[go: up one dir, main page]

WO2006013920A1 - Ester de 2-substitué-3-(4-tétrahydropyranyle)-3-oxopeopanoïque et procédé pour le produire - Google Patents

Ester de 2-substitué-3-(4-tétrahydropyranyle)-3-oxopeopanoïque et procédé pour le produire Download PDF

Info

Publication number
WO2006013920A1
WO2006013920A1 PCT/JP2005/014289 JP2005014289W WO2006013920A1 WO 2006013920 A1 WO2006013920 A1 WO 2006013920A1 JP 2005014289 W JP2005014289 W JP 2005014289W WO 2006013920 A1 WO2006013920 A1 WO 2006013920A1
Authority
WO
WIPO (PCT)
Prior art keywords
tetrahydrovinyl
formula
oxopropanoate
represented
group
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/JP2005/014289
Other languages
English (en)
Japanese (ja)
Inventor
Shigeyoshi Nishino
Kenji Hirotsu
Hidetaka Shima
Keiji Iwamoto
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.)
Ube Corp
Original Assignee
Ube Industries 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 Ube Industries Ltd filed Critical Ube Industries Ltd
Priority to JP2006531536A priority Critical patent/JP4552939B2/ja
Publication of WO2006013920A1 publication Critical patent/WO2006013920A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D309/06—Radicals substituted by oxygen atoms

Definitions

  • the present invention relates to 2-substituted-3- (4-tetrahydrovinyl) -3-oxopropanoic acid ester and a process for producing the same, and more specifically, 2-halogeno-3- (4-tetrahydroviral). ) 3-oxopropanoic acid ester or 2-acyloxy-3- (4-tetrahydrobiral) -3-oxopropanoic acid ester and their production method.
  • 2-Substituted-3- (4-tetrahydrobiranyl) -3-oxopropanoic acid ester is a useful compound as a raw material for pharmaceuticals and agricultural chemicals and as a synthetic intermediate. Background art
  • the 2-substituted-3- (4-tetrahydrovinyl) -3-oxopropanoic acid ester of the present invention is a novel compound, and its existence and production method have never been known so far.
  • An object of the present invention is to solve the above-mentioned problems and to produce 2-substituted-3- (4 by a simple method.
  • the subject of the present invention is the general formula (1): [0007]
  • Y represents a halogen atom or an acyloxy group
  • R represents a hydrocarbon group
  • R 1 represents a hydrogen atom or a hydrocarbon group, and R is as defined above.
  • 2-Asiloxy-3- (4-tetrahydrovinyl) -3-oxopropanoic acid ester represented by Compound (lb) is preferred.
  • the subject of the present invention is further a 2-halogeno-3- (4-tetrahydropyral) -3-oxopropanoate represented by the above general formula (la), and a general formula (3):
  • the novel compound (1) of the present invention is represented by the general formula (1).
  • Y is a halogen atom or an acyloxy group, and specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a chlorine atom and a bromine atom are preferred.
  • R 1 in the acyloxy group is a hydrogen atom or a hydrocarbon group.
  • a hydrogen atom methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl Group, octyl group, nonyl group, decyl group and the like alkyl group having 1 to 12 carbon atoms; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclonyl group Group, cycloalkyl group having 3 to 12 carbon atoms such as cyclodecyl group; benzyl group, Forces such as aralkyl groups such as a netyl group; aryl groups such as a phenyl group, a tolyl group, a xylyl group and a naphthyl group, preferably a hydrogen atom, an alkyl group having 1 to 6 carbon
  • R is a hydrocarbon group. Specifically, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, An alkyl group having 1 to 12 carbon atoms such as a ruthel group; a aralkyl group such as a benzyl group or a phenethyl group; a force such as an aryl group such as a phenyl group, a tolyl group, a xylyl group, or a naphthyl group; -6 alkyl groups, most preferably a methyl group or an ethyl group. These groups include various isomers.
  • the compound (la) represented by the formula (la) in which Y is a halogen atom is obtained by reacting the compound (2) with a halogenating agent.
  • the compound (2) used in the reaction of the present invention is represented by the general formula (2).
  • R has the same meaning as described above.
  • Compound (2) is represented by reaction process formula (1)
  • R is as defined above.
  • the halogenating agent used in the reaction of the present invention is not particularly limited as long as it is a halogenating agent capable of leading compound (2) to compound (1).
  • Fluorine fluoride such as hydrofluoric acid, pyridinium fluoride, N-fluorobis (trifluoromethyl) sulfonamide; chlorine molecule, phosphorus oxychloride, sulfuryl chloride, thiol chloride, N-chlorosuccinimide, Chlorinating agents such as 1,3-dichloro-5,5-dimethylhydantoin, pentasalt phosphorus, concentrated hydrochloric acid, perchloric acid t-butyl ester, copper chloride, iron chloride; bromine molecule, oxyodor Brominating agents such as phosphorus, sulfuryl bromide, thionyl bromide, N-bromosuccinimide, hydrobromic acid, copper bromide, iron bromide, etc .; iodizing agents such as iodine molecule, N-odosuccinimide, etc.
  • the amount of the halogenating agent to be used is preferably 0.5 to 2.0 mol, more preferably 0.8 to 1.5 mol, per 1 mol of compound (2).
  • the reaction of the present invention is carried out in the presence or absence of a solvent.
  • a solvent is not particularly limited as long as it does not inhibit the reaction.
  • aromatic hydrocarbons such as benzene, toluene and xylene; black benzene, dichlorobenzene, etc.
  • Halogenated aromatic hydrocarbons such as nitrobenzene, etc .
  • Halogenated aliphatic hydrocarbons such as methylene chloride and 1,2-dichloroethane
  • ⁇ , ⁇ -dimethylformamide, ⁇ , ⁇ -Amides such as dimethylacetamide
  • ethers such as diisopropyl ether, dioxane, cyclopropyl methyl ether
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone
  • Aromatic hydrocarbons, halogenated aliphatic hydrocarbons, ethers, more preferably aromatic hydrocarbons, Rogeni spoon aliphatic hydrocarbons are used. These solvents may be used alone or in combination of two or more.
  • the amount of the solvent to be used is appropriately adjusted depending on the uniformity and stirrability of the reaction solution, and is preferably 0 to 20 g, more preferably 0 to 5 g, relative to compound (2) lg.
  • the reaction of the present invention is carried out, for example, by mixing the compound (2) and the halogenating agent and stirring them. It is performed by a method such as adapting.
  • the reaction temperature at that time is preferably ⁇ 30 to 100 ° C., more preferably ⁇ 20 to 50 ° C., and the reaction pressure is not particularly limited!
  • the compound (la) is obtained by the above reaction of the present invention, and this is generally performed after the reaction, such as neutralization, extraction, filtration, concentration, distillation, recrystallization, crystallization, column chromatography, etc. Isolated and purified by appropriate methods.
  • the compound (la) represented by the formula (la) obtained by the present invention includes, for example,
  • the compound (lb) represented by the formula (lb) wherein Y is an acyloxy group is the compound (la) and the organic carboxylic acid compound (3 ) To react.
  • the organic carboxylic acid compound (3) used in the reaction of the present invention is represented by the general formula (3).
  • R 1 has the same meaning as described above.
  • Examples of the salt of the organic carboxylic acid compound (3) include, for example, alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as calcium salt; There are quaternary ammonia salts such as -um salt.
  • Examples of the organic carboxylic acid compound (3) used in the present invention include formic acid, acetic acid, propionic acid, butyric acid, 2-methylpropionic acid, valeric acid, hexanoic acid, bivalic acid, heptanoic acid, Octanoic acid, nonanoic acid, decanoic acid, cyclopentylcarboxylic acid, cyclohexylcarboxylic acid, cycloheptylcarboxylic acid, cyclooctylcarboxylic acid, benzoic acid and their sodium, potassium, calcium, and ammonium salts Or tetrabutyl ammonium salt, etc.
  • the amount of the compound (3) or a salt thereof used is preferably 0.
  • the reaction of the present invention is carried out in the presence of a base.
  • a base examples include tertiary amines such as triethylamine and tributylamine; pyridines such as pyridine, methylpyridine and dimethylaminopyridine. ; Alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; alkali metal carboxylates such as sodium acetate and potassium acetate; sodium methoxide and potassium methoxide Powers that can be used are preferably tertiary amines and pyridines.
  • Alkali metal carboxylates more preferably tertiary amines, particularly preferably triethylamine and triptylamin are used. In addition, you may use these bases individually or in mixture of 2 or more types.
  • the amount of the base to be used is preferably 0 to 10 mol, more preferably 1 mol, per 1 mol of compound (la). Preferably it is 0-5.0 mol.
  • the reaction of the present invention is preferably carried out in a solvent, and the solvent used is not particularly limited as long as it does not inhibit the reaction.
  • a solvent for example, water; amines such as trytylamine, tryptylamine and the like Pyridines such as pyridine, methylpyridine and dimethylaminopyridine; quinolines such as quinoline, isoquinoline and methylisoquinoline; amides such as ⁇ , ⁇ -dimethylformamide, ⁇ , ⁇ -dimethylacetamide and ⁇ -methylpyrrolidone Ureas such as ⁇ , ⁇ '-dimethylimidazolidinone; sulfoxides such as dimethyl sulfoxide; sulfones such as sulfolane; alcohols such as ⁇ -propyl alcohol and ⁇ -butyl alcohol; diisopropyl ether, dioxane, cyclohexane Ethers such as propyl methyl ether
  • the amount of the solvent to be used is appropriately adjusted depending on the uniformity and stirrability of the reaction solution, but is preferably 0.5 to 50 g, more preferably 1 to 20 g based on the compound (la) lg.
  • the reaction of the present invention is carried out, for example, by a method of mixing the compound (la), the compound (3) or a salt thereof, a base and a solvent and reacting them with stirring.
  • the reaction temperature at that time is preferably ⁇ 20 to 150 ° C., more preferably 0 to 120 ° C., particularly preferably 10 to 100 ° C., and the reaction pressure is not particularly limited!
  • the compound (lb) is obtained by the above reaction of the present invention, and this is generally performed after neutralization, extraction, filtration, concentration, distillation, recrystallization, crystallization, column chromatography, etc. Isolated and purified by conventional methods.
  • the compound (lb) represented by the formula (lb) obtained by the present invention includes, for example,
  • 2-Chloro-3-methyl (4-tetrahydrovinyl) -3-oxopropanoate is a novel compound with the following physical properties.
  • Example 1 methyl bromide-3- (4-tetrahydrovinyl) -3-oxopropanoate can be synthesized in good yield by carrying out the same reaction by replacing the halogenating agent with bromine.
  • the residue was washed with 50 ml of toluene, and the filtrate and the washing solution were combined and concentrated under reduced pressure.
  • Methyl 2-acetoxy-3- (4-tetrahydroviranyl) -3-oxopropanoate is a novel compound represented by the following physical properties.
  • the filtrate was washed with 20 ml of toluene, and the filtrate and washings were combined and concentrated under reduced pressure.
  • 2-Bivaloyloxy-3- (4-tetrahydrovinyl) -3-oxopropanoate methyl is a novel compound represented by the following physical properties.
  • reaction solution was cooled to ⁇ 10 to ⁇ 5 ° C., and 14 ml of water was slowly added dropwise and stirred for 30 minutes.
  • 14 ml of saturated aqueous sodium chloride solution, 14 ml of 5% by weight aqueous sodium hydrogen carbonate solution and 4.8 ml of saturated aqueous sodium hydrogen carbonate solution 9.6 ml of 5% by weight aqueous sodium hydrogen carbonate solution
  • 4.8 ml of a saturated aqueous sodium chloride solution was washed in that order to obtain 4.8 ml of a toluene solution of methyl 2-chloro-3- (4-tetrahydrovinyl) -3-oxopropanoate.
  • the reaction was allowed to proceed for 18 hours at room temperature. After completion of the reaction, 24 ml of water and 24 ml of ethyl acetate were added to the reaction solution, the organic layer was separated, and the aqueous layer was extracted with 24 ml of acetyl acetate. Next, the organic layer and the extract were combined, washed twice with 9.8 ml of saturated aqueous sodium chloride solution, and then concentrated under reduced pressure.
  • Methyl 2-cycloheptylcarboxy-3- (4-tetrahydrovinyl) -3-oxopropanoate is a novel compound represented by the following physical properties.
  • the present invention relates to 2-substituted-3- (4-tetrahydrovinyl) -3-oxopropanoic acid ester and a process for producing the same, and the resulting 2-substituted-3- (4-tetrahydrovinanyl) ) -3-oxopropanoic acid ester is a useful compound as a raw material for pharmaceuticals and agricultural chemicals, and as a synthetic intermediate.

Landscapes

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

Abstract

Cette invention concerne un ester de 2-substitué-3-(4-tétrahydropyranyle)-3-oxopropanoïque représenté par la formule générale (1) dans laquelle Y représente un atome d'halogène ou un groupement acyloxy, et R représente un groupement hydrocarbure, et un procédé pour le produire.
PCT/JP2005/014289 2004-08-04 2005-08-04 Ester de 2-substitué-3-(4-tétrahydropyranyle)-3-oxopeopanoïque et procédé pour le produire Ceased WO2006013920A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2006531536A JP4552939B2 (ja) 2004-08-04 2005-08-04 ２−置換−３−（４−テトラヒドロピラニル）−３−オキソプロパン酸エステル及びその製法

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2004-227629 2004-08-04
JP2004-227630 2004-08-04
JP2004227630 2004-08-04
JP2004227629 2004-08-04
JP2005068467 2005-03-11
JP2005-068467 2005-03-11

Publications (1)

Publication Number Publication Date
WO2006013920A1 true WO2006013920A1 (fr) 2006-02-09

Family

ID=35787199

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2005/014289 Ceased WO2006013920A1 (fr) 2004-08-04 2005-08-04 Ester de 2-substitué-3-(4-tétrahydropyranyle)-3-oxopeopanoïque et procédé pour le produire

Country Status (2)

Country Link
JP (1) JP4552939B2 (fr)
WO (1) WO2006013920A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1700852A4 (fr) * 2003-12-19 2009-07-22 Ube Industries Procede de production d'un compose 3-(4-tetrahydropyranyl)-3-oxopropionate alkyle et de 4-acyltetrahydropyran

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040082651A1 (en) * 2000-10-16 2004-04-29 Wessjohann Ludger A. Epothilone synthesis building blocks III and IV: asymmetrically substituted acyloins and acyloin derivatives, methods for their production and methods for the production of epothilones B, D and epothilone derivatives
WO2005058859A1 (fr) * 2003-12-19 2005-06-30 Ube Industries, Ltd. Procede de production d'un compose 3-(4-tetrahydropyranyl)-3-oxopropionate alkyle et de 4-acyltetrahydropyran

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040082651A1 (en) * 2000-10-16 2004-04-29 Wessjohann Ludger A. Epothilone synthesis building blocks III and IV: asymmetrically substituted acyloins and acyloin derivatives, methods for their production and methods for the production of epothilones B, D and epothilone derivatives
WO2005058859A1 (fr) * 2003-12-19 2005-06-30 Ube Industries, Ltd. Procede de production d'un compose 3-(4-tetrahydropyranyl)-3-oxopropionate alkyle et de 4-acyltetrahydropyran

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
VARTANYAN R.S.: "Synthesis of some novel biheterocyclic systems - derivatives of piperidine, tetrahydropyran and tetrahydropthiopyran", TEZISY DOKL.-SOV.-INDIISKII SIMP.KHIM.PRIR.SOEDIN, 5TH, 1978, pages 16, XP002991718 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1700852A4 (fr) * 2003-12-19 2009-07-22 Ube Industries Procede de production d'un compose 3-(4-tetrahydropyranyl)-3-oxopropionate alkyle et de 4-acyltetrahydropyran
US7741497B2 (en) 2003-12-19 2010-06-22 Ube Industries, Ltd. Processes for preparing alkyl 3-(4-tetrahydropyranyl)-3-oxopropanoate compound and 4-acyltetrahydropyrane

Also Published As

Publication number Publication date
JP4552939B2 (ja) 2010-09-29
JPWO2006013920A1 (ja) 2008-05-01

Similar Documents

Publication Publication Date Title
JP5993860B2 (ja) ４，４−ジフルオロ−３，４−ジヒドロイソキノリン誘導体の製造方法
WO2022002116A1 (fr) Procédé de préparation d'un composé de phénylisoxazoline
JP7399850B2 (ja) 芳香族ニトリル化合物の製造方法
WO2006013920A1 (fr) Ester de 2-substitué-3-(4-tétrahydropyranyle)-3-oxopeopanoïque et procédé pour le produire
JP6139667B2 (ja) ３，４，５−トリカフェオイルキナ酸の製造方法
JP4513517B2 (ja) ３−（ｎ−アシルアミノ）−２−アシルオキシ−３−（４−テトラヒドロピラニル）−２−プロペン酸エステル及びその製法
US7915418B2 (en) Intermediates and process for the production of optically active quinolonecarboxylic acid derivatives
JP4239473B2 (ja) ピリドン化合物の製造法およびその中間体
JP5205971B2 (ja) テトラヒドロピラン化合物の製造方法
JP2006137693A (ja) ２−アシルオキシ−３−（４−テトラヒドロピラニル）−３−アミノ−２−プロペン酸エステルのカルボン酸塩及びその製法
JP5034277B2 (ja) ３−（ｎ−アシルアミノ）−３−（４−テトラヒドロピラニル）−２−オキソプロパン酸エステル及び３−（ｎ−アシルアミノ）−３−（４−テトラヒドロピラニル）−２−オキソプロパノヒドラジドの製造方法
WO2010122793A1 (fr) Procédé de production d'un dérivé de pyrazine et intermédiaire pour la production
JP4869739B2 (ja) 含フッ素ジヒドロキノリン化合物及び含フッ素キノリン化合物の製造方法
JP4216012B2 (ja) ５−ブロモ−２−アルコキシピリジンの製造方法
JP2920557B2 (ja) ２−（５−アミノ−２−クロロ−４−フルオロフエニルチオ）酢酸メチルエステルの製造法およびその中間体
JP2010083798A (ja) ω−ヒドロキシ長鎖脂肪酸誘導体の製造方法
JP3918468B2 (ja) ３，３−ビス（アルコキシカルボニル−メチルチオ）プロピオニトリル及びその製造方法
JP2002316972A (ja) 光学活性３−シアノ−２−メチルプロパノール誘導体の製造法
JP2003342211A (ja) ４，４−ジフルオロ−３−ブテン−１−オール誘導体の製造法
WO2004089921A1 (fr) Nouveau procede de production de derive de benzylidene
JP2008174452A (ja) ２，２−ジクロロ−１２−（４−ハロフェニル）ドデカン酸塩の製法
JP2002201169A (ja) ４−シアノ−３−オキソブタン酸エステルの製造法
JP2002322153A (ja) キノリンカルボン酸エステル誘導体又はそのスルホン酸塩の製造法
JP2004002247A (ja) ４−ジフルオロメトキシ−３−ヒドロキシベンズアルデヒドの製造方法
JPWO2004033411A1 (ja) エノンエステルの製造法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KM KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU LV MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2006531536

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase