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WO2003043977A1 - Procede de preparation de sulfones de geranyle aryle - Google Patents

Procede de preparation de sulfones de geranyle aryle Download PDF

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Publication number
WO2003043977A1
WO2003043977A1 PCT/JP2002/011904 JP0211904W WO03043977A1 WO 2003043977 A1 WO2003043977 A1 WO 2003043977A1 JP 0211904 W JP0211904 W JP 0211904W WO 03043977 A1 WO03043977 A1 WO 03043977A1
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WO
WIPO (PCT)
Prior art keywords
formula
represented
aryl
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.)
Ceased
Application number
PCT/JP2002/011904
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English (en)
Japanese (ja)
Inventor
Shinzo Seko
Noriyuki Doi
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.)
Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Filing date
Publication date
Application filed by Sumitomo Chemical Co Ltd filed Critical Sumitomo Chemical Co Ltd
Publication of WO2003043977A1 publication Critical patent/WO2003043977A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides

Definitions

  • the present invention relates to a method for producing geranylaryl sulfone, which is a raw material for vitamin A derivatives and various terpene compounds used as pharmaceuticals, feed additives, food additives, and the like.
  • arylsulfonyl chloride which is already less expensive than arylsulfinate, is reduced in an aqueous solvent to produce arylsulfinate in the system, and without isolation
  • geranylyaryl sulfone represented by the following formula (4) can be obtained in one pot (Japanese Patent Application Laid-Open No. 2001-218386). No. 0).
  • This method gives geranyl aryl sulfone (4), even if the aqueous solvent used in the reduction step of aryl aryl sulfoxide is present during the subsequent reaction with aryl halide compound (3).
  • the present inventors have conducted intensive studies to achieve a further improvement in the yield, and as a result, reacted the arylsulfinate with the aryl halide compound (3) in the presence of a phase transfer catalyst and an inorganic salt. As a result, they have found that the yield is improved, and have completed the present invention. Disclosure of the invention
  • Equation (3) [In the formula, X represents a halogen atom, and a wavy line represents either one of the EZZ geometric isomers or a mixture thereof.]
  • Ar represents an aryl group which may have a substituent, and M represents sodium or potassium]
  • phase transfer catalyst selected from a quaternary ammonium iodide salt, a quaternary phosphonium iodide salt or a sulfonium iodide salt, and an inorganic salt, or
  • phase transfer catalyst selected from salts, alkali metal halides and inorganic salts,
  • Ar represents an aryl group which may have a substituent
  • the substituent Ar in the compounds represented by the formulas (1), (2) and (4) of the present invention represents an aryl group which may have a substituent, and the aryl group is a phenyl group or a naphthyl group. and the like, as the substituent, Ji ⁇ C 5 or branched al kill group (e.g., methyl, Echiru, n - propyl, i- propyl, n- butyl, t-heptyl, n- pentyl group ), A C ⁇ Cs linear or branched alkoxy group (eg, methoxy, ethoxy, n-propoxy, i-propoxy, n-butyloxy, t-butyloxy, n-, t-, neo-pentyloxy) Group), a halogen atom, a nitro group, and the like.
  • Ji ⁇ C 5 or branched al kill group e.g., methyl, Echiru,
  • phenyl, naphthyl, 0-tolyl, m-tolyl, p-tolyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, o-clohpheninole, m-clohfener Nore, p-black mouth, o-bromophenyl, m-bromophenyl, p-bromophene, 0-eodophenyl, m-edofenore, p-eodofenore, 0-fuenoreno, m— Examples include fuoreno-rofenore, p-funore-norofenore, o-nitropheninole, m-nitropheninole, and p-nitrophenyl.
  • the substituent X in the aryl halide compound represented by the formula (3) represents a halogen atom, and specific examples include a chlorine atom, a bromine atom and an iodine atom.
  • the arylsulfinic acid salt used in the present invention can be obtained, for example, by reducing an arylsulfuric acid mouth chloride represented by the formula (1).
  • the reduction reaction is carried out in the presence of a reducing agent and a base. It is preferable to carry out in an aqueous solvent.
  • a sulfite or a hydrogen sulfite is preferable, and specific examples thereof include sodium sulfite, potassium sulfite, sodium hydrogen sulfite, and hydrogen sulfite.
  • the amount used is usually in the range of 1 to 2.5 mol times, preferably about 102 to 2.00 mol times, relative to arylsulfonyl chloride (1).
  • the coexisting base is preferably an alkali metal hydroxide, an alkali metal carbonate, an alkali metal bicarbonate, and the like. Specifically, sodium hydroxide, potassium hydroxide , Sodium carbonate, carbon dioxide lime, sodium hydrogen carbonate, hydrogen hydride, etc.
  • the amount used is usually in the range of about 1 to 5 moles, preferably about 1.02 to 2.50 moles, per mole of arylsulfoylc mouth ride (1).
  • the reaction temperature is usually in the range of 0 ° C to 100 ° C, but preferably in the range of about 20 ° C to 70 ° C.
  • the reaction time is usually in the range of 1 hour to 24 hours.
  • the reaction mixture may be isolated by concentration or the like.
  • the geranyl aryl sulfone represented by is obtained.
  • the amount of the arylhalide compound (3) to be added is usually in the range of about 0.3 to 1.2 mol times, preferably about 0.7 to 1 mol times, relative to the arylsulfoylc mouth ride (1). You.
  • the reaction is preferably carried out in the presence of a phase transfer catalyst, in the presence of an inorganic salt or the like, and in a water-hydrophobic organic solvent two-phase system or only an aqueous solvent.
  • the hydrophobic organic solvent When performed in a two-phase system, the hydrophobic organic solvent includes hydrocarbon solvents such as n-hexane, n-heptane, cyclohexane, benzene, toluene, and xylene, 1-chlorobutane, 1,2-dichloroethane, Halogen solvents such as benzene, onoletodichlorobenzene, trifluoromethylbenzene, etc .; carbonyl solvents such as methyl isobutyl ketone, methyl ethyl ketone, methyl acetate, and ethyl acetate; etc. And ether solvents such as methyl t-butyl ether.
  • hydrocarbon solvents such as n-hexane, n-heptane, cyclohexane, benzene, toluene, and xylene, 1-chlorobutane, 1,2-dichloroethan
  • phase transfer catalyst used examples include quaternary ammonium salts, quaternary phosphonium salts, and sulfonium salts.
  • quaternary ammonium salts include tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetrapentylammonium chloride, tetrahexylammonium chloride, and tetrahexylammonium chloride.
  • Tetraheptylammonium chloride Tetraoctylammonium chloride, Trioctylmethylammonium chloride, Tetradecylammonium chloride, Tridecylmethylammonium chloride, Didecyldimime chloride, Diammonium chloride, Tetradodecyl chloride Ammonium, Shiodii Tridodecylmethylammonium, Didodecyldimethylammonium chloride, Dodecinoletrimethyl chloride Ammonia, Hidodedecyltriethylammonium, Hidanitetradecyltrimethylammonium, Hidanitetratetrahexadecylammonium, Hidanihexadecyltrimethylammonium, Hexadecyldimethylethyl chloride Ammonia, tetraoctadecylammonium chloride, octadecyltrimethylammonium chloride
  • Examples of the quaternary phosphonium salts include, for example, Shiridani tributylmethylphosphonium, Shiridani triethylmethylphosphonium, Shiridani methyltriphenoxyphosphonium, Shiridani butyltriphenylphosphonium, and Salt Tetrabutylphosphonium chloride, benzyltriphenylphosphonium chloride, tetraoctylphosphochloride chloride, hexadecyltrimethylphosphonium chloride, hexadecyltributylphosphonium chloride, chloride Compounds obtained by converting the oxadecyldimethylethylphosphonium chloride, the tetraphenylphosphonium chloride, or the chloride salt thereof into the corresponding bromide salt, iodide salt, or hydrogen sulfate salt, respectively.
  • sulfonium salt examples include, for example, sodium chloride benzylmethylethylsulfonium, benzyldimethylsulfonyl chloride, sodium benzylbenzylethylsulfonium, dibutylmethylsulfonium chloride, trimethylsulfonyl chloride And triethylsulfonium chloride, tributylsulfonium chloride, or compounds in which these chloride salts have been converted to the corresponding bromide, iodide, or hydrogen sulfate salts, respectively.
  • phase transfer catalysts iodide salts are preferred, and quaternary ammonium iodide is particularly preferred.
  • a hydrogen sulfate salt, chloride salt or bromide salt it is preferable that an alkali metal iodide such as sodium iodide or potassium iodide coexist.
  • phase transfer catalyst and the alkali metal iodide used are It is usually in the range of about 0.001 to 0.2 mol, preferably about 0.01 to 0.1 mol, per mol of the halide compound (3).
  • the addition of an inorganic salt is effective for reducing the amount of use of a phase transfer catalyst, particularly expensive quaternary ammonium iodide, or for improving the reactivity.
  • inorganic salts examples include alkali metal or alkaline earth metal salt salts or bromide salts. Specifically, for example, sodium chloride, sodium chloride, sodium bromide, odor, etc. Potassium chloride, calcium chloride, calcium bromide, Shiridani magnesium, magnesium bromide and the like.
  • the amount of strong inorganic salt used also depends on the amount of aqueous solvent used in the previous step. The content is usually in the range of 20 to 300% by weight, preferably 50 to 200% by weight, based on the aryl halide compound (3).
  • the reaction temperature is usually in the range of 30 ° C to 110 ° C, preferably in the range of about 50 ° C to 100 ° C.
  • the reaction time is usually in the range of 1 hour to 24 hours.
  • geranylyaryl sulfone (4) can be produced with a high yield from an inexpensive arylsulfoylc mouth ride in one pot.
  • This method is industrially advantageous because inexpensive raw materials can be used, and the amount of phase transfer catalysts, especially expensive quaternary ammonium iodide, can be reduced, and the product can be obtained in a high yield using only an aqueous solvent. It is a way.

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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

L'invention concerne un procédé de préparation de sulfones de géranyle aryle représentés par la formule générale (4) [dans laquelle Ar représente aryle facultativement substitué; et la ligne ondulée représente l'un des isomères géométriques E/Z ou un mélange des deux], caractérisé par la réaction d'un halogénure d'allyle représenté par la formule générale (3) [dans laquelle X représente halogéno; et la ligne ondulée a la notation ci-définie] avec un sel d'acide arylsulfinique en la présence d'un catalyseur à transfert de phase et d'un sel inorganique.
PCT/JP2002/011904 2001-11-19 2002-11-15 Procede de preparation de sulfones de geranyle aryle Ceased WO2003043977A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2001352799 2001-11-19
JP2001-352799 2001-11-19
JP2002241512 2002-08-22
JP2002-241512 2002-08-22

Publications (1)

Publication Number Publication Date
WO2003043977A1 true WO2003043977A1 (fr) 2003-05-30

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PCT/JP2002/011904 Ceased WO2003043977A1 (fr) 2001-11-19 2002-11-15 Procede de preparation de sulfones de geranyle aryle

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WO (1) WO2003043977A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006078833A3 (fr) * 2005-01-21 2006-11-16 Janssen Pharmaceutica Nv Utilisation de nouveaux derives de la coumarine comme agents d'ouverture de canaux ioniques
CN103694153A (zh) * 2013-12-20 2014-04-02 华南理工大学 肉桂酸与芳基亚磺酸盐反应合成烯基砜类化合物的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63250364A (ja) * 1987-04-06 1988-10-18 Kuraray Co Ltd ゲラニルフエニルスルホンの製造方法
JPS63250363A (ja) * 1987-04-06 1988-10-18 Kuraray Co Ltd シクロゲラニルフエニルスルホンの製造方法
JP2001213860A (ja) * 2000-02-01 2001-08-07 Sumitomo Chem Co Ltd アリールアリ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
JPS63250364A (ja) * 1987-04-06 1988-10-18 Kuraray Co Ltd ゲラニルフエニルスルホンの製造方法
JPS63250363A (ja) * 1987-04-06 1988-10-18 Kuraray Co Ltd シクロゲラニルフエニルスルホンの製造方法
JP2001213860A (ja) * 2000-02-01 2001-08-07 Sumitomo Chem Co Ltd アリールアリルスルホンの製造方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006078833A3 (fr) * 2005-01-21 2006-11-16 Janssen Pharmaceutica Nv Utilisation de nouveaux derives de la coumarine comme agents d'ouverture de canaux ioniques
US7662975B2 (en) 2005-01-21 2010-02-16 Janssen Pharmaceutica, Nv Coumarin derivatives as ion channel openers
US8067619B2 (en) 2005-01-21 2011-11-29 Janssen Pharmaceutica N.V. Coumarin derivatives as ion channel openers
CN103694153A (zh) * 2013-12-20 2014-04-02 华南理工大学 肉桂酸与芳基亚磺酸盐反应合成烯基砜类化合物的方法
CN103694153B (zh) * 2013-12-20 2016-01-20 华南理工大学 肉桂酸与芳基亚磺酸盐反应合成烯基砜类化合物的方法

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