FR2503152A1 - PROCESS FOR THE PREPARATION OF A- (3,4,5-TRIMETHOXYBENZOYLTHIO) -PROPIONYL GLYCINE - Google Patents
PROCESS FOR THE PREPARATION OF A- (3,4,5-TRIMETHOXYBENZOYLTHIO) -PROPIONYL GLYCINE Download PDFInfo
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- FR2503152A1 FR2503152A1 FR8206097A FR8206097A FR2503152A1 FR 2503152 A1 FR2503152 A1 FR 2503152A1 FR 8206097 A FR8206097 A FR 8206097A FR 8206097 A FR8206097 A FR 8206097A FR 2503152 A1 FR2503152 A1 FR 2503152A1
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- Prior art keywords
- trimethoxybenzoylthio
- glycine
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- propionyl
- cooh
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/21—Esters, e.g. nitroglycerine, selenocyanates
- A61K31/265—Esters, e.g. nitroglycerine, selenocyanates of carbonic, thiocarbonic, or thiocarboxylic acids, e.g. thioacetic acid, xanthogenic acid, trithiocarbonic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C325/00—Thioaldehydes; Thioketones; Thioquinones; Oxides thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C327/00—Thiocarboxylic acids
- C07C327/20—Esters of monothiocarboxylic acids
- C07C327/28—Esters of monothiocarboxylic acids having sulfur atoms of esterified thiocarboxyl groups bound to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C327/00—Thiocarboxylic acids
- C07C327/20—Esters of monothiocarboxylic acids
- C07C327/32—Esters of monothiocarboxylic acids having sulfur atoms of esterified thiocarboxyl groups bound to carbon atoms of hydrocarbon radicals substituted by carboxyl groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/21—Esters, e.g. nitroglycerine, selenocyanates
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Abstract
PROCEDE DE PREPARATION DE L'A-(3,4,5-TRIMETHOXYBENZOYLTHIO)-PROPIONYL GLYCINE, COMPOSE UTILE POUR SES PROPRIETES THERAPEUTIQUES. CE PROCEDE CONSISTE A FAIRE REAGIR UNE A-HALOGENOPROPIONYL GLYCINE AVEC DES SELS DE L'ACIDE 3,4,5-TRIMETHOXYBENZOYLTHIOBENZOIQUE OU A ACYLER LA GLYCINE AVEC L'ACIDE A-(3,4,5-TRIMETHOXYBENZOYLTHIO)-PROPIONIQUE.PROCESS FOR THE PREPARATION OF A- (3,4,5-TRIMETHOXYBENZOYLTHIO) -PROPIONYL GLYCINE, A COMPOUND USEFUL FOR ITS THERAPEUTIC PROPERTIES. THIS PROCESS CONSISTS OF REACTING AN A-HALOGENOPROPIONYL GLYCINE WITH SALTS OF 3,4,5-TRIMETHOXYBENZOYLTHIOBENZOIC ACID OR IN ACYLING GLYCIN WITH A- (3,4,5-TRIMETHOXYBENZOYLTHIO-ACID).
Description
ii
1 La présente invention concerne un nouveau procédé de préparation de 1' c- The present invention relates to a novel process for the preparation of
(3, 4, 5 - triméthoxybenzoylthio) - propionyl glycine: (3,4,5-trimethoxybenzoylthio) propionyl glycine:
CH3 - CH - CO- NH - CH2 - COOHCH3 - CH - CO - NH - CH2 - COOH
S OCHS OCH
S 3S 3
CO OCH3CO OCH3
OCH3 (I)OCH3 (I)
H3 Le composé () décrit dans la demande de brevet italien n 25 883 A/80 du 11/ 11/1980, possède d'utiles propriétés thérapeutiques pour le traitement des H3 The compound () described in Italian Patent Application No. 25883 A / 80 of 11/11/1980 has useful therapeutic properties for the treatment of
bronchopathies, des hêpatopathies et des suites d'empoisonnement. bronchopathies, hepatopathies and poisoning suites.
Selon la demande de brevet mentionné ci-dessus, celui-ci est obtenu par According to the patent application mentioned above, it is obtained by
acylation de 1' K - mercaptopropionyl glycine avec le chlorure de 3, 4, 5- acylation of K-mercaptopropionyl glycine with the chloride of 3, 4, 5
triméthoxybenzoyle. Cela implique évidement l'utilisation d' oC mercapto- trimethoxybenzoyl. This obviously involves the use of mercapto
propionyl glycine, produit cher et qui possède une odeur persistante et propionyl glycine, an expensive product with a persistent odor and
désagréable; de plus, les rendements de réaction ne sont pas très satis- unpleasant; moreover, the reaction yields are not very satisfactory.
faisants. A présent, on a trouvé qu'il était possible d'obtenir le composé (I) avec des rendements élevés et un coût nettement plus bas, en faisant réagir un pheasants. Now it has been found that it is possible to obtain the compound (I) in high yields and a much lower cost by reacting a
sel de l'acide 3, 4, 5 - triméthoxythiobenzoique (II)avec une c halogéno- salt of 3,4,5-trimethoxythiobenzoic acid (II) with a halogeno
propionyl glycine (III) selon leschémaA ci-dessous: propionyl glycine (III) according to Scheme A below:
SCHEMA ASCHEME A
Ar - C + CH3 -CH - CO - NH - CH2 - COOH--I) SMe Ar - C + CH3 - CH - CO - NH - CH2 - COOH - I) SMe
(II) (III)(II) (III)
dans lequel Ar représente le résidu 3, 4, 5 - triméthoxyphényle, alors que Me représente un métal alcalin, de préférence le sodium ou le potassium, ou l'équivalent d'un métal alcalino-terreux, de préférence le magnésium, et wherein Ar represents the residue 3, 4, 5-trimethoxyphenyl, while Me represents an alkali metal, preferably sodium or potassium, or the equivalent of an alkaline earth metal, preferably magnesium, and
X représente un halogène, de préférence le chlore ou le brome. X represents a halogen, preferably chlorine or bromine.
On effectue la réaction illustrée ci-dessus à des températures comprises entre O et 50 C, de préférence à température ambiante; sa progression est facilement suivie par CCM ( chromatographiesur couche mince). A température ambiante, la réaction est complète au bout de 24 heures; par acidification, The reaction illustrated above is carried out at temperatures between 0 and 50 ° C, preferably at room temperature; its progression is easily followed by TLC (thin layer chromatography). At room temperature, the reaction is complete after 24 hours; by acidification,
on obtient (I) dans un état de pureté satisfaisant. (I) is obtained in a state of satisfactory purity.
1 En alternative, on a trouvé qu'il est possible d'obtenir (I) de façon satis- Alternatively, it has been found that it is possible to obtain (I) satisfactorily
faisante par acylation de la glycine (V) avec un dérivé activé de l'acideo- by acylation of glycine (V) with an activated derivative of
(3, 4, 5 - triméthoxybenzoylthio) propionique (IV),selonle scnmra B ci- (3,4,5-trimethoxybenzoylthio) propionic acid (IV) according to
dessous:below:
SCH4EMA BSCH4EMA B
CH3 - CH - COY NH2 - CH2 -COOH - (I) CH3 - CH - COY NH2 - CH2 - COOH - (I)
S +S +
CO - ArCO - Ar
(IV) (V)(IV) (V)
dans lequel Ar a la même signification que ci-dessus, tandis que Y repré- in which Ar has the same meaning as above, while Y represents
sente un groupe activant, tel que Cl, -O-CO-O alkyle, alcoxyle. Le produit intermédiaire (IV) est quant à lui facilement accessible, par exemple par an activating group, such as Cl, -O-CO-O alkyl, alkoxyl. The intermediate product (IV) is in turn easily accessible, for example by
acylation de l'acide thiopropionique avec le chlorure de 3,4,5 triméthoxy- acylation of thiopropionic acid with 3,4,5-trimethoxy chloride
benzoyle. La réaction selon le schémaB se déroule de préférence à des 1mpé- benzoyl. The reaction according to scheme B preferably takes place at
ratures inférieures à 20 C, pour des durées comprises entre 4 et 20 heures. eratures below 20 C, for periods of between 4 and 20 hours.
On sépare le produit par filtration puis par recristallisation ultérieure. The product is separated by filtration and subsequent recrystallization.
Les exemples suivants illustrent les procédés selon l'invention. The following examples illustrate the processes according to the invention.
Exemple 1Example 1
a) 3,4,5 -triméthoxythiobenzoate de potassium On dissout 7,5 kg de KOH en paillettes dans 50 litres de méthanol; tout en refroidissant extérieurement jusqu'à environ 15 C, on ajoute 4,1 Kg de a) Potassium 3,4,5-trimethoxythiobenzoate 7.5 kg of flaky KOH are dissolved in 50 liters of methanol; while cooling externally to approximately 15 ° C., 4.1 kg of
H2S, jusqu'à disparition de l'alcalinité. En maintenant encore la tempéra- H2S, until disappearance of the alkalinity. Keeping the temperature still
ture à 15 C, on ajoutepar portions 15 Kg de chlorure de 3,4,5 - trimétho- at 15 ° C., 15 kg of 3,4,5-trimethoxychloride are added portionwise
xybenzoyle et on laisse toute la nuit l'agitateur en fonctionnement. On élimine ensuite, à pression réduite, presque tout le méthanol, et on reprend - le résidu avec une solution de 9 kg de K CO dans 100 litres d'eau. On 2 3 xybenzoyl and the stirrer is left running overnight. Then, under reduced pressure, almost all the methanol is removed, and the residue is taken up with a solution of 9 kg of K CO in 100 liters of water. On 2 3
filtre la solution et on l'utilise pour la réaction suivante. filter the solution and use it for the next reaction.
b) o -(3,4,5, - triméthoxybenzoylthio) propionyl glycine (I) b) o - (3,4,5,4-trimethoxybenzoylthio) propionyl glycine (I)
On ajoute la solutionobtenue en a) à une solution de 13,6 kg d' l - bromo- The solution obtained in (a) is added to a solution of 13.6 kg of bromine.
propionyl glycine et de 9 kg de K2 CO3 dans 50 litres d'eau et on laisse l'ensemble pendant 24 heures en maintenant l'agitateur en marche. A ce moment là, les produits de départ ne sont plus identifiés parCCM. On amène la propionyl glycine and 9 kg of K 2 CO 3 in 50 liters of water and the mixture is left for 24 hours while keeping the stirrer running. At this point, the starting products are no longer identified by CCM. We bring the
solution dans un mélange de 200 litres d'eau et de 150 litres de HC1 concen- solution in a mixture of 200 liters of water and 150 liters of concentrated HC1
tré. On centrifuge le précipité, on le lave à l'eau, on le sèche et on le tré. The precipitate is centrifuged, washed with water, dried and
recristallise dans l'éthanol. On obtient 18 kg (80%) d' D -(3,4,5 - recrystallizes in ethanol. We obtain 18 kg (80%) of D - (3,4,5 -
triméthoxybenzoylthio) propionyl glycine, p.f. 174 - 175 C, dont la pureté trimethoxybenzoylthio) propionyl glycine, m.p. 174 - 175 C, whose purity
est confirmée par CCM.is confirmed by CCM.
Exemple 2Example 2
1 On opère selon la même procédure que dans l'exemple 1, mais en utilisant le sel de sodium de l'acide 3,4,5 - triméthoxythiobenzoique. On obtient (I) The procedure is as in Example 1, but using the sodium salt of 3,4,5-trimethoxythiobenzoic acid. We get (I)
avec un rendement de 66,5 %.with a yield of 66.5%.
Exemple 3Example 3
On opère comme dans l'exemple 1, mais en remplaçant 1' u -bromopropionyl glycine par une quantité équivalente du dérivé chloro correspondant. On The procedure is as in Example 1, but replacing 1-u-bromopropionyl glycine with an equivalent amount of the corresponding chloro derivative. We
obtient (I) avec un rendement de 73%. obtains (I) with a yield of 73%.
Exemple 4Example 4
On procède comme dans l'exemple 1-mais en utilisant le sel de magnésium de The procedure is as in Example 1 but using the magnesium salt of
l'acide 3,4,5 -triméthoxythiobenzoique. Le rendement en (I) est de 46%. 3,4,5-trimethoxythiobenzoic acid. The yield in (I) is 46%.
Exemple 5Example 5
a) acide "-(3,4,5 - triméthoxybenzoylthio) propionique A une solution de 3,3 kg de K2 CO3 dans 9 litres d'eau, on ajoute, entre et 20 C, 767 ml d'acide c -thiopropionique ( acide thiolactique commercial, densité 1,2); ensuite, à la même température et en 2 fractions, on ajoute 2 kg de chlorure de 3,4,5 - triméthoxybenzoyle. Après une nuit d'agitation à température ambiante, on acidifie avec HCl 1:1 et on extrait avec 3 portions de 15 litres de toluene. Après lavage àl'eau et évaporation de la solution de toluene, on recueille 2,6 kg d'un produit huileux dont les a) - (3,4,5-trimethoxybenzoylthio) propionic acid To a solution of 3.3 kg of K 2 CO 3 in 9 liters of water, 767 ml of c-thiopropionic acid ( commercial thiolactic acid, density 1,2), then at the same temperature and in 2 fractions, 2 kg of 3,4,5-trimethoxybenzoyl chloride are added, and after stirring overnight at room temperature, the mixture is acidified with HCl. 1: 1 and extracted with 3 portions of 15 liters of toluene After washing with water and evaporation of the toluene solution, 2.6 kg of an oily product are collected.
données analytiques concordent avec l'analyse calculée. Analytical data is consistent with the calculated analysis.
b). -(3,4,5 -triméthoxybenzoylthio) propionYl glycine (I) On ajoute graduellement le composé obtenu dans l'exemple 5a) ( 2,6 kg) à 7 litres de chlorure de thionyle.On laisse sous agitation toute la nuit, on évapore l'excès de SOCl2, on traite avec 3 litres de benzène et on évapore à nouveau sous vide. On ajoute graduellement le résidu obtenu (2, 7 kg) à une solution de 730 g de glycine et 290 g de K2 C0O3 dans 10 litres d'eau, en évitant que la température n'excède 20 C. Une fois l'addition terminée, on laisse sous agitation toute la nuit à température ambiante, puis on ajoute une solution glacée de HC1 1:1 pour obtenir un pH2. On sépare le précipité par filtration, on lave vigoureusement à l'eau et on recristallise dans le méthanol. On obtient 2,03 kg de produit avec un p. f. de 172 - 174 C b). - (3,4,5-Trimethoxybenzoylthio) propionyl glycine (I) The compound obtained in Example 5a) (2.6 kg) is gradually added to 7 liters of thionyl chloride. The mixture is stirred overnight. evaporates the excess SOCl 2, treated with 3 liters of benzene and evaporated again under vacuum. The obtained residue (2.7 kg) is gradually added to a solution of 730 g of glycine and 290 g of K 2 CO 3 in 10 liters of water, avoiding that the temperature exceeds 20 C. After the addition is complete The mixture is left stirring overnight at room temperature and an ice-cold 1: 1 solution of HCl is added to obtain pH2. The precipitate is filtered off, washed vigorously with water and recrystallized from methanol. We obtain 2.03 kg of product with a p. f. from 172 - 174 C
(rendement environ 68 %).(yield about 68%).
Exemple 6Example 6
On dissout 288 g ( 1 mole) d'acide. -(3,4,5 - triméthoxybenzoylthio) propionique, obtenu selon l'exemple 5a), dans 5 litres de chloroforme, auquel on ajoute en refroidissant à 10-15 C, 108 g (lmole) de chlorocarbonate d' éthyle puis 101 g ( 1 mole) de triéthylamine. A la solution d'anhydride mixte ainsi obtenue on ajoute 75 g (1 mole) de glycine, en brassant. Après 36 heures 1 d'agitation à température ambiante, on traite avec 2 kg de glace pilée et on ajoute HC1 1:1 jusqu'à ce que la solution soit acide (pH 1-2). Cn sépare la solution de chloroforme, on lave à l'eau et on évapore jusqu'à siccité. On recristallise le résidu dans l'éthanol; on obtient (1) avec un rendement de 63 %, p.f. 173 - 1750 C. 288 g (1 mole) of acid are dissolved. - (3,4,5-trimethoxybenzoylthio) propionic acid, obtained according to Example 5a), in 5 liters of chloroform, to which is added while cooling at 10-15 C, 108 g (lmol) of ethyl chlorocarbonate and then 101 g (1 mole) triethylamine. To the mixed anhydride solution thus obtained was added 75 g (1 mole) of glycine, stirring. After 36 hours stirring at room temperature, treated with 2 kg of crushed ice and added HCl 1: 1 until the solution is acidic (pH 1-2). The chloroform solution is separated, washed with water and evaporated to dryness. The residue is recrystallized from ethanol; (1) is obtained with a yield of 63%, m.p. 173 - 1750C
Claims (9)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT20976/81A IT1144700B (en) | 1981-04-07 | 1981-04-07 | PROCEDURE FOR THE PREPARATION OF A GLYCINE DERIVATIVE |
Publications (2)
Publication Number | Publication Date |
---|---|
FR2503152A1 true FR2503152A1 (en) | 1982-10-08 |
FR2503152B1 FR2503152B1 (en) | 1985-10-25 |
Family
ID=11174880
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
FR8206097A Expired FR2503152B1 (en) | 1981-04-07 | 1982-04-07 | PROCESS FOR THE PREPARATION OF A- (3,4,5-TRIMETHOXYBENZOYLTHIO) -PROPIONYL GLYCINE |
FR8214305A Expired FR2510565B1 (en) | 1981-04-07 | 1982-08-18 | PROCESS FOR THE PREPARATION OF A- (3,4,5-TRIMETHOXYBENZOYLTHIO) -PROPIONYL GLYCINE |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
FR8214305A Expired FR2510565B1 (en) | 1981-04-07 | 1982-08-18 | PROCESS FOR THE PREPARATION OF A- (3,4,5-TRIMETHOXYBENZOYLTHIO) -PROPIONYL GLYCINE |
Country Status (7)
Country | Link |
---|---|
JP (1) | JPS5941985B2 (en) |
CA (1) | CA1171877A (en) |
DE (1) | DE3212766A1 (en) |
FI (1) | FI821046L (en) |
FR (2) | FR2503152B1 (en) |
GB (1) | GB2096144B (en) |
IT (1) | IT1144700B (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3243369A1 (en) * | 1982-11-24 | 1984-05-24 | Basf Ag, 6700 Ludwigshafen | BIS- (BENZOYLTHIO) CARBONIC ACIDS, THEIR PRODUCTION AND USE FOR THE PRODUCTION OF ACTIVE SUBSTANCES |
DE3533124A1 (en) * | 1985-09-17 | 1987-03-26 | Bosch Gmbh Robert | SPARK PLUG WITH GLIDING RANGE |
JPH0745461B2 (en) * | 1985-12-19 | 1995-05-17 | 旭化学工業株式会社 | Thiobenzoic acid derivative, sensitizer for heat-sensitive recording comprising the derivative, and heat-sensitive recording material containing the same |
JP5947726B2 (en) * | 2011-08-17 | 2016-07-06 | 日本特殊陶業株式会社 | Gas sensor |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3246025A (en) * | 1961-11-02 | 1966-04-12 | Santen Pharmaceutical Co Ltd | Mercaptopropionic acid derivatives |
FR2495145A1 (en) * | 1980-11-11 | 1982-06-04 | Ausonia Farma Srl | A- (3,4,5-TRIMETHOXYBENZOYLTHIO) PROPIONYLGLYCIN, PROCESS FOR PREPARING THE SAME, AND PHARMACEUTICAL COMPOSITIONS CONTAINING THE SAME |
-
1981
- 1981-04-07 IT IT20976/81A patent/IT1144700B/en active
-
1982
- 1982-03-24 FI FI821046A patent/FI821046L/en not_active Application Discontinuation
- 1982-03-31 CA CA000400230A patent/CA1171877A/en not_active Expired
- 1982-04-05 GB GB8209992A patent/GB2096144B/en not_active Expired
- 1982-04-06 JP JP57057466A patent/JPS5941985B2/en not_active Expired
- 1982-04-06 DE DE19823212766 patent/DE3212766A1/en not_active Ceased
- 1982-04-07 FR FR8206097A patent/FR2503152B1/en not_active Expired
- 1982-08-18 FR FR8214305A patent/FR2510565B1/en not_active Expired
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3246025A (en) * | 1961-11-02 | 1966-04-12 | Santen Pharmaceutical Co Ltd | Mercaptopropionic acid derivatives |
FR2495145A1 (en) * | 1980-11-11 | 1982-06-04 | Ausonia Farma Srl | A- (3,4,5-TRIMETHOXYBENZOYLTHIO) PROPIONYLGLYCIN, PROCESS FOR PREPARING THE SAME, AND PHARMACEUTICAL COMPOSITIONS CONTAINING THE SAME |
Also Published As
Publication number | Publication date |
---|---|
FR2510565B1 (en) | 1985-08-30 |
FR2510565A1 (en) | 1983-02-04 |
GB2096144B (en) | 1984-12-19 |
DE3212766A1 (en) | 1982-11-04 |
JPS5941985B2 (en) | 1984-10-11 |
FR2503152B1 (en) | 1985-10-25 |
GB2096144A (en) | 1982-10-13 |
CA1171877A (en) | 1984-07-31 |
JPS57179155A (en) | 1982-11-04 |
FI821046L (en) | 1982-10-08 |
IT1144700B (en) | 1986-10-29 |
FI821046A0 (en) | 1982-03-24 |
IT8120976A0 (en) | 1981-04-07 |
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