JPS6054941B2 - Method for producing m-benzoylhydroatropaic acid - Google Patents
Method for producing m-benzoylhydroatropaic acidInfo
- Publication number
- JPS6054941B2 JPS6054941B2 JP7589878A JP7589878A JPS6054941B2 JP S6054941 B2 JPS6054941 B2 JP S6054941B2 JP 7589878 A JP7589878 A JP 7589878A JP 7589878 A JP7589878 A JP 7589878A JP S6054941 B2 JPS6054941 B2 JP S6054941B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- benzoylhydroatropaic
- reaction
- anhydride
- manufacturing
- 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.)
- Expired
Links
- 239000002253 acid Substances 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003377 acid catalyst Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- QMBSRJCMJQPYRS-UHFFFAOYSA-N 3-methyl-4-(5-oxo-5-phenylpentyl)furan-2,5-dione Chemical compound C/C=1/C(=O)OC(C1CCCCC(=O)C1=CC=CC=C1)=O QMBSRJCMJQPYRS-UHFFFAOYSA-N 0.000 claims 1
- 150000008064 anhydrides Chemical class 0.000 description 11
- 239000000543 intermediate Substances 0.000 description 5
- 150000002596 lactones Chemical class 0.000 description 5
- PVHNKILPLXXDDZ-UHFFFAOYSA-N 2-phenylcycloheptan-1-one Chemical compound O=C1CCCCCC1C1=CC=CC=C1 PVHNKILPLXXDDZ-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229940076788 pyruvate Drugs 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YTVQIZRDLKWECQ-UHFFFAOYSA-N 2-benzoylcyclohexan-1-one Chemical compound C=1C=CC=CC=1C(=O)C1CCCCC1=O YTVQIZRDLKWECQ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 2
- -1 pyruvate ester Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LCTONWCANYUPML-UHFFFAOYSA-M Pyruvate Chemical compound CC(=O)C([O-])=O LCTONWCANYUPML-UHFFFAOYSA-M 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000007273 lactonization reaction Methods 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/76—Unsaturated compounds containing keto groups
- C07C59/84—Unsaturated compounds containing keto groups containing six membered aromatic rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Furan Compounds (AREA)
Description
【発明の詳細な説明】
本発明はｍ−ベンゾイルヒドロアトロパ酸の新規製造方
法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing m-benzoylhydroatropaic acid.
式Ｉで示されるｍ−ベンゾイルヒドロアトロパ酸は、ヒ
トの病気の治療において、広い有用性を有することが知
られている化合物である。m-Benzoylhydroatropaic acid of formula I is a compound known to have wide utility in the treatment of human diseases.
Ｏ、（Ｉ）
”ＣＨ−ＣＯＯＨ
この化合物の製造方法としては、３種の異なつた方法が
知られている。O, (I) "CH-COOH Three different methods are known for producing this compound.
フランス特許番号１５４６４７８号に記載されている第
１の方法は、工程数が多く、毒性の強い試剤（例えばＫ
ＣＮ）または刺激性を有する試剤（例えばＮ−ベンゾイ
ルベンジルブロミド）を必要とする、フランス特許番号
１５４６４７８号第１追加および２１６３８５７号に記
載されている第２および第３の方法は、明らかに実験室
的なものであり、工業的規模で実施し得る可能性がほと
んどないものである。The first method, described in French patent no.
The second and third methods described in French patent no. There is little possibility of it being implemented on an industrial scale.
イタリア特許第４９９２５Ａ／７５号に記載されている
第４の方法は、本願発明者によるものであり、全く新し
い反応を使用したものであつて、容易に入手し得る出発
物質を用いて、好収率でｍ−ベンゾイルヒドロアトロパ
酸を製造するものである。この反応は以下の反応式で表
すことができる。本発明は、この方法の改良方法に関す
るものである。A fourth method, described in Italian patent no. It produces m-benzoylhydroatropaic acid at a high rate. This reaction can be expressed by the following reaction formula. The present invention relates to an improvement to this method.
この改良方法は、取扱いの容易な、より安定な中間体を
経由するものであつて、最終工程において副産物を含ま
ない生成物を与え、従つて精製がより簡単であるという
特徴を有する。この反応は以下の反応式で示すことがで
きる。This improved process is characterized by being via easier-to-handle, more stable intermediates, giving a by-product-free product in the final step, and therefore simpler purification. This reaction can be shown by the following reaction formula.
２−フエニルーシクロヘプタノン（■）をピルビン酸の
エステル（エチルまたはメチルエステル）と、無溶媒て
、酸触媒の存在下で縮合させると不飽和ラクトン（■）
が得られる。When 2-phenyl-cycloheptanone (■) is condensed with an ester of pyruvic acid (ethyl or methyl ester) without a solvent in the presence of an acid catalyst, an unsaturated lactone (■) is produced.
is obtained.
この反応は使用するピルビン酸エステルの沸謄温度で行
われる。この条件下では、中間体（■）を得るのに必要
な３つの反応（アルドール化反応（ＡｌｄＯｌｙｚａｔ
ｉＯｎ）、クロトン化反応（ＣｒＯｔＯｎｉｚａｔｊＯ
ｎ）およびラクトン化反応（１ａｃｔ０ｎｉｚａｔｉ０
ｎ）を単一工程で行なうことができる。この反応混合物
から、通常の方法で、例えば蒸留法で中間体（■）を単
離する。このラクトン（■）は、クロム酸酸化により容
易に、好収率で２−メチルー３−（５−フェニルー５−
ケトーペンチル）一無水マレイン直■）に変換すること
ができ、これを、密閉容器中、過剰の濃ＨＣｌと共に数
時間２００〜２４０℃で加熱するか、あるいは開放容器
中、複素環式塩基の塩酸塩（例えばピリジンＨＣりと共
に温度で加熱することにより、ｍ−ベンゾイルヒドロア
トロパ酸０）が好収率で得られる。This reaction is carried out at the boiling temperature of the pyruvate ester used. Under these conditions, the three reactions necessary to obtain the intermediate (■) (aldolization reaction (AldOlyzat
iOn), crotonation reaction (CrOtOnizatjO
n) and lactonization reaction (1act0nizati0
n) can be carried out in a single step. The intermediate (■) is isolated from this reaction mixture in a conventional manner, for example by distillation. This lactone (■) can be easily converted into 2-methyl-3-(5-phenyl-5-5-
ketopentyl) monoanhydride), which can be heated at 200-240° C. for several hours with excess concentrated HCl in a closed container or converted into the hydrochloride of the heterocyclic base in an open container. (For example, by heating at temperature with pyridine HC, m-benzoylhydroatropaic acid 0) is obtained in good yield.
本発明方法の要所は最終工程、即ち、ｍ−ベンゾイルヒ
ドロアトロパ酸（１）を製造するに際し、２−メチルけ
３−（５−フェニルー５−ケトーペンチル）一無水マレ
イン醜■）を酸性雰囲気中で加熱することにある。The key point of the method of the present invention is the final step, that is, when producing m-benzoylhydroatropaic acid (1), 2-methyl-3-(5-phenyl-5-ketopentyl) monoanhydride (maleic anhydride) is mixed in an acidic atmosphere. The purpose is to heat it inside.
この無水物は、実際に、種々の方法で得ることもできる
。This anhydride can in fact also be obtained in various ways.
例えば前記イタリア特許出願第４９９２５Ａ／７５号に
記載されている。For example, it is described in the aforementioned Italian Patent Application No. 49925A/75.
２−ベンゾイルシクロヘキサノン（■）とピルビン酸エ
ステル（■）との縮合を、ある特定の条件下で行なうと
、ラクトン（■）と共に、かなりの収量でこの無水物（
■）を得ることができる。When the condensation of 2-benzoylcyclohexanone (■) and pyruvate ester (■) is carried out under certain conditions, this anhydride (■) is produced in considerable yield along with the lactone (■).
■) can be obtained.
ラクトン（■）の製造においては、粗反応混合物を希ア
ルカリで処理するだけで、実際に、この無水物を副産物
として分離して来た。この条件下では、無水物は醜■）
のナトリウム塩として溶解している。周知の如く、２．
３−ジ置換マレイン酸は遊離の状態では存在しにくく、
無水物の形で存在しやすい傾向があるので、この溶液を
酸性化することにより、直接その無水物を得ることがで
きる。In the production of lactone (■), this anhydride has actually been separated as a by-product simply by treating the crude reaction mixture with dilute alkali. Under these conditions, the anhydride is ugly■)
It is dissolved as the sodium salt of As is well known, 2.
3-disubstituted maleic acid is difficult to exist in a free state;
Since it tends to exist in the anhydride form, the anhydride can be obtained directly by acidifying this solution.
いずれにせよ、前記イタリア特許出願に記載された条件
下で、２−ベンゾイルーシクロヘキサノンをピルビン酸
エチル（またはメチル）と縮合させると、３つの実施例
全てにおいて示されている様に、実質的にはラクトンが
生成し、この無水物（■）は無視し得る程度の量の不純
物として存在するに過ぎない。一方、もしこの縮合反応
をＰ−トルエンースルホン酸の存在下で行なうと、無水
物の収量は、得られる縮合生成物全量の１１３となる。
この無水物が分離し得るのは、事実、この種の混合物か
らである。以下の実施例においては、２−フエニルーシ
クロヘプタノンを出発物質とするこの無水物中間体の選
択的合成法および、次いでこの中間体を芳香環化してｍ
−ベンゾイルヒドロアトロパ酸を得る合成法について述
べる。In any case, condensation of 2-benzoylcyclohexanone with ethyl (or methyl) pyruvate under the conditions described in the said Italian patent application results in substantially A lactone is formed, and this anhydride (■) is only present as an impurity in a negligible amount. On the other hand, if this condensation reaction is carried out in the presence of P-toluene-sulfonic acid, the yield of anhydride will be 113 of the total amount of condensation product obtained.
It is in fact from mixtures of this kind that this anhydride can be separated. The following examples describe the selective synthesis of this anhydride intermediate starting from 2-phenyl-cycloheptanone and the subsequent aromatic cyclization of this intermediate to m
- A synthetic method for obtaining benzoylhydroatropaic acid will be described.
実施例
Ａ２−ケトー３−メチルー８−フェニルー２，５．６，
７−テトラヒドロー止ージシクロヘプタ〔ｂ〕フラン２
−フエニルーシクロヘプタノン９．４ｆ１ピルビン酸メ
チル１５．３ｇおよびＰ−トルエンスルホン酸０．５ｙ
の混合物を還流条件下で１６時間加熱する。Example A 2-keto 3-methyl-8-phenyl-2,5.6,
7-Tetrahydro dicyclohepta[b]furan 2
-Phenyl-cycloheptanone 9.4f1 Methyl pyruvate 15.3g and P-toluenesulfonic acid 0.5y
The mixture is heated under reflux conditions for 16 hours.
加熱を終了したら、この反応混合物をエーテルに溶かし
、この溶液を重炭酸ナトリウム溶液で洗浄する。溶媒を
留去した後の残留物を蒸留する。低沸点フラクシヨンに
おいて、２−フエニルーシクロヘプタノン４ｙを回収し
、２０２〜２０５１７ｆｒＩ！ＬＨｇの留分４．７ｙを
得る。この生成物を放置すると固化するのでこれをヘキ
サンー酢酸エチルで再結晶する。融点：１１８〜１２０
℃元素分析 ＣＨＮＭＲ
スペクトル（ＣＤＣｌ３、ＴＭＳ）
７．３５δにマルチプレツト、５Ｈ（芳香族ｑ旦）２．
７５δにマルチプレツト、４Ｈ（ＣＨ２−Ｃ＝Ｃ）１．
９δにマルチプレツト、７Ｈ（９■−Ｃ＝ＣおよびＣＨ
２）Ｂ２−メチルー３−（５−フェニルー５−ケトーペ
ンチル）一無水マレイン酸上で得た生成物９．９ｙをベ
ンゼン１２０ｃｃに溶解する。After heating has ended, the reaction mixture is dissolved in ether and the solution is washed with sodium bicarbonate solution. The residue after distilling off the solvent is distilled. In the low-boiling fraction, 2-phenyl-cycloheptanone 4y was recovered, giving 202-20517frI! A fraction of 4.7y of LHg is obtained. Since this product solidifies if left to stand, it is recrystallized from hexane-ethyl acetate. Melting point: 118-120
°C Elemental Analysis CHNMR Spectrum (CDCl3, TMS) Multiplet at 7.35δ, 5H (aromatic qdan)2.
Multiplet at 75δ, 4H(CH2-C=C)1.
Multiplet at 9δ, 7H (9■-C=C and CH
2) 9.9y of the product obtained on B2-methyl-3-(5-phenyl-5-ketopentyl)monomaleic anhydride is dissolved in 120 cc of benzene.
次いでこれに、水４０ｍＬに溶解したクロム酸ナトリウ
ム溶液を少量づつ加える。次いでこれに、反応混合物の
温度が２５℃を超えない様に激しく攪拌しながら、濃硫
酸４４ｍ１を水４４ｍ１で希釈した溶液を滴下する。添
加が終了してから４時間、この混合物を室温で激しく攪
拌し続ける。次いで有機層を分離し、溶媒を減圧下で留
去すると、油７．０ｙが得られ、これは急速に固化する
。この一部をヘキサンー酢酸エチルで再結晶する。融点
：７２〜５℃ノ
ＮＭＲスペクトル（ＣＤＣｌ３、ＴＭＳ）７．９５δに
複雑なマルチプレツト、２Ｈ（芳香族オルト位ＣＨ）７
．５５δに複雑なマルチプレツト、３Ｈ（芳香族メタお
よびバラ位ＣＪＪ）３δにトリプレツト（Ｊ＝６ｃｐｓ
）２Ｈ（Ｃ？ＣＯ）２．５３δにトリプレツト （Ｊ＝
６ＣｐＳ）、２Ｈ（Ｃ川一Ｃ＝Ｃ）２．０８δにシング
レット、３１（（ＣＨ３−）１．７δに複雑なマルチプ
レツト、４Ｈ（−Ｃ川一Ｃ曳−）Ｃｍ−ベンゾイルヒド
ロアトロパ酸
リービツヒ冷却器を備えた丸底フラスコ中で、Ｂによつ
て得た生成物１０．２ｙおよびピリジンＨＣｌ５Ｏｑの
混合物を、浴温を２３０〜２４０℃に保ちながら６時間
加熱する。A sodium chromate solution dissolved in 40 ml of water is then added in portions to this. Next, a solution prepared by diluting 44 ml of concentrated sulfuric acid with 44 ml of water is added dropwise to this while stirring vigorously so that the temperature of the reaction mixture does not exceed 25°C. The mixture is kept under vigorous stirring at room temperature for 4 hours after the addition is complete. The organic layer is then separated and the solvent is distilled off under reduced pressure, yielding 7.0y of an oil which solidifies rapidly. A portion of this is recrystallized from hexane-ethyl acetate. Melting point: 72-5°C NMR spectrum (CDCl3, TMS) 7.95 δ complex multiplet, 2H (aromatic ortho position CH) 7
．． Complex multiplet at 55δ, 3H (aromatic meta and rose position CJJ) triplet at 3δ (J=6cps
)2H(C?CO)2.53δ triplet (J=
6CpS), 2H (C=C) singlet at 2.08δ, 31 ((CH3-) complex multiplet at 1.7δ, 4H(-C-)Cm-benzoylhydroatropaic acid In a round bottom flask equipped with a Liebig condenser, a mixture of 10.2y of the product obtained from B and 5Oq of pyridine HCl is heated for 6 hours, keeping the bath temperature at 230-240°C.
Claims (1)
チル）−無水マレイン酸を酸触媒の存在下で加熱するこ
とを特徴とするｍ−ベンゾイルヒドロアトロパ酸の製造
方法。 ２ 約２００〜２４０℃で加熱することを特徴とする第
１項記載の製造方法。 ３ 酸触媒が塩酸である第１項または第２項のいずれか
に記載の製造方法。 ４ 反応を密閉容器中で実施する第１項ないし第３項の
いずれかに記載の製造方法。 ５ 酸触媒が複素環式塩基の塩酸塩であり、反応を開放
容器中で実施する第１項または第２項のいずれかに記載
の製造方法。 ６ 複素環方塩基がピリジンである第５項記載の製造方
法。[Claims] 1. A method of preparing m-benzoylhydroatropaic acid by heating 2-methyl-3-(5-phenyl-5-keto-pentyl)-maleic anhydride in the presence of an acid catalyst. Production method. 2. The manufacturing method according to item 1, which comprises heating at about 200 to 240°C. 3. The manufacturing method according to any one of Items 1 and 2, wherein the acid catalyst is hydrochloric acid. 4. The manufacturing method according to any one of Items 1 to 3, wherein the reaction is carried out in a closed container. 5. The production method according to any one of paragraphs 1 and 2, wherein the acid catalyst is a hydrochloride of a heterocyclic base and the reaction is carried out in an open vessel. 6. The manufacturing method according to item 5, wherein the heterocyclic base is pyridine.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT2491977 | 1977-06-22 | ||
| IT24919A/77 | 1977-06-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS549251A JPS549251A (en) | 1979-01-24 |
| JPS6054941B2 true JPS6054941B2 (en) | 1985-12-03 |
Family
ID=11215138
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7589878A Expired JPS6054941B2 (en) | 1977-06-22 | 1978-06-21 | Method for producing m-benzoylhydroatropaic acid |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS6054941B2 (en) |
| FR (1) | FR2395248A1 (en) |
| GB (1) | GB2000502B (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1035947B (en) * | 1975-06-05 | 1979-10-20 | Acraf | SYNTHESIS OF HYDRATROPIC M. BENZOIL ACID |
-
1978
- 1978-06-15 GB GB7827038A patent/GB2000502B/en not_active Expired
- 1978-06-21 JP JP7589878A patent/JPS6054941B2/en not_active Expired
- 1978-06-22 FR FR7818758A patent/FR2395248A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| FR2395248A1 (en) | 1979-01-19 |
| JPS549251A (en) | 1979-01-24 |
| GB2000502A (en) | 1979-01-10 |
| GB2000502B (en) | 1982-01-06 |
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