WO2000018729A1 - Procede permettant de produire des alkylsulfonylbenzaldehydes - Google Patents

Procede permettant de produire des alkylsulfonylbenzaldehydes Download PDF

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Publication number
WO2000018729A1
WO2000018729A1 PCT/JP1999/005190 JP9905190W WO0018729A1 WO 2000018729 A1 WO2000018729 A1 WO 2000018729A1 JP 9905190 W JP9905190 W JP 9905190W WO 0018729 A1 WO0018729 A1 WO 0018729A1
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WIPO (PCT)
Prior art keywords
reaction
general formula
hydrogen peroxide
represented
producing
Prior art date
Application number
PCT/JP1999/005190
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English (en)
Japanese (ja)
Inventor
Hirokazu Kagano
Mikio Yamamoto
Koji Fujita
Original Assignee
Sumitomo Seika Chemicals Co., 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 Sumitomo Seika Chemicals Co., Ltd. filed Critical Sumitomo Seika Chemicals Co., Ltd.
Publication of WO2000018729A1 publication Critical patent/WO2000018729A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
    • C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides

Definitions

  • the present invention relates to a method for producing an alkylsulfonyl penzaldehyde. More specifically, the present invention relates to a method for producing alkylsulfonyl pentaldehydes useful as intermediates of pharmaceuticals. Background art
  • Conventional methods for producing alkylsulfonyl penzaldehydes include, for example, a method of oxidizing alkylthiobenzaldehyde with hydrogen peroxide in an acetic acid solvent.
  • the present invention has been made in view of the prior art, and has as its object to provide a method for industrially easily producing an alkylsulfonylpentaldehyde in a high yield.
  • the inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, by oxidizing alkylthiobenzaldehydes under specific pH conditions, alkylsulfonylbenzaldehydes can be selectively obtained in high yield. We found that we were able to do this and completed this invention.
  • R represents an alkyl group having 1 to 4 carbon atoms
  • R represents an alkyl group having 1 to 4 carbon atoms
  • R represents an alkyl group having 1 to 4 carbon atoms.
  • alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a tert-butyl group.
  • the alkylthiobenzaldehydes represented by the general formula (I) can be prepared, for example, by the method described in JP-A-5-331114, that is, by converting a halobenzaldehyde and an alkyl mercaptan into It can be easily obtained by reacting in a heterogeneous system in water or a mixed solvent of water and a water-insoluble organic solvent in the presence of a base and a quaternary ammonium salt catalyst.
  • the oxidation of the alkylthiobenzaldehyde represented by the general formula (I) is carried out, for example, by the reaction of the alkylthiobenzaldehyde represented by the general formula (I), a solvent, and p After mixing an acid for adjusting H and the like, the reaction can be performed by adding aqueous hydrogen peroxide to the obtained reaction mixture.
  • the amount of the aqueous hydrogen peroxide used is usually 1.5 to 10 molar equivalents, preferably 2 to 4 molar equivalents, based on the alkylthiobenzaldehydes represented by the general formula (I). It is preferable to adjust as follows.
  • the solvent examples include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, and the like.
  • Hydrocarbons such as hexane, cyclohexane and heptane; halogenated hydrocarbons such as dichloroethane, dichloromethane, and chloroform; aromatics such as benzene, toluene, xylene, cyclobenzene, dichlorobenzene and trichlorobenzene Group hydrocarbons; water and the like, which can be used alone or as a mixture of two or more.
  • ketones and alcohols are preferred, and acetone and methanol are more preferred, from the viewpoints of reaction selectivity and economy.
  • the amount of the solvent to be used is not particularly limited, but it is usually preferably from 100 to 100 parts by weight based on 100 parts by weight of the alkylthiobenzaldehyde represented by the general formula (I).
  • alkylthiobenzaldehydes are oxidized by adjusting the pH of the reaction solution.
  • the alkylthiobenzaldehyde represented by the general formula (I) is oxidized under the condition that the pH of the reaction solution is 2 or less
  • the alkylsulfonyl pentaldehyde represented by the general formula (II) is oxidized.
  • the pH of the reaction solution is 2 or less, preferably 1 or less from the viewpoint of reaction selectivity.
  • the pH of the reaction solution can be adjusted by adding an acid. Examples of the acid include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.
  • the amount of the acid used is usually the amount of the alkylthio compound represented by the formula (I). It is preferable that the amount is 1 to 100 parts by weight based on 100 parts by weight of ndusaldehyde.
  • the alkylthiobenzaldehyde represented by the general formula (I) is preferably oxidized in the presence of a catalyst, so that the reaction can proceed more smoothly.
  • the catalyst include sodium tungstate.
  • the amount of the catalyst used is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the alkylthiobenzaldehydes represented by the general formula (I).
  • the reaction conditions for oxidizing the alkylthiobenzaldehyde represented by the general formula (I) are not particularly limited.
  • the reaction temperature is usually about 0 to 100 ° C. It is desirable that the temperature be 20 to 70 ° C. If the reaction temperature is too low, the reaction rate is low. On the other hand, if it is too high, a side reaction occurs to cause a decrease in yield, which is not preferable.
  • the reaction atmosphere may be air or an inert gas such as nitrogen gas or argon gas. Since the reaction time varies depending on the reaction conditions and the like, it cannot be determined unconditionally, but is usually preferably about 1 to 10 hours.
  • the desired alkylsulfonyl pentaldehydes represented by the general formula (II) can be industrially easily obtained with a high yield.
  • the obtained alkylsulfonyl penzaldehydes can be isolated by conventional methods such as extraction, crystallization, and distillation.
  • alkylsulfonylbenzaldehyde represented by the general formula ( ⁇ ) obtained by the present invention examples include 2-methylsulfonylbenzaldehyde, 3-methylsulfonylbenzaldehyde, 4-methylsulfonylbenzaldehyde, 2-ethylsulfonyl Benzaldehyde, 3-ethylsulfonylbenzaldehyde, 4-ethylsulfonylbenzaldehyde, 2-n-propylsulfonylbenzaldehyde, 3-n-propylsulfonylbenzaldehyde, 4-n-propyls Ruphonylbenzaldehyde, 2-isopropylsulfonylbenzaldehyde, 3-isopropylsulfonylbenzaldehyde, 4-isopropylsulfonylbenzaldehyde, 2-n-butylsulfon
  • Example 1 the present invention will be described in more detail based on examples, but the present invention is not limited to only these examples.
  • Example 1
  • alkylsulfonylbenzaldehydes useful as intermediates of pharmaceuticals and the like can be obtained industrially easily and in high yield.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Procédé permettant de produire un alkylsulfonylbenzaldéhyde représenté par la formule générale (II), dans laquelle R représente alkyle C1-C4. Le procédé consiste à oxyder un alkylthiobenzaldéhyde représenté par la formule générale (I), dans laquelle R est tel que défini ci-dessus, au moyen d'une solution de peroxyde d'hydrogène aqueux dans un solvant à un pH égal ou inférieur à 2. Le procédé permet d'obtenir facilement, à l'échelle industrielle et avec un rendement élevé, un alkylsulfonylbenzaldéhyde utile, par exemple, comme intermédiaire de médicaments.
PCT/JP1999/005190 1998-09-30 1999-09-22 Procede permettant de produire des alkylsulfonylbenzaldehydes WO2000018729A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP10/278366 1998-09-30
JP10278366A JP2000103779A (ja) 1998-09-30 1998-09-30 アルキルスルホニルベンズアルデヒド類の製造方法

Publications (1)

Publication Number Publication Date
WO2000018729A1 true WO2000018729A1 (fr) 2000-04-06

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1999/005190 WO2000018729A1 (fr) 1998-09-30 1999-09-22 Procede permettant de produire des alkylsulfonylbenzaldehydes

Country Status (3)

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JP (1) JP2000103779A (fr)
CN (1) CN1187323C (fr)
WO (1) WO2000018729A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103819371A (zh) * 2012-11-16 2014-05-28 中国科学院大连化学物理研究所 一种对甲砜基苯甲醛的合成方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010055744A1 (fr) 2008-11-17 2010-05-20 住友精化株式会社 Composé sulfone
WO2010143578A1 (fr) * 2009-06-09 2010-12-16 住友精化株式会社 Procédé de préparation de composés d'alkyl-sulfone
CN102675167B (zh) * 2012-05-16 2014-06-25 山东汉兴医药科技有限公司 一种对甲砜基苯甲醛的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6429352A (en) * 1987-07-03 1989-01-31 Oreal Novel polycyclic aromatic compound, medicine and cosmetic composition
JPH01113361A (ja) * 1987-09-22 1989-05-02 Hoechst Ag オキシエチルメルカプト‐ベンズアルデヒド及びそれらの酸化生成物の製法
JPH08143534A (ja) * 1994-11-24 1996-06-04 Sumitomo Seika Chem Co Ltd アルキルフェニルスルホンの製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6429352A (en) * 1987-07-03 1989-01-31 Oreal Novel polycyclic aromatic compound, medicine and cosmetic composition
JPH01113361A (ja) * 1987-09-22 1989-05-02 Hoechst Ag オキシエチルメルカプト‐ベンズアルデヒド及びそれらの酸化生成物の製法
JPH08143534A (ja) * 1994-11-24 1996-06-04 Sumitomo Seika Chem Co Ltd アルキルフェニルスルホンの製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103819371A (zh) * 2012-11-16 2014-05-28 中国科学院大连化学物理研究所 一种对甲砜基苯甲醛的合成方法
CN103819371B (zh) * 2012-11-16 2016-05-04 中国科学院大连化学物理研究所 一种对甲砜基苯甲醛的合成方法

Also Published As

Publication number Publication date
CN1321146A (zh) 2001-11-07
CN1187323C (zh) 2005-02-02
JP2000103779A (ja) 2000-04-11

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