum yield mainly is the function of three parameters:
  • the molar ratio of chlorine gas and compound of formula (II) is 1 : 1.5 to 1 : 5. In particular, the molar ratio of chlorine gas and compound of formula (II) is 1 : 1.5 to 1 : 2.5.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé de préparation de chlorure de 4-alcoxy carbonyl thiophène 3-sulfonyle substitué de formule (I), connu en tant qu'intermédiaires pour des principes actifs en agriculture, en particulier utilisés pour la préparation d'un composé actif herbicide de formule (X).
PCT/IL2024/050974 2023-10-03 2024-10-01 Procédé de préparation de chlorure de thiophène 3-sulfonyle substitué Pending WO2025074365A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CNPCT/CN2023/123085 2023-10-03
CN2023123085 2023-10-03

Publications (1)

Publication Number Publication Date
WO2025074365A1 true WO2025074365A1 (fr) 2025-04-10

Family

ID=93291877

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IL2024/050974 Pending WO2025074365A1 (fr) 2023-10-03 2024-10-01 Procédé de préparation de chlorure de thiophène 3-sulfonyle substitué

Country Status (1)

Country Link
WO (1) WO2025074365A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001005788A1 (fr) 1999-07-15 2001-01-25 Bayer Aktiengesellschaft Thien-3-yl-sulfonylamino(thio)carbonyl-triazolin(thi)ones substituees
CN109265436A (zh) * 2018-11-29 2019-01-25 常州沃腾化工科技有限公司 一种4-甲氧羰基-2-甲基噻吩-3-磺酰氯的合成方法
CN111732568A (zh) * 2020-06-23 2020-10-02 北京怡力生物科技有限公司 一种4-甲氧基羰基-2-甲基噻吩-3-磺酰氯的合成方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001005788A1 (fr) 1999-07-15 2001-01-25 Bayer Aktiengesellschaft Thien-3-yl-sulfonylamino(thio)carbonyl-triazolin(thi)ones substituees
CN109265436A (zh) * 2018-11-29 2019-01-25 常州沃腾化工科技有限公司 一种4-甲氧羰基-2-甲基噻吩-3-磺酰氯的合成方法
CN111732568A (zh) * 2020-06-23 2020-10-02 北京怡力生物科技有限公司 一种4-甲氧基羰基-2-甲基噻吩-3-磺酰氯的合成方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ROSSY, P.A. ET AL.: "Aromatization of dihydrothiophenes. Thiophenesaccharin: a sweet surprise", THE JOURNAL OF ORGANIC CHEMISTRY, vol. 45, no. 4, 1980, pages 617 - 620, XP055817029, ISSN: 0022-3263, Retrieved from the Internet <URL:https://pubs.acs.org/doi/pdf/10.1021/jo01292a012> DOI: 10.1021/jo01292a012 *

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