WO2000002843A1 - Procede de preparation de 1-arylalkylamines optiquement actifs et de leurs intermediaires - Google Patents

Procede de preparation de 1-arylalkylamines optiquement actifs et de leurs intermediaires Download PDF

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Publication number
WO2000002843A1
WO2000002843A1 PCT/JP1999/003576 JP9903576W WO0002843A1 WO 2000002843 A1 WO2000002843 A1 WO 2000002843A1 JP 9903576 W JP9903576 W JP 9903576W WO 0002843 A1 WO0002843 A1 WO 0002843A1
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Prior art keywords
optically active
acid
toluene
formula
represented
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PCT/JP1999/003576
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English (en)
Japanese (ja)
Inventor
Koji Hagiya
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Sumitomo Chemical Company, Limited
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Priority to AU43965/99A priority Critical patent/AU4396599A/en
Publication of WO2000002843A1 publication Critical patent/WO2000002843A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
    • C07D319/14—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems
    • C07D319/16—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D319/18—Ethylenedioxybenzenes, not substituted on the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/82—Purification; Separation; Stabilisation; Use of additives
    • C07C209/86—Separation
    • C07C209/88—Separation of optical isomers
    • 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
    • C07D317/58—Radicals substituted by nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers

Definitions

  • the present invention relates to a method for producing optically active 1-arylalkylamines.
  • Optically active 1-arylalkylamines are extremely useful compounds as pharmaceutical intermediates, agricultural chemical intermediates, artificial sweetener raw materials, etc. (for example, ⁇ 97 16448 publication, W095Z32948 publication, US Pat. No. 5,286,509). Gazette, JP-A-601 486, etc.).
  • a racemic 1-arylalkylamine can be prepared, for example, by adding an optically active cis-12-benzamide cyclohexanecarboxylic acid (JP-A-63-54342). Official Gazette), optically active calcium-amino acid (Japanese Patent Laid-Open No. 8-3120), optically active 2-methyl-2-phenylbutanediioic acid (Synthesis, 410 (1988)), optical A method for optical resolution using an active isopropylidene glycerol phthalate (Tetrahedron: Asymme try, 8, 1069 (1997)) or the like as an optical resolving agent has been reported.
  • a main object of the present invention is to provide an industrially advantageous method for producing optically active 1-arylalkylamines.
  • the present inventors have studied a method for producing an industrially advantageous optically active 1-arylalkylamine, and have found that the optically active ⁇ -isoalkylamine is industrially easily available.
  • the present inventors have found that optically active 1-arylalkylamines can be obtained with high yield and high optical purity by optical resolution with propylphenyldiacids, and the present invention has been completed.
  • the present invention provides a compound represented by the general formula (1):
  • R 1 represents a lower alkyl group having 26 carbon atoms
  • R 2 and R 3 are the same or different and each represent a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group. And when R 2 and R 3 are adjacent to each other, R 2 and R 3 may be linked together to form a methylenedioxy group or an ethylenedioxy group.
  • X represents a hydrogen atom, a halogen atom or a lower alkoxy group.
  • B represents the absolute configuration of R or S.
  • Examples of the lower alkyl group having 2 to 6 carbon atoms represented by the substituent R 1 include ethyl. Group, n-propyl group, isopropyl group, n -butyl group, isobutyl group, sec-butyl group, t_butyl group, n-pentyl group, n-hexyl group, etc. Examples thereof include a lower alkyl group having 2 to 6 carbon atoms, particularly preferably an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group.
  • the substituents R 2 and R 3 are the same or different and each represent a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group.
  • halogen atom examples include a fluorine atom, a chlorine atom, and a bromine atom.
  • Examples of the lower alkyl group include straight-chain or branched chains such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butynole, and t -butynole. And a lower alkyl group having 1 to 4 carbon atoms.
  • Lower alkoxy groups include, for example, methoxy, ethoxy, n-propoxy Examples thereof include a linear or branched lower alkoxy group having 1 to 4 carbon atoms such as a silyl group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a t -butoxy group.
  • R 2 and R 3 when R 2 and R 3 are adjacent to each other, R 2 and R 2 may be bonded to each other at their ends to form a methylenedioxy group or an ethylenedioxy group.
  • Specific examples thereof include, for example, Examples thereof include a 3,4-methylenedioxy group, a 3,4-ethylenedioxy group, a 2,3-methylenedioxy group, and a 2,3-ethylenedioxy group.
  • Such 1-arylalkylamines have two types of optical isomers, R-form and S-form, depending on the absolute configuration of the asymmetric carbon atom to which the amino group is bonded.
  • the 1-arylalkylamines those containing these optical isomers in an arbitrary ratio can be used. For example, any one of the isomers is contained in excess. Or a racemic form containing an equal amount.
  • Examples of the 1-arylalkylamines represented by the general formula (1) include, for example, 1-phenylpropynoleamine, 1- (2-chlorophenyl) propylamine, and 1- (3-chlorophenyl). Nore) Propinoleamine, 1- (4-fluorophene) Propyramine, 1-1 (2-fluorophenyl) propylamine, 1- (3-fluorophene) Propinoleamine, 1- (4-fenoleo-phen) Nore) Propylamine, 1- (3,4-dichlorophenol) Propinoleamine, 1-1 (4-methylphenyl) propylamine, 1- (4-Methoxyphenyl) propylamine, 1- (3,4-methylenedione) Xyphenyl) Propylamine, 1- (3,4-Ethylenedioxyphene / propyl) Propylamine, 1-Pheninolebutynoleamine, 1- (2-Chlorophenol) Butylamine, 1— (3-
  • optically active monoisopropylphenyl diacid represented by the general formula (2) will be described.
  • X represents a hydrogen atom, a halogen atom or a lower alkoxy group. More specifically, examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. In terms of availability and the like, a fluorine atom or a chlorine atom is preferred.
  • lower alkoxy group for example, main butoxy group, an ethoxy group, n - propoxy group, an isopropoxy group, a linear or branched carbon atoms, such as n- butoxy group: 1-4 lower alkoxy group
  • a methoxy group and an ethoxy group are preferable, and a methoxy group is particularly preferable.
  • optically active ⁇ - isopropyl phenylalanine acetic acids represented by, for example, in the formula (2), "b" represents an absolute configuration of S or R alpha - isopropyl-phenylalanine acid, alpha -Isopropyl-p-fluorophenylacetic acid, a-isopropyl-p-p-chlorophenylacetic acid, ⁇ -isopropyl-p-bromophenylacetic acid, ⁇ -isopropyl- ⁇ -methoxyphenylacetic acid, ⁇ -isopropyl- ⁇ -ethoxyphenyl ⁇ Acid, etc., from the viewpoint of availability and the like, among the above compounds, ⁇ -isopropizolefene / reacetic acid, a-isopropinole-p-funoreo-mouth feninoleacetic acid, ⁇ -isopropyl-p-chloro Preferred are optical iso
  • the two optical isomers of the R-form and the S-form of the optically active ⁇ -isopropylphenylacetic acids are appropriately selected and used according to the intended optically active 1-arylalkylamines. Also, the purity of the optical isomers of S-form and R-form need not be 100%, It is sufficient that one of them is contained in excess, and preferably one containing 90% or more is used.
  • the amount of the optically active ⁇ -isopropylphenylacetic acid used is usually 0.1 to 1 mol times, preferably 0.2 to 0.8 mol times, relative to 1-alkylalkylamines. .
  • the inert solvent examples include aromatic hydrocarbon solvents such as toluene, xylene, and benzene, aliphatic hydrocarbon solvents such as hexane and heptane, and ether solvents such as getyl ether and methyl t-butyl ether.
  • Solvents alcohol solvents such as methanol, ethanol, and 2-propanol; ester solvents such as ethyl acetate; nitrile solvents such as acetonitrile; water; and the like. These solvents may be used alone. May be used as a mixed solvent.
  • aromatic hydrocarbon solvents, ether solvents, alcohol solvents, and mixed solvents of these solvents and water are preferred.
  • the amount of the inert solvent to be used is generally 0.5 to 100 times by weight, preferably 1 to 50 times by weight, relative to 1-arylalkylamines represented by the general formula (1). .
  • the reaction between a 1-arylalkylamine represented by the general formula (1) and an optically active ⁇ -isopropylphenylacetic acid represented by the general formula (2) is usually performed by reacting the 1-arylalkylamine represented by the general formula (1).
  • An optically active ⁇ -isopropylphenylacetic acid represented by the general formula (2) is added to a solution in which a reel alkylamine is dissolved in a solvent as it is or by dissolving it in a solvent and adding it as a solution.
  • the method of using the inert solvent is not particularly limited. The addition may be performed continuously.
  • the reaction temperature may be in the range of usually 0 ° C. or higher and the reflux temperature of the reaction mixture or lower.
  • a diastereomeric monosalt mixture of optically active 1-arylalkylamines and optically active "isopropylpropyl acetic acid is obtained.
  • one diastereomer salt represented by the formula (3) is isolated. This is the alkali treatment
  • an optically active 1-arylalkylamine represented by the formula (4) can be obtained.
  • part of one diastereomer salt of the diastereomer salt mixture is crystallized in the reaction mass. This may be taken out as it is, but it is preferable that the reaction mass is cooled or concentrated to thereby crystallize out more diastereomer monosalt and taken out. Depending on the conditions, the desired diastereomer monosalt may be completely dissolved in the reaction mass.In this case, the desired diastereomer monosalt is crystallized by cooling the reaction mass or by concentrating the reaction mass. Let me take it out.
  • One of the crystallized diastereomeric salts of the optically active 1-arylalkylamines and the optically active sodium propylphenylacetic acids can be easily removed by a usual filtration operation.
  • the diastereomer salts of the optically active 1-arylalkylamines represented by the formula (4) and the optically active ⁇ -isopropylphenylacetic acids represented by the formula (4) can be directly treated with an alkali or washed, for example, by washing or rewashing. After further purification by crystallization or the like, an optically active 1-arylalkylamine can be easily obtained by subjecting it to an alkaline treatment.
  • the fermentation treatment is usually carried out by mixing diastereomer monosalt and ferrite, and the mixing temperature is usually in the range of 0 to: I 0 ° C.
  • alkali used examples include water solutions such as potassium hydroxide and sodium hydroxide, and the concentration thereof is generally in the range of 1 to 50% by weight, preferably 5 to 20% by weight.
  • the amount of the alkali used is usually about 1 to 5 moles per mole of the diastereomer salt.
  • the optically active 1-arylalkylamines are usually separated as an oil layer from the alkali-treated mass, and may be separated and taken out as it is. Further, an organic solvent insoluble in water is added to the alkali-treated mass and the mixture is extracted. The organic solvent is distilled off from the obtained organic layer, and the optically active 1-aryl represented by the formula (4) is removed. Alkylamines may be removed.
  • water-insoluble organic solvents examples include getyl ether and methyl t-butyl ester.
  • Ether solvents such as mono-ter, for example, ester solvents such as ethyl ester, for example, aromatic hydrocarbon solvents such as toluene, xylene, and benzene, for example, aliphatic hydrocarbons such as hexane and heptane
  • Solvents include, for example, halogenated hydrocarbon solvents such as dichloromethane, chlorophonolem and the like, and the amount of the solvent is usually in the range of 0.1 to 5 times by weight based on the diastereomer used. There is no problem if an organic solvent insoluble in water or water is added in advance when diastereomer monosalt is alkali-treated.
  • the diastereomer salt is subjected to an acid treatment in advance and then subjected to an alkaline treatment, whereby the optically active 1-arylalkylamines can be taken out. If the diastereomer salt is treated with an acid in advance, optically active sodium propylphenylacetic acids are released. Therefore, it is preferable to carry out an alkali treatment after removing the released optically active sodium propylphenylacetic acids.
  • the acid treatment is usually performed by mixing an aqueous solution of a diastereomer salt and an acid, and the mixing temperature is usually 0 to 10 ° C.
  • an aqueous solution of a mineral acid such as hydrochloric acid, sulfuric acid, phosphoric acid or the like is usually mentioned, and its concentration is usually 1 to 50% by weight, preferably 5 to 40% by weight.
  • the amount of the acid to be used is usually 1 to 5 moles per 1 mole of the diastereomer salt, preferably:! ⁇ 2 mole times.
  • a method for removing the liberated optically active ⁇ -isopropylphenylacetic acid for example, a method in which an organic solvent insoluble in water is added to a mass obtained by previously treating a diastereomer salt with an acid, and an extraction treatment is performed.
  • the organic solvent insoluble in water include the same ones as described above, and the amount of the organic solvent is usually 0.5 to 5 times by weight based on the diastereomer salt used.
  • the water-insoluble organic solvent can be added to the diastereomer salt in the acid treatment without any problem.
  • optically active ⁇ -isopropylphenylacetic acids may be precipitated in the acid-treated mass, and may be released as it is or after further cooling and then filtration. It is also possible to remove the optically active bis (propylphenylacetic acid).
  • hydroxide hydroxide and sodium hydroxide are used in the acid treatment.
  • ⁇ alkaline aqueous solution such as beam is used, its concentration is usually 1 to 5 0 wt%, rather preferably is 5-2 0 weight 0/0. Strong alkali is added until the pH value of the treated mass is usually 10 or more.
  • the processing temperature is usually 0 to 100 ° C.
  • the optically active 1-arylalkylamines are usually separated as an oil layer from the alkali-treated mass, and the oil layer can be separated and taken out as it is. Good.
  • an organic solvent insoluble in water may be added to the alkali-treated mass and subjected to an extraction treatment, and the organic solvent may be distilled off from the obtained organic layer to extract optically active 1-arylalkylamines.
  • the water-insoluble organic solvent include the same ones as described above, and the amount of the organic solvent is usually in the range of 0.1 to 5 times by weight based on the diastereomer used in the treatment. The water-insoluble organic solvent does not pose any problem even if it is added in advance during the alkali treatment.
  • the diastereomer salt thus obtained is treated with an alkali or with an acid beforehand to remove the optically active iso-isopropylphenylacetic acid which has been liberated and then treated with an alcohol to obtain an optically active 1-arylalkyl acrylate. Mines are obtained.
  • the optically active ⁇ -isopropylphenyl diacids used can be easily recovered, for example, by the following operation, and the recovered optically active ⁇ -isopropylphenyl acetic acid can be obtained from 1-arylalkylamine. Can be reused for the reaction of the compounds with optically active ⁇ -isopropylphenylacetic acids.
  • the treated mass after removing the optically active 1-arylalkylamines is acid-treated to obtain an optically active monoisopropylamine.
  • the enylacetic acids can be recovered.
  • an aqueous solution of a mineral acid such as hydrochloric acid, sulfuric acid, phosphoric acid or the like is used, and its concentration is usually 1 to 50% by weight, preferably 5 to 40% by weight.
  • a mineral acid such as hydrochloric acid, sulfuric acid, phosphoric acid or the like
  • concentration is usually 1 to 50% by weight, preferably 5 to 40% by weight.
  • acids are added until the treated mass has a ⁇ of usually 2.5 or less, preferably 2 or less.
  • optically active ⁇ -isopropylphenyldiacids When the treated mass after removing the optically active 1-arylalkylamines is subjected to an acid treatment, a part of the optically active ⁇ -isopropylphenyldiacids usually crystallizes in the acid-treated mass, and the acid Filtration of the treated mass as it is or after further cooling By the treatment, optically active "isopropylphenylacetic acids" can be recovered. Further, an organic solvent insoluble in water is added to the acid-treated mass, and an extraction treatment is performed. The solvent can be distilled off to recover the optically active bis (propylphenylacetic acid) .
  • the organic solvents insoluble in water include the same as those described above, and are insoluble in water. The organic solvent may be added in advance during the acid treatment.
  • a solvent used for the reaction between 1-arylalkylamines and optically active ⁇ -isopropylphenyl diacids may be used.
  • the organic layer containing the optically active ⁇ -isopropylphenylacetic acid obtained by the extraction treatment is directly reacted with the 1-arylalkylamines and the optically active ⁇ -isopropylphenylacetic acid. It is possible to re-use.
  • the diastereomer monosalt is preliminarily acid-treated and then alkali-treated, a part of the optically active isopropyl phenylacetic acid is usually crystallized in the acid-treated mass, and the acid-treated mass is left as it is.
  • an optically active iso-isopropylphenylacetic acid can be recovered by filtration.
  • the acid-treated mass may be subjected to an extraction treatment by adding an organic solvent insoluble in water, and the organic solvent may be distilled off from the obtained organic layer to recover optically active ⁇ -isopropylphenylacetic acids. it can.
  • the water-insoluble organic solvent include the same ones as described above.
  • the strong water-insoluble organic solvent may be added in advance during the acid treatment.
  • a solvent used for the reaction between 1-arylalkylamines and optically active polyphenylpyranic acid is used as an organic solvent insoluble in water
  • the optically active ⁇ -alkyl obtained by the extraction treatment is used.
  • the organic layer containing isopropylpropyl acetic acid can be reused as it is for the reaction of 1-arylalkylamines with the optically active ⁇ -isopropylphenylacetic acid.
  • the other optically active isomer having an enantiomeric relationship with the diastereomer salt-formed 1-arylalkylamines is contained in the filtrate after removing the diastereomer salt by filtration.
  • the ability to obtain high optical purity by distilling off the solvent from the filtrate In general, the filtrate contains diastereomeric salts dissolved in the crystallization medium, unreacted optically active 1-arylalkylamine And optically active isopropyl phenolic acids.
  • the reaction between 1-arylalkylamines and the optically active a-sopropylphenylacetic acid is carried out in a hydrophilic solvent such as methanol
  • the filtrate after removing the diastereomer salt is concentrated, It is preferable to subject the resulting concentrated residue to an alkali treatment or an acid treatment beforehand, followed by an alkaline treatment.
  • Such an acid treatment or an acid treatment after an acid treatment in advance is carried out according to the above-mentioned method for extracting optically active 1-arylalkylamines from diastereomeric salts.
  • optically active 1-arylalkylamines represented by the formula (4) are obtained, and specific examples thereof include the examples of the 1-arylalkylamines represented by the above formula (1).
  • the desired optical activity can be obtained by optically resolving 1-arylalkylamines with ⁇ -isopropylphenylacetic acids which are industrially easy to obtain.
  • the arylalkylamines can be obtained with high yield and high optical purity.
  • the optically active c_-isopropylphenyl diacids used as the optical resolving agent can be easily recovered and reused, which is industrially advantageous.
  • optical purity of the obtained optically active 1-arylalkylamines was determined by high performance liquid chromatography using an optically active column.
  • the diastereomeric salt of min and ⁇ - ⁇ fsopropyl-p-fluorophenylacetic acid was precipitated.
  • the precipitated diastereomer salt was separated by filtration and washed with 10 g of toluene to obtain 3.4 g of diastereomer monosalt.
  • 40 g of toluene was added to 3.35 g of the diastereomer salt, the internal temperature was raised to 60 ° C, and the mixture was stirred and maintained at the same temperature for 1 hour. Thereafter, the mixture was cooled to 30 ° C. over 6 hours, and 2.7 g of diastereomer salt was collected by filtration (melting point:
  • the diastereomeric salt was subjected to X-ray single crystal structure analysis, and the obtained crystal data is shown below.
  • diastereomer monosalt was added 10 g of a 5% by weight aqueous sodium hydroxide solution, and the mixture was stirred and maintained at an internal temperature of 40 ° C. for 30 minutes. After that, toluene was added for extraction, and the toluene layer and the aqueous layer were separated.
  • the mixture was cooled to an inner temperature of 0 ° C over a period of between 3:00, 1 _ - to precipitate the Jiasutereoma salt (3, 4-methylenedioxy-O carboxymethyl phenylene Honoré) butyrate Ruamin and ⁇ - isopropyl one P- black port phenylacetic acid
  • the precipitated diastereomer salt was separated by filtration and washed with 10 g of toluene to obtain 4.2 g of diastereomer monosalt.
  • To 4.2 g of the diastereomer salt was added 40 g of 2-propanol, the internal temperature was raised to 60 ° C, and the mixture was stirred and maintained at the same temperature for 2B. Thereafter, the mixture was cooled to 0 ° C over 3 hours, and 2.2 g of diastereomer salt was collected by filtration (melting point: 148 to 150 ° C).
  • hydrochloric acid 36% by weight hydrochloric acid was added to the above aqueous layer to adjust its pH to 1.5, and the mixture was extracted with toluene. After the obtained toluene layer was washed with water, the toluene was distilled off, and 3.lg of (R) -aT-sopropyl-p-chlorophenylphenylacetic acid was recovered.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)

Abstract

L'invention porte sur un procédé de préparation de 1-arylalkylamines optiquement actifs représentés par la formule générale (4) (dans laquelle R1 représente alkyl inférieur C¿2?-C6; R?2 et R3¿ représentent chacun, indépendamment, hydrogène, halogéno, alkyl inférieur ou alcoxy inférieur, à condition que, lorsque R2 et R3 sont adjacents, ils puissent être réunis au niveau de leurs extrémités de façon à former méthylènedioxy ou éthylènedioxy; et a représente une configuration R- ou S-). On utilise, pour cette préparation, un acide α-isopropylphénylacétique optiquement actif représenté par la formule générale (2) (dans laquelle X représente hydrogène, halogéno ou alcoxy inférieur; et b représente une configuration R- ou S-).
PCT/JP1999/003576 1998-07-09 1999-07-02 Procede de preparation de 1-arylalkylamines optiquement actifs et de leurs intermediaires WO2000002843A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU43965/99A AU4396599A (en) 1998-07-09 1999-07-02 Process for the preparation of optically active 1-arylalkylamines and intermediates therefor

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP19461998 1998-07-09
JP10/194619 1998-07-09
JP12452599A JP2000080062A (ja) 1998-07-09 1999-04-30 光学活性１―アリ―ルアルキルアミン類の製造方法およびその中間体
JP11/124525 1999-04-30

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Publication Number Publication Date
WO2000002843A1 true WO2000002843A1 (fr) 2000-01-20

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61293949A (ja) * 1985-06-20 1986-12-24 Sumitomo Chem Co Ltd ａ−イソプロピル−ｐ−クロルフエニル酢酸の光学分割法
JPH05229986A (ja) * 1991-08-23 1993-09-07 Nagase Sangyo Kk ２−（４−イソブチルフェニル）プロピオン酸の光学分割方法
JPH09104663A (ja) * 1995-10-09 1997-04-22 Sumitomo Chem Co Ltd 光学活性 １−（ｍ−ベンジルオキシフェニル） アルキルアミン類の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61293949A (ja) * 1985-06-20 1986-12-24 Sumitomo Chem Co Ltd ａ−イソプロピル−ｐ−クロルフエニル酢酸の光学分割法
JPH05229986A (ja) * 1991-08-23 1993-09-07 Nagase Sangyo Kk ２−（４−イソブチルフェニル）プロピオン酸の光学分割方法
JPH09104663A (ja) * 1995-10-09 1997-04-22 Sumitomo Chem Co Ltd 光学活性 １−（ｍ−ベンジルオキシフェニル） アルキルアミン類の製造方法

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