WO1995035291A1 - Process for producing phthalide compound - Google Patents

Process for producing phthalide compound Download PDF

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Publication number
WO1995035291A1
WO1995035291A1 PCT/JP1995/000850 JP9500850W WO9535291A1 WO 1995035291 A1 WO1995035291 A1 WO 1995035291A1 JP 9500850 W JP9500850 W JP 9500850W WO 9535291 A1 WO9535291 A1 WO 9535291A1
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Prior art keywords
compound
acid
formula
represented
producing
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PCT/JP1995/000850
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French (fr)
Japanese (ja)
Inventor
Sachio Mori
Sumio Shimizu
Makoto Hajima
Shiro Kida
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Shionogi & Co., Ltd.
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Priority to AU23530/95A priority Critical patent/AU2353095A/en
Priority to JP50191796A priority patent/JP3655311B2/en
Publication of WO1995035291A1 publication Critical patent/WO1995035291A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0204—Ethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0205—Oxygen-containing compounds comprising carbonyl groups or oxygen-containing derivatives, e.g. acetals, ketals, cyclic peroxides
    • B01J31/0208—Ketones or ketals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0231—Halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
    • C07D307/88—Benzo [c] furans; Hydrogenated benzo [c] furans with one oxygen atom directly attached in position 1 or 3

Definitions

  • the present invention relates to a novel method for producing a phthalide compound. More specifically, the present invention relates to a method for producing a pentoalkoxyphthalide compound in one step, which comprises condensing a trialkoxybenzoic acid derivative and a dialkoxybenzaldehyde with an acid.
  • the pentaalkoxyphthalide compound produced according to the present invention is disclosed in Japanese Unexamined Patent Application Publication No. 5-31034 and WO93 / 08155 by the present applicant. It is a raw material for the production of lignan derivatives that are useful compounds. Problems to be solved by the prior art and the invention
  • the present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found that tricarboxylic acid or methanesulfonic acid can be used as a condensing agent. It was found that a penoxyalkoxy phthalide compound can be produced in one step from a benzoic acid derivative and a dialkoxybenzaldehyde. Detailed description of the invention
  • the present invention provides a compound of formula (II)
  • R 1 and R 2 are independently a lower alkyl group, and E 3 is a hydroxy group or a halogen atom]
  • lower alkyl in the definition of R RK R and R 5 means straight or branched C! -Ce alkyl, which includes methyl, ethyl, n-propyl, i-propyl, n -Butyl, i-butyl, s-butyl, n-pentyl, n-hexyl and the like.
  • it is d-alkyl.
  • B 1 , ⁇ 2 , ⁇ and ⁇ 5 are methyl groups.
  • halogen atom in the definition of R 3 include chlorine and bromine.
  • the invention includes the following embodiments:
  • beta 3 when it is Gahi Dorokishi group a method of reacting in the presence of polyphosphoric acid.
  • the ratio of the compound (II) and the compound (III) to be used is not particularly limited, but usually, the compound (II) is used in an equivalent amount or an excess amount, preferably 1: 1 to 1: 3 with respect to the compound (II) I do.
  • Examples of the condensing agent used, polyphosphoric acid can be used methanesulfonic acid, preferably poly phosphoric acid
  • E 3 is a halogen compound ([pi) when the R 3 Gahi Dorokishi group of the compound ([pi) For atoms, methanesulfonic acid is used.
  • the amount of polyphosphoric acid used is equal to or more than that of compound ( ⁇ ), preferably 2 to 3 times, and the amount of methanesulfonic acid is 5 to 5 times that of compound ( ⁇ ). Use the amounts, preferably equal amounts.
  • the reaction solvent may be, for example, halogenated hydrocarbons such as methylene chloride, methylene bromide, 1,2-dichloroethane, and chloroform, halogenated aromatic hydrocarbons such as benzene and dichloro-7benzene, and ethyl acetate.
  • Esters such as ethyl propionate and methyl benzoate can be used alone or in combination.
  • polyphosphoric acid uses chlorobenzene and 1,2-dichloroethane, while methanesulfonic acid uses 1,2-dichloroethane.
  • This reaction is completed usually at room temperature to 150 ° C, preferably at 50 ° C to 100 ° C, and more preferably at 60 ° C to 90 ° C in several tens minutes to several tens of hours.
  • Compounds (II) and (III), which are raw materials for the method of the present invention, can be produced by a conventional method.
  • the condensing agent used in the method of the present invention is commercially available.
  • the present inventors have studied many known condensing agents as the condensing agent in this reaction. As a result, only when polyphosphoric acid or methanesulfonic acid was used, the desired compound (I) was obtained in a relatively high yield I got it.
  • polyphosphoric acid, methanesulfonic acid, other known condensing agent e.g. P 2 0 5, H 2 S0 4, H 2 S0 4 / P 2 0 5.

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

Abstract

A novel process for producing a phthalide compound represented by general formula (I), by the reaction of a trialkoxybenzoic acid derivative represented by general formula (II), with a dialkoxybenzaldehyde represented by general formula (III), in the presence of a condensing agent (in the above formulae, R?1, R2, R4 and R5¿ represent each independently lower alkyl; and R3 represents hydroxy or halogen).

Description

明 細 書 フタリ ド化合物の製造方法 発明の詳細な説明  Description Method for producing phthalide compound Detailed description of the invention
本発明はフタリ ド化合物の新規な製造方法に関する。 より詳細には、 本 発明は、 トリアルコキシ安息香酸誘導体とジアルコキシベンズアルデヒ ド とを酸により縮合させることを特徴とする、 一工程でペン夕アルコキシフ タリ ド化合物を製造する方法に関する。 産業上の利用分野  The present invention relates to a novel method for producing a phthalide compound. More specifically, the present invention relates to a method for producing a pentoalkoxyphthalide compound in one step, which comprises condensing a trialkoxybenzoic acid derivative and a dialkoxybenzaldehyde with an acid. Industrial applications
本発明により製造されるペンタアルコキシフタリ ド化合物は、 本出願人 により特開平 5— 3 1 0 6 3 4号、 WO 9 3 / 0 8 1 5 5号に開示されて いる、 抗高脂血症剤として有用な化合物であるリグナン誘導体の製造原料 である。 従来技術および発明が解決しょうとする課題  The pentaalkoxyphthalide compound produced according to the present invention is disclosed in Japanese Unexamined Patent Application Publication No. 5-31034 and WO93 / 08155 by the present applicant. It is a raw material for the production of lignan derivatives that are useful compounds. Problems to be solved by the prior art and the invention
従来、 本発明に係るペンタアルコキシフタリ ド化合物の製法としては、 前記特開平 5— 3 1 0 6 3 4号の参考例 1 6に記載の方法が知られている。 し力、し、 該方法は、 多工程を要する上に、 n— B u L i等の高価な試薬を用 いる必要があり、 工業的製法として望ましいものではなかった。 課題を解決するための手段  Conventionally, as a method for producing a pentaalkoxyphthalide compound according to the present invention, a method described in Reference Example 16 of JP-A-5-310634 is known. This method requires multiple steps and requires the use of expensive reagents such as n-BuLi, which is not desirable as an industrial production method. Means for solving the problem
本発明者らは、 上記課題を解決するために鋭意検討した結果、 ポリ リン 酸又はメタンスルホン酸を縮合剤として用いることにより、 卜リアルコキ シ安息香酸誘導体及びジアルコキシベンズアルデヒドよりペン夕アルコキ シフタリ ド化合物が一工程で製造できることを見いだした。 発明の詳しい説明 The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found that tricarboxylic acid or methanesulfonic acid can be used as a condensing agent. It was found that a penoxyalkoxy phthalide compound can be produced in one step from a benzoic acid derivative and a dialkoxybenzaldehyde. Detailed description of the invention
本発明は式 (II) The present invention provides a compound of formula (II)
Figure imgf000004_0001
Figure imgf000004_0001
[式中、 R1 及ひ Ί2 は個別に低級アルキル基であり、 E3 はヒ ドロキシ基 又はハロゲン原子である] [Wherein R 1 and R 2 are independently a lower alkyl group, and E 3 is a hydroxy group or a halogen atom]
で示されるトリアルコキシ安息香酸誘導体と式（III) ：
Figure imgf000004_0002
And a trialkoxybenzoic acid derivative represented by the formula (III):
Figure imgf000004_0002
[式中、 及び は個別に低級アルキル基である]  [Wherein and are independently lower alkyl groups]
で示されるジアルコキシベンズアルデヒ ドとをポリ リン酸又はメタンスル ホン酸の存在下に反応させることにより式（ I ) ：
Figure imgf000004_0003
Is reacted with a dialkoxybenzaldehyde represented by the following formula in the presence of polyphosphoric acid or methanesulfonic acid to obtain a compound of the formula (I):
Figure imgf000004_0003
[式中、 I？1、 R R4 及び R5 は前記の定義と同意義である] [Where I? 1, RR 4 and R 5 are the same meanings as defined in the '
で示されるペンタアルコキシフタリ ド化合物を製造する方法を提供するも のである。 本発明方法により、 ペンタアルコキシフタリ ド化合物を安価で 大量に製造することが可能となる。 R RK R 及び R5 の定義における 「低級アルキル基」 とは、 直鎖又は 分枝鎖状の C! -Ceアルキルを意味し、 それにはメチル、 ェチル、 n-プロピ ル、 i-プロピル、 n-ブチル、 i-ブチル、 s-ブチル、 n-ペンチル、 n-へキシ ル等が例示される。 好ましくは、 d - アルキルである。 より好ましくは、 B1 , β2、 β 及び Β5 がメチル基である。 And a method for producing a pentaalkoxyphthalide compound represented by the formula: According to the method of the present invention, it is possible to mass-produce pentaalkoxyphthalide compounds at low cost. The term "lower alkyl" in the definition of R RK R and R 5 means straight or branched C! -Ce alkyl, which includes methyl, ethyl, n-propyl, i-propyl, n -Butyl, i-butyl, s-butyl, n-pentyl, n-hexyl and the like. Preferably, it is d-alkyl. More preferably, B 1 , β 2 , β and Β 5 are methyl groups.
R3 の定義におけるハロゲン原子としては、 塩素、 臭素等が例示される。 本発明には、 以下の態様が含まれる ： Examples of the halogen atom in the definition of R 3 include chlorine and bromine. The invention includes the following embodiments:
(1) Β3がヒ ドロキシ基である時、 ポリ リン酸の存在下に反応させる方法。 (1) beta 3 when it is Gahi Dorokishi group, a method of reacting in the presence of polyphosphoric acid.
(2) Ε3がハロゲン原子である時、 メタンスルホン酸の存在下に反応させ る方法。 反応条件 (2) When 方法3 is a halogen atom, the reaction is carried out in the presence of methanesulfonic acid. Reaction conditions
化合物（II)及び化合物（III)の使用割合は特に制限されないが、 通常は、 化合物（ΠΙ)を化合物（II)に対して等量もしくは過剰量、 好ましくは 1 : 1〜 1 : 3で使用する。  The ratio of the compound (II) and the compound (III) to be used is not particularly limited, but usually, the compound (II) is used in an equivalent amount or an excess amount, preferably 1: 1 to 1: 3 with respect to the compound (II) I do.
使用する縮合剤としては、 ポリ リン酸、 メタンスルホン酸を用いること ができ、 好ましくは、 化合物（Π)の R3 がヒ ドロキシ基の時にはポリ リン 酸を、 化合物（Π)の Ε3 がハロゲン原子の時にはメタンスルホン酸を用い る。 ポリ リン酸の使用量は、 化合物（Π)に対して等量以上、 好ましくは 2 倍から 3倍を用い、 メタンスルホン酸の使用量は、 化合物（Π)に対して 5倍量から 5倍量、 好ましくは等量を用いる。 Examples of the condensing agent used, polyphosphoric acid, can be used methanesulfonic acid, preferably poly phosphoric acid, E 3 is a halogen compound ([pi) when the R 3 Gahi Dorokishi group of the compound ([pi) For atoms, methanesulfonic acid is used. The amount of polyphosphoric acid used is equal to or more than that of compound (Π), preferably 2 to 3 times, and the amount of methanesulfonic acid is 5 to 5 times that of compound (Π). Use the amounts, preferably equal amounts.
反応溶媒は、 例えば、 塩化メチレン、 臭化メチレン、 1, 2-ジクロロエタ ン、 クロ口ホルム等のハロゲン化炭化水素類、 クロ口ベンゼン、 ジクロロ 7ベンゼン等のハロゲン化芳香族炭化水素類、 酢酸ェチル、 プロピオン酸 ェチル、 安息香酸メチル等のエステル類を単独で、 又は混合して使用でき る。 好ましくは、 ポリ リン酸の時はクロ口ベンゼン、 1， 2—ジクロロェ タンを用い、 他方メタンスルホン酸の時は 1, 2—ジクロロェタンを用い る。 The reaction solvent may be, for example, halogenated hydrocarbons such as methylene chloride, methylene bromide, 1,2-dichloroethane, and chloroform, halogenated aromatic hydrocarbons such as benzene and dichloro-7benzene, and ethyl acetate. , Esters such as ethyl propionate and methyl benzoate can be used alone or in combination. You. Preferably, polyphosphoric acid uses chlorobenzene and 1,2-dichloroethane, while methanesulfonic acid uses 1,2-dichloroethane.
本反応は、 通常、 室温から 150°C、 好ましくは 50°Cから 100°C、 さらに好 ましくは 60°Cから 90°Cにて、 数十分から数十時間で完結する。  This reaction is completed usually at room temperature to 150 ° C, preferably at 50 ° C to 100 ° C, and more preferably at 60 ° C to 90 ° C in several tens minutes to several tens of hours.
本発明方法の製造原料である化合物（II)及び化合物（III)は常法により 製造することができる。 本発明方法に使用する縮合剤は市販されている。 尚、 本発明者らは、 本反応における縮合剤として、 多くの公知の縮合剤 を検討した結果、 ポリ リン酸またはメタンスルホン酸を使用した時にのみ、 目的化合物（I)を比較的収率よく得ることが出来た。 本縮合反応において は、 ポリリン酸、 メタンスルホン酸は、 その他の公知縮合剤 （たとえば P 205、 H2S04、 H2S04/P 205. パラ トルエンスルホン酸、 CF3C 02H、 HC1、 （CF3C〇）2OZH2S04、 無水酢酸、 無水ホウ酸、 ルイ ス酸（CF3S〇3SiMe3、 TiCl4、 A1C13、 SnCl4、 ZnCl2、 B F3- 〇Et2等） ） に比べて、 原料基質に対する特異性が高いといえる。 Compounds (II) and (III), which are raw materials for the method of the present invention, can be produced by a conventional method. The condensing agent used in the method of the present invention is commercially available. The present inventors have studied many known condensing agents as the condensing agent in this reaction. As a result, only when polyphosphoric acid or methanesulfonic acid was used, the desired compound (I) was obtained in a relatively high yield I got it. In condensation reaction, polyphosphoric acid, methanesulfonic acid, other known condensing agent (e.g. P 2 0 5, H 2 S0 4, H 2 S0 4 / P 2 0 5. P-toluenesulfonic acid, CF 3 C 0 2 H, HC1, (CF 3 C_〇) 2 OZH 2 S0 4, acetic anhydride, boric acid anhydride, Louis scan acid (CF 3 S_〇 3 SiMe 3, TiCl 4, A1C1 3, SnCl 4, ZnCl 2, BF 3 -〇Et 2 etc.) It can be said that the specificity for the raw material substrate is higher than that of).
以下に実施例を記載し、 本発明をさらに詳細に説明するが、 これらは本 範囲の限定を意図するものでない。 実施例 1  Hereinafter, the present invention will be described in more detail by way of Examples, but these are not intended to limit the scope. Example 1
3- (3， 4-ジメ トキシフエニル） -4， 5， 6 -トリメ トキシ- 1(3H)-イソべンゾフ ラノン ： 1の合成  Synthesis of 3- (3,4-dimethoxyphenyl) -4,5,6-trimethoxy-1 (3H) -isobenzofuranone: 1
3， 4, 5-トリメ トキシ安息香酸 254.4gと 3, 4 -ジメ トキシベンズアルデヒ ド 240gのクロ口ベンゼン 750ml溶液にポリ リン酸 （85%市販品） 600gを加 え、 80°Cで 4時間攪拌する。 反応液に水を加え、 クロ口ベンゼンで抽出す る。 減圧濃縮した反応液残渣をメタノール 900 ml より結晶化して融点： 139 〜 141°Cの目的とするフタリ ド化合物 1 を 211 g 得る。 さらに、 メ タノールより再結晶して融点： 141 〜 142 °Cの結晶を 200 g 得る。 To a solution of 254.4 g of 3,4,5-trimethoxybenzoic acid and 240 g of 3,4-dimethoxybenzaldehyde in 750 ml of chlorobenzene, 600 g of polyphosphoric acid (85% commercial product) is added, and the mixture is treated at 80 ° C for 4 hours. Stir. Add water to the reaction mixture and extract with benzene. The reaction solution residue concentrated under reduced pressure was crystallized from 900 ml of methanol to give There are obtained 211 g of the desired phthalide compound 1 at 139-141 ° C. Furthermore, recrystallization from methanol gives 200 g of crystals having a melting point of 141 to 142 ° C.
!H-N R: δ (CDC13) 3.52 (3H, s) 3.83 (3H, s) 3.89 (3H, s) 3.92 (3H, s) 3.95 (3H, s) 6.32 (1H, s) 6.72 (1H, s) 6.86 (2H, s) 7.21 (1H, s) 実施例 2 ! HN R: δ (CDC1 3 ) 3.52 (3H, s) 3.83 (3H, s) 3.89 (3H, s) 3.92 (3H, s) 3.95 (3H, s) 6.32 (1H, s) 6.72 (1H, s ) 6.86 (2H, s) 7.21 (1H, s) Example 2
3^(3, 4-ジメ トキシフエ二ル） - 4, 5， 6-トリメ トキシ- 1(3H)-イソべンゾフ ラノン： 1の合成  Synthesis of 3 ^ (3,4-dimethoxyphenyl) -4,5,6-trimethoxy-1 (3H) -isobenzofuranone: 1
3,4,5-トリメ トキシベンゾイルクロリ ド 2.30gと 3, 4-ジメ トキシベンズ アルデヒ ド 4.98gの 1， 2-ジクロロエタン 10ml溶液にメタンスルホン酸 0.65m 1を加え、 70°Cで 6時間攪拌する。 反応液に水を加え、 塩化メチレンで抽出 する。 減圧濃縮した残渣を中圧シリカゲルカラムクロマトグラフィー精製 (シリカゲル； 60 g， 酢酸ェチルー n—へキサン = 1 ： 2)し、 更にメタノ —ルより結晶化して目的とするフタリ ド化合物 1 を 1.12 g 得る。 融点： 141 〜 142°Cc  0.65 ml of methanesulfonic acid was added to a solution of 2.30 g of 3,4,5-trimethoxybenzoyl chloride and 4.98 g of 3,4-dimethoxybenzaldehyde in 10 ml of 1,2-dichloroethane, and the mixture was stirred at 70 ° C for 6 hours. . Add water to the reaction mixture and extract with methylene chloride. The residue concentrated under reduced pressure was purified by medium pressure silica gel column chromatography (silica gel; 60 g, ethyl acetate-n-hexane = 1: 2), and crystallized from methanol to obtain 1.12 g of the desired phthalide compound 1. . Melting point: 141-142 ° Cc
JH-NMR：実施例 1に同じ  JH-NMR: same as in Example 1

Claims

請 求 の 範 囲 The scope of the claims
1 . 式 (π)
Figure imgf000008_0001
1. Equation (π)
Figure imgf000008_0001
[式中、 R1 及び!?2 は個別に低級アルキル基であり、 E3 はヒ ドロキシ基 又はハロゲン原子である] [Wherein, R 1 and!? 2 are independently a lower alkyl group, and E 3 is a hydroxy group or a halogen atom]
で示される トリアルコキシ安息香酸誘導体と式（III)：
Figure imgf000008_0002
And a trialkoxybenzoic acid derivative represented by the formula (III):
Figure imgf000008_0002
[式中、 E4 及び！?5 は低級アルキル基である] [Where E 4 and! ? 5 is a lower alkyl group]
で示されるジアルコキシベンズアルデヒ ドとをポリリン酸又はメ夕ンスル ホン酸の存在下に反応させることにより式（I ) ： Is reacted with a dialkoxybenzaldehyde represented by the following formula in the presence of polyphosphoric acid or maleic sulfonate to obtain a compound of the formula (I):
Figure imgf000008_0003
Figure imgf000008_0003
[式中、 R】、 R\ 4 及び R5 は前記の定義と同意義である〕 [Wherein, R], R \ 4 and R 5 are as defined above.]
で示されるフタリ ド化合物を製造する方法。 A method for producing a phthalide compound represented by the formula:
2 . β R2、 R 及び！?5 がメチル基である請求項 1に記載の方法。 2. β R 2 , R and! The method according to claim 1, wherein? 5 is a methyl group.
3 . R3 がヒ ドロキン基である時、 ポリ リン酸の存在下に反応させる請求 項 1又は請求項 2に記載の方法。 3. R 3 Gahi when Dorokin a group A method according to claim 1 or claim 2 is reacted in the presence of polyphosphoric acid.
4 . R3 がハロゲン原子である時、 メタンスルホン酸の存在下に反応させ る請求項 1又は請求項 2に記載の方法 c 4. When R 3 is a halogen atom, react in the presence of methanesulfonic acid. Method c as claimed in claim 1 or claim 2
PCT/JP1995/000850 1994-06-22 1995-04-28 Process for producing phthalide compound WO1995035291A1 (en)

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AU23530/95A AU2353095A (en) 1994-06-22 1995-04-28 Process for producing phthalide compound
JP50191796A JP3655311B2 (en) 1994-06-22 1995-04-28 Method for producing phthalide compound

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JP14006194 1994-06-22
JP6/140061 1994-06-22

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WO1995035291A1 true WO1995035291A1 (en) 1995-12-28

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PCT/JP1995/000850 WO1995035291A1 (en) 1994-06-22 1995-04-28 Process for producing phthalide compound

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JP (1) JP3655311B2 (en)
AU (1) AU2353095A (en)
WO (1) WO1995035291A1 (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63301878A (en) * 1987-05-30 1988-12-08 Ricoh Co Ltd Novel phthalide compound and production thereof
JPH05310634A (en) * 1991-10-17 1993-11-22 Shionogi & Co Ltd Lignan analogue and its production and antihyperlipidemia agent

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63301878A (en) * 1987-05-30 1988-12-08 Ricoh Co Ltd Novel phthalide compound and production thereof
JPH05310634A (en) * 1991-10-17 1993-11-22 Shionogi & Co Ltd Lignan analogue and its production and antihyperlipidemia agent

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AU2353095A (en) 1996-01-15
JP3655311B2 (en) 2005-06-02

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