WO2004000779A1 - Procede pour produire des derives d'ester phenyloxocarboxylique - Google Patents

Procede pour produire des derives d'ester phenyloxocarboxylique Download PDF

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WO2004000779A1
WO2004000779A1 PCT/JP2003/007814 JP0307814W WO2004000779A1 WO 2004000779 A1 WO2004000779 A1 WO 2004000779A1 JP 0307814 W JP0307814 W JP 0307814W WO 2004000779 A1 WO2004000779 A1 WO 2004000779A1
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group
general formula
producing
acid
phenyloxocarboxylic
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Taichi Shintou
Isamu Itoh
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Fujifilm Finechemicals Co Ltd
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Fujifilm Finechemicals Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/02—Formation of carboxyl groups in compounds containing amino groups, e.g. by oxidation of amino alcohols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/22—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound oxygen atoms
    • C07C311/23—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound oxygen atoms having the sulfur atoms of the sulfonamide groups bound to acyclic carbon atoms
    • C07C311/27—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound oxygen atoms having the sulfur atoms of the sulfonamide groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing rings
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/22—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound oxygen atoms
    • C07C311/29—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound oxygen atoms having the sulfur atom of at least one of the sulfonamide groups bound to a carbon atom of a six-membered aromatic ring
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
    • C07D209/32—Oxygen atoms
    • C07D209/34—Oxygen atoms in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
    • C07D233/30—Oxygen or sulfur atoms
    • C07D233/32—One oxygen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
    • C07D317/60—Radicals substituted by 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
    • C07D409/06—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 carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/04—Systems containing only non-condensed rings with a four-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • the present invention relates to a method for producing a phenyloxocarboxylic acid ester derivative which is an important intermediate in the production of medicines, agricultural chemicals, fragrances, and the like.
  • Phenyloxocarboxylic acid ester derivatives have long been useful in the fields of medicine, agricultural chemicals, fragrances, and the like, and have become important key compounds particularly as pharmaceuticals or intermediates thereof.
  • These production methods include a method in which an aromatic compound and a carboxylic anhydride are converted into phenyloxobutenoic acid by a free-delta-ruff reaction in the presence of aluminum chloride, and then esterification is performed using an alkylating agent (J. Am. Chem. M. Soc., (65) 1943, 1572-15776; J. Org. Chem., (23) 1958, 633; J. Chem. Soc. C, 1968. , 893-900) have been used for a long time.
  • An object of the present invention is to provide a production method capable of stably supplying a phenyloxocarboxylic acid ester derivative which is useful as an intermediate of a medicine, a pesticide, a fragrance or the like at low cost and high purity on an industrial scale. .
  • the present inventor has conducted intensive studies and researches to achieve the above object, and as a result, has found the following method, and has accomplished the present invention.
  • the present invention is a method for producing a fenoxo-oxo sulfonic acid ester derivative having the following constitution.
  • R 1 R5 each independently represents a hydrogen atom, an electron donating group or an electron withdrawing group. Further, adjacent groups of R 1 R 5 may be linked to form a ring.
  • R6 to 19, 110, Rll, and R12 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carbonyl group, or a sulfonyl group.
  • R 1 to R 9, X, and n are as defined above.
  • R 13 represents an alkyl group.
  • the general formula (I) has at least one electron-donating group and one electron-withdrawing group, and the sum of Hammett's substituent constants ⁇ values of R 1 to R 5 is 0 or more.
  • R 1 to R 9, X and n have the same meanings as described above.
  • the reaction used in the production method of the present invention falls in the category of the free delta reaction.
  • the scope of the present invention is by no means limited to this.
  • an aromatic hydrocarbon represented by the general formula (I) (hereinafter sometimes referred to as an aromatic hydrocarbon (I))
  • the reaction with the carboxylic anhydride derivative (II) represented by the formula (II) proceeds according to the following formula, and the phenyloxo carboxylic acid ester derivative ( III) is generated. Therefore, according to the method of the present invention, there is no need to provide a step of purifying intermediates during the reaction by extracting and crystallization, and the aromatic hydrocarbon (I) and the carboxylic anhydride derivative ( ⁇ ) can be simultaneously used. Alternatively, the target substance can be easily produced in one step by continuously adding the compound to the reaction system. Of course, after the reaction is completed, it is optional to provide a purification step to make the target product highly pure.
  • the amount of acyl cations generated in the reaction system is small, and the generation of phenyloxocarboxylic acid is In the method (1), the target compound, phenyloxocarboxylic acid ester, must be further esterified.
  • R 1 to R 5 are as defined above.
  • R 1 to R 5 are each independently a hydrogen atom, an electron donating group. Or represents an electron-withdrawing group.
  • at least one of R 1 to R 5 is an electron donating group.
  • the electron donating group is not particularly limited as long as it is a substituent having an electron donating action.
  • a linear alkyl group such as methyl, ethyl, n_otatyl, n-dodecyl; i-propyl, ert_butyl, iso-decyl
  • a cyclic alkyl group such as pentyl, hexyl and the like; an alkenyl group such as vinyl, arylene, butenyl and pentenyl; an alkynyl group such as ethynyl, 1-propyl and 1-butynyl;
  • Aryl groups such as naphthyl; alkoxy groups such as methoxy, ethoxy, tert-butoxy, n-hexyloxy and n-dodecinoleoxy; aryloxy groups such as phenoxy and naphthyloxy; hydroxyl groups; methylamino, ethylamin
  • a group via a hetero atom is mentioned, and specific examples thereof include an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, and an amino group. No. Among them, an alkoxy group having 1 to 8 carbon atoms is more preferable, and a methoxy group and an ethoxy group are particularly preferable.
  • the electron-withdrawing group is not particularly limited as long as it is a substituent having an electron-withdrawing action.
  • examples thereof include a halogen atom such as chlorine, bromine and iodine; a nitro group; a cyano group; a fluoroalkyl group such as trifluoromethyl; — Snorrephonyl groups such as propinoles norehonire, huenoresolehonore, etc .; canolepoenole groups such as acetinole, n-hexinolecanoleponinole, benzinole, naphthoinole, etc .; power norebamoisle, N-fueninorenomorebamoinore Sulfamoyl groups such as sulfamoyl, N-methylsulfamoyl, N, N-getylsulfamoyl, etc .; heterocyclic residues such as 2-pyr
  • halogen atom a sulfamoyl group, a sulfamoyl group, and the like are used, and a halogen atom is more preferable.
  • These electron donating group and electron withdrawing group may further have a substituent, and the substituent is not particularly limited as long as it does not participate in the reaction.
  • groups adjacent to R 1 to R 5 may be linked to form a ring.
  • cyclobutane, cyclopentene, cyclohexane, 1,3-dioxo Examples include solan, 1,3-oxazolan, 1,3-oxazolan-1-one, and 2-pyrrolidinone.
  • R 1 to R 5 are preferably a hydrogen atom or an electron donating group.
  • a combination having at least one electron-withdrawing group and one electron-donating group is also preferable.
  • the combination in this case is not particularly limited as long as the sum of the Hammett's substituent constant ⁇ values of R 1 to R 5 is 0 or more.
  • an alkoxy group and a halogen atom, and an alkoxy group and a sulfamoyl group are used. And alkoxy groups and rubamoyl groups.
  • the combination of Hammett's substituent constant ⁇ values of R 1 to R 5 is 0.5 or more.
  • X is one C (R 1 0) (R 1 1) -, one o-, one S-, one S_ ⁇ 2 - or a N (R 1 2), - represents, n Is 0 or 1.
  • R 6 to R 9 and R 10, R ll, and R 12 each independently represent a hydrogen atom; methinole, ethynole, n-octynole, i-propynole, tert-butynole, iso-decyl, cyclopentyl, cyclohexyl
  • a linear or branched cyclic alkyl group such as xyl; an alkenyl group such as vinyl, aryl, butenyl or pentenyl; an anolequinyl group such as ethininole, 1-propyninole, and 1 phenyl; an aryl group such as phenyl or naphthyl; Alkoxy groups such as methoxy, ethoxy, tert-butoxy, n-hexynoleoxy, and n-dodecyloxy; aryloxy groups such as phenoxy and naphthyloxy; amino, methyl
  • Sulfolemoinyl groups such as canolebamoinole, N-phenylcarbamoyl, N, N-getylcarbamoyl; sulfamoyl groups such as sulfamoyl, N-methylsulfamoyl, N, N-getylsulfamoyl; Cyano group; ethylthio Alkylthio groups such as n_hexylthio and iso_tetradecylthio; arylthio groups such as phenylthio and naphthylthio; heterocyclic residues such as 2-pyridyl, 1-piperidyl, and 2-phenyl; chlorine and bromine Represents a halogen atom such as iodine.
  • R 6 and R 7, R 8 and R 9, and R 10 and R 11 may form a double bond in each combination to represent a methylene group, an oxo group, or an imino group.
  • a hydrogen atom Preferable are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkoxy group having 1 to 20 carbon atoms, and a halogen atom. More preferred are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a halogen atom. These groups may further have a substituent, and the substituent is not particularly limited as long as it does not participate in the reaction.
  • two groups of R 6 to R 12 may be linked to form a ring structure.
  • the ring structure include saturated rings such as cyclopropane, cyclobutane, cyclopentane, and cyclohexane; Partially saturated rings such as cyclopropene, cyclobutene, cyclopentene, and cyclohexene; aromatic rings such as benzene and naphthalene; and ring structures such as heterocyclic rings such as tetrahydrothiophene, pyrrolidine, pyridine, pyrimidine, quinoline, and pyrrole. .
  • These ring structures It may be condensed with the nucleus carboxylic anhydride, spiro-bonded with the nucleus carboxylic anhydride, or may be cross-linked to the nucleus anhydride ruponic acid. These ring structures may further have a substituent, and the substituent is not particularly limited as long as it does not participate in the reaction.
  • n 0, it represents a single bond.
  • the amount of the carboxylic anhydride derivative ( ⁇ ) used in the present invention is usually 1 mol 1 or more per 1 mol of aromatic hydrocarbon (I), and is preferably in the range of 1 lmo 1 to 2 Omo 1.
  • R 13 represents an anoalkyl group such as methyl, ethyl, n-octyl, i-propynole, tert-butynole, iso-decinole, and n-octadecinole. It is preferably a straight-chain or branched alkyl group having 1 to 20 carbon atoms, and more preferably a straight-chain or branched lower alkyl group having 1 to 4 carbon atoms. These groups may further have a substituent, and the substituent is not particularly limited as long as it does not participate in the reaction.
  • R 14 is a hydrogen atom; an alkyl group such as methyl, ethyl, n-octynole, i-propyl, tert-butynole, iso-decinole, n-octadecyl, etc .; phenyl, naphthyl, etc.
  • Amino group hydroxyl group; amino, N-methynoleamino, N- (tert-butyl) amino, N- (n-decyl) amino, N-phenylamino, N, N-ethylamino, N, N- (di-amino) amino such as iso-propyl) amino, N, N-diphenylamino Group; or a hydroxylamino group.
  • These groups may further have a substituent, and the substituent is not particularly limited as long as it does not participate in the reaction.
  • any acid catalyst can be used as long as it is used for the Friedel-Crafts reaction.
  • Tetraclo-mouth aluminum salt 1-ethyl-3-methinolyl 1-imidazolym) Kisafluo-anchimonium salt, 1-ethyl-3-1-methyl-1H-imidazoli Trifluoromethanesulfonium salt, 1-butyl-3-methyl-11-imidazolym-tetrachloroaluminum salt, 1-butyl-3-methyl-1-amino-1-imidazolylhexafluorophosphonium salt, 1 Monobutyl-2,3-dimethyl-1-imidazolium / tetrachloroanoreminium salt, etc.).
  • aluminum chloride stannic chloride, boron trifluoride, bismuth chloride, ferric chloride, hafnium triflate, scandium triflate, zeolite, zeolite zeolite, and ionic liquid are more preferable.
  • the amount of the acid catalyst used in the present invention is not limited as long as it is 0.01 mol or more per 1 mol of the aromatic hydrocarbon represented by the general formula (I). In such a case, it is preferable that 1. O mo] to 10. Preferably it is 2.0 to 3.5 mol, and in the case of other acid catalysts it is preferably 0.01 to 0.5 mol, more preferably 0.02 to 0.2 mol.
  • alkylating agents used in the present invention are commercially available, easily available, and can be used as they are. Specifically, the following are mentioned.
  • Halogenated quinolenes Chloroptinole, bromomethinole, promochinole, promopropinole, promobutinole, methinolide iodide, trimethyl thiol, butyl iodide pill, butyl iodide and the like.
  • Sulfites dimethyl sulfite, getyl sulfite, dipropyl sulfite, dibutyl sulfite and the like.
  • Phosphate esters trimethyl phosphate, triethyl phosphate, tripropyl phosphate, triptyl phosphate, triotatyl phosphate, tris (2-ethylhexyl) phosphate, tris (2-chloroethyl) phosphate, phosphoric acid Tris (2-chloro-1-methylethyl), dimethyl phosphate, getyl phosphate, dipropyl phosphate, dibutyl phosphate, etc.
  • Phosphite esters trimethyl phosphite, triethyl phosphite, tripropyl phosphite, triptyl phosphite, dimethyl phosphite, getyl phosphite, dipropyl phosphite, dipropyl phosphite, dibutyl phosphite Diradiryl phosphate and the like.
  • Carbonates dimethyl carbonate, getyl carbonate, dipropyl carbonate, dibutyl carbonate and the like.
  • Ortho acid esters methyl orthoformate, ethyl orthoformate, propyl orthoformate, butyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, tripropyl orthoformate, triptyl orthoformate, triethyl orthopropionate, getyl orthoformate, Trimethyl orthovalerate, tetraethyl orthoketo, tetrabutyl orthoketo, tetramethyl orthotitanate, tetraethyl orthotitanate, tetrapropyl orthotitanate, tetrabutyl orthotitanate and the like.
  • alkylating agents preferred are sulfates and sulfonates, and more preferred are dimethyl sulfate, getyl sulfate, methinole benzenesnolephonate, ethinole benzenesnolenate, methyl monotoluene oleate, p- Ethyl toluenesulfonate, methyl methanesulfonate, ethyl methanesulfonate, methyl trifluoromethanesulfonate, Ethyl trifluoromethanesulfonate, particularly preferably sulfates, most preferably getyl sulfate.
  • the amount of the alkylating agent to be used is usually 0.5 mO 1 or more, preferably 0.5 to 2 Omo 1 and more preferably 1.0 to 1.0 with respect to the aromatic hydrocarbon (I) lmo 1. ⁇ ; L O. Omol, more preferably 1.'2 to 3.5mol.
  • a sufficient reaction rate can be obtained without using a reaction accelerator, but a reaction accelerator may be added.
  • Halogen compounds such as copper iodide, potassium iodide, iodine, copper bromide, and copper chloride; and quaternary compounds such as tetra (n-butyl) ammonium bromide and tetra (n-butynole) ammonium bromide.
  • Examples include nitrile compounds such as ammonium salt, acetonitrile, propionitrile, and benzonitrile.
  • nitrile compounds such as ammonium salt, acetonitrile, propionitrile, and benzonitrile.
  • Preferred are copper iodide, tetra (n-butyl) ammonium monoxide, and acetonitrile, and more preferred are copper iodide and acetonitrile.
  • the amount of the reaction accelerator used is usually in the range of 0.001 to 0.1 mol per 1 mol of the aromatic hydrocarbon (I). It is preferably 0.001 to 0.05 mol, more preferably 0.001 to 0.1 mol.
  • the nitrile compound it is usually in the range of 0.001 to 2mo1, preferably 0.001 to 1mo1, more preferably 0 to 1 for the aromatic hydrocarbon (I) lmo1. .01 to 0.6 mol.
  • a reaction solvent may or may not be used, but any solvent which is generally inert to the reaction can be used.
  • Solvents that are inert to ordinary Friedel-Crafts reactions include the following.
  • Aliphatic halogenated hydrocarbon compounds dichloromethane, chloroform, carbon tetrachloride, dibromomethane, 1,2-dichloroethane and the like.
  • Ionic liquid 1-Ethyl-3-methyl-1H-imidazolium tetrachloroanoleminium salt, 1-Ethyl-13-methyl-1H-1 ⁇ midazolylhexafluorophosphonium salt, 1- 3-methyl-1-H-imidazolium hexamonal antimonium salt, 1-butyl-1-3-methynol-1-H-imidazolime hexaphonoleo-phosphonium salt, 1-ethynolae 3-methyl-1H-imidazolium trifinoleo Methane sulphonium salt, methyl imidazolium bis (trifluoromethane sulphone) imide salt, 1,2-dimethinolate 3-propylimidazo rim hexafluorophosphonium salt, trimethyl propyl ammonium salt Mutetrafluoroborate, tetra-n-ptinolephospho-dimethylbromide and the like.
  • solvents can be used alone or in combination of two or more as a reaction solvent.
  • benzene, nitrobenzene, dichloromethane, chlorophonolem and 1,2-dichloroethane are preferred, and benzene and dichloromethane are more preferred.
  • the amount of the reaction solvent to be used is generally within a range from 1 to 100 Om1, preferably from 5 to 50 Om1, with respect to the aromatic hydrocarbon (I) 0.1 mol1. Preferably 35 to: L5Om1.
  • the reaction temperature is usually in the range of 120 to 150 ° C, preferably in the range of 0 to 80 ° C, and more preferably in the range of 5 to 50 ° C.
  • the reaction time is usually 1 to 10 hours, and usually 1 to 4 hours.
  • the acid catalyst is decomposed or filtered, and then the organic layer is neutralized with a base such as sodium hydrogen carbonate to remove the excess carboxylic anhydride derivative (II). Further, after concentrating the solvent under reduced pressure, high-purity phenyloxocarboxylic acid esternole derivative can be obtained by crystallization by adding alcohol, hexane or the like.
  • the present invention relates to compounds represented by the above general formula (IV), for example, 4-phenyl-14-oxo-12-butanoic acid amides, 5-phenyl-5-oxo-12-pentenoic acid amides
  • Existing esters such as 4-phenyl-2-butanoic acid, 4-phenyl-2-butanoic acid, 4-phenyl-2-pentenehydroxamic acid, 4-phenyl-2-butane-1,4-dione, etc. It is particularly effective as a method for producing intermediates when synthesizing compounds that can be easily derived by functional group conversion of derivatives.
  • These compounds can be derived by various conventional methods after obtaining the phenyloxocarboxylate derivative according to the present invention and then directly or once withdrawn in the reaction system. In addition, these compounds are not limited to the above.
  • HPLC high performance liquid chromatography
  • reaction solution was added dropwise to 200 ml of a 1N-hydrochloric acid aqueous solution cooled to 0 ° C. to decompose excess aluminum chloride.
  • the mixture was extracted with 400 ml of ethyl acetate, and washed twice with 200 ml of a 1N aqueous hydrochloric acid solution.
  • the organic layer was extracted with 200 ml of a saturated aqueous solution of sodium hydrogen carbonate, and this operation was performed three times.
  • Table 1 shows the results of Examples 1 and 2 and Comparative Example 1.
  • the reaction time of Comparative Example 1 is the total reaction time of Step 1 and Step 2.
  • Example 1 the combination of 1,2-dimethoxybenzene, getyl sulfate, and 2,2-dimethyl-glutaric anhydride is shown in Table 4 below.
  • the synthesis was carried out under the same conditions as in Example 1 except for using a hydrocarbon, an alkylating agent and a sulfonic acid anhydride derivative, respectively.
  • Table 4 shows the results.
  • reaction solution was added dropwise to 200 ml of a 1 N aqueous solution of hydrochloric acid cooled to 0 ° C to decompose excess aluminum chloride. After liquid separation, the organic layer was washed with 100 ml of 10% aqueous sodium bicarbonate to remove excess 2,2-dimethyl-glutaric anhydride. After evaporating the solvent under reduced pressure, add 20 Om1 of concentrated aqueous ammonia and operate at 0 ° C for 1 hour, extract with 20 Om1 of ethyl acetate, evaporate the solvent under reduced pressure, and then add 5 ml of ethanol.
  • reaction solution was added dropwise to 20 Oml of a 1N aqueous hydrochloric acid solution cooled to 0 ° C. to decompose excess aluminum chloride.
  • organic layer was washed with 10% aqueous sodium bicarbonate (20 Om 1) to remove excess 2,2-dimethyl-glutaric anhydride, and then 42.9 g of sodium iodide (0.26 mol 1) was added to the organic layer.
  • trimethyl silane chloride 31.1 g (0.286 mol 1) were added and heated.
  • the fluoro-niloxo carboxylate derivative useful as an intermediate of pharmaceuticals, agricultural chemicals, fragrances, etc. can be stably supplied on an industrial scale in a short time, at low cost and with high purity. It is possible to industrially have extremely high practicality.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé pour produire des dérivés d'ester phényloxocarboxylique, ledit procédé consistant à faire réagir un hydrocarbure aromatique avec un dérivé d'anhydride d'acide carboxylique en présence d'un catalyseur acide et d'un agent d'alkylation. Ledit procédé permet de produire de manière stable, rapidement, à faible coût, à l'échelle industrielle, des dérivés d'ester d'acide phényloxocarboxylique présentant une pureté élevée.
PCT/JP2003/007814 2002-06-20 2003-06-19 Procede pour produire des derives d'ester phenyloxocarboxylique Ceased WO2004000779A1 (fr)

Priority Applications (2)

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AU2003244315A AU2003244315A1 (en) 2002-06-20 2003-06-19 Process for producing phenyloxocarboxylic ester derivative
JP2004515525A JP4436754B2 (ja) 2002-06-20 2003-06-19 フェニルオキソカルボン酸エステル誘導体の製造方法

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JP2002-180161 2002-06-20

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007204460A (ja) * 2006-02-06 2007-08-16 Air Water Inc インドールカルボン酸エステル類の製造方法
US20110160371A1 (en) * 2009-12-24 2011-06-30 Exxonmobile Research And Engineering Company Aromatic acylation with cyclic anhydride for plasticizer production
US8461684B2 (en) 2007-04-09 2013-06-11 President And Fellows Of Harvard College Cobalt nitride layers for copper interconnects and methods for forming them
WO2015037381A1 (fr) * 2013-09-13 2015-03-19 日本電気株式会社 Nouveau composé, électrolyte et batterie secondaire
WO2016152028A1 (fr) * 2015-03-25 2016-09-29 セイコーエプソン株式会社 Composition de formation de couche fonctionnelle, procédé de fabrication de composition de formation de couche fonctionnelle, procédé de fabrication d'élément el organique, dispositif el organique, et équipement électronique
US12509884B2 (en) 2006-07-11 2025-12-30 Välinge Innovation AB Mechanical locking of floor panels with a flexible bristle tongue

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53111033A (en) * 1977-03-08 1978-09-28 Sankyo Co Ltd 4-phenyl-4-oxolactic acid derivatives and their preparation
US4223013A (en) * 1978-12-29 1980-09-16 Syva Company Amitriptyline conjugates to antigenic proteins and enzymes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53111033A (en) * 1977-03-08 1978-09-28 Sankyo Co Ltd 4-phenyl-4-oxolactic acid derivatives and their preparation
US4223013A (en) * 1978-12-29 1980-09-16 Syva Company Amitriptyline conjugates to antigenic proteins and enzymes

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007204460A (ja) * 2006-02-06 2007-08-16 Air Water Inc インドールカルボン酸エステル類の製造方法
US12509884B2 (en) 2006-07-11 2025-12-30 Välinge Innovation AB Mechanical locking of floor panels with a flexible bristle tongue
US8461684B2 (en) 2007-04-09 2013-06-11 President And Fellows Of Harvard College Cobalt nitride layers for copper interconnects and methods for forming them
US20110160371A1 (en) * 2009-12-24 2011-06-30 Exxonmobile Research And Engineering Company Aromatic acylation with cyclic anhydride for plasticizer production
US8604114B2 (en) * 2009-12-24 2013-12-10 Exxonmobil Research And Engineering Company Aromatic acylation with cyclic anhydride for plasticizer production
WO2015037381A1 (fr) * 2013-09-13 2015-03-19 日本電気株式会社 Nouveau composé, électrolyte et batterie secondaire
JPWO2015037381A1 (ja) * 2013-09-13 2017-03-02 日本電気株式会社 新規化合物、電解液及び二次電池
WO2016152028A1 (fr) * 2015-03-25 2016-09-29 セイコーエプソン株式会社 Composition de formation de couche fonctionnelle, procédé de fabrication de composition de formation de couche fonctionnelle, procédé de fabrication d'élément el organique, dispositif el organique, et équipement électronique
JP2016181648A (ja) * 2015-03-25 2016-10-13 セイコーエプソン株式会社 機能層形成用組成物、機能層形成用組成物の製造方法、有機ｅｌ素子の製造方法、有機ｅｌ装置、電子機器

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AU2003244315A1 (en) 2004-01-06
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