DE1543893C3 - Process for the preparation of N- (diethylaminoethyl) -2-methoxy-4-amino-5-chlorobenzamide - Google Patents

Process for the preparation of N- (diethylaminoethyl) -2-methoxy-4-amino-5-chlorobenzamide

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Publication number
DE1543893C3
DE1543893C3 DE1543893A DE1543893A DE1543893C3 DE 1543893 C3 DE1543893 C3 DE 1543893C3 DE 1543893 A DE1543893 A DE 1543893A DE 1543893 A DE1543893 A DE 1543893A DE 1543893 C3 DE1543893 C3 DE 1543893C3
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DE
Germany
Prior art keywords
methoxy
amino
diethylaminoethyl
nitro
chlorobenzamide
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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
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DE1543893A
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German (de)
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DE1543893B2 (en
DE1543893A1 (en
Inventor
Gerard Paris Bulteau
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D'ETUDES SCIENTIFIQUES ET INDUSTRIELLES DE L'ILE-DE-FRANCE PARIS Ste
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D'ETUDES SCIENTIFIQUES ET INDUSTRIELLES DE L'ILE-DE-FRANCE PARIS Ste
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Priority to DE19661793772 priority Critical patent/DE1793772B2/en
Publication of DE1543893A1 publication Critical patent/DE1543893A1/en
Publication of DE1543893B2 publication Critical patent/DE1543893B2/en
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Publication of DE1543893C3 publication Critical patent/DE1543893C3/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/42—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/44—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C235/50—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by nitrogen atoms not being part of nitro or nitroso groups

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Hydrogenated Pyridines (AREA)

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von N-(Diäthylaminoäthyl)-2-methoxy-4-amino-5-chlorbenzamid aus 2-Amino-4-chlor-5-nitroanisol. The invention relates to a method of manufacture of N- (diethylaminoethyl) -2-methoxy-4-amino-5-chlorobenzamide from 2-amino-4-chloro-5-nitroanisole.

Die erfindungsgemäß hergestellte Verbindung ist unter dem internationalen Freinamen Metoclopramid als wirksames Antiemetikum bekannt. Stellt man diese Verbindung gemäß dem aus der französischen Patentschrift 1 313 758 bekannten Verfahren durch Umsetzung des entsprechend substituierten Benzoylchlorids mit Diäthylaminoäthylamin her, so erhält man ein Produkt mit einem Schmelzpunkt von 134 bis 135° C und einem im Tierversuch ermittelten DEso-Wert von 22,5 mg/kg.The compound produced according to the invention is available under the international non-proprietary name metoclopramide known as an effective anti-emetic. If one puts this connection according to the one from the French Patent 1,313,758 known method by reacting the appropriately substituted benzoyl chloride with diethylaminoethylamine, a product with a melting point of 134 is obtained up to 135 ° C and a DE 50 value of 22.5 mg / kg determined in animal experiments.

Es wurde nun gefunden, daß man die genannte Verbindung wesentlich reiner, d. h. mit einem Schmelzpunkt von 148° C und einem DEso-Wert von 37,9 mg/kg erhalten kann, wenn man aus der Diazoniumverbindung des Ausgangsprodukts mit Kupfer(I)-cyanid in an sich bekannter Weise nach der Sandmeyerreaktion 2-Cyan-4-chlor-5-nitroanisol herstellt, dieses mit Methanol in Gegenwart von rauchender Schwefelsäure zum Methylester der 2-Methoxy-4-nitro-5-chlorbenzoesäure hydrolysiert, der dann in an sich bekannter Weise mit Diäthylaminoäthylamin zum N-(Diäthylaminoäthyl)-2-methoxy-4-nitro-5-chlorbenzamid umgesetzt wird, und man die so erhaltene Verbindung in an sich bekannter Weise zum N-(Diäthylaminoäthyl)-2-methoxy-4-amino-5-chlorbenzamid reduziert.It has now been found that the compound mentioned can be obtained in a much more pure manner, i.e. H. with a Melting point of 148 ° C and a DE 50 value of 37.9 mg / kg can be obtained if one from the Diazonium compound of the starting product with copper (I) cyanide in a manner known per se the Sandmeyer reaction produces 2-cyano-4-chloro-5-nitroanisole, this with methanol in the presence of fuming Sulfuric acid hydrolyzed to the methyl ester of 2-methoxy-4-nitro-5-chlorobenzoic acid, the then in a known manner with diethylaminoethylamine to give N- (diethylaminoethyl) -2-methoxy-4-nitro-5-chlorobenzamide is reacted, and the compound thus obtained is converted in a manner known per se to N- (diethylaminoethyl) -2-methoxy-4-amino-5-chlorobenzamide reduced.

Das Ausgangsprodukt, 2-Amino-4-chlor-5-nitroanisol, kann erhalten werden, indem man p-Chlorphenol nitriert, das gebildete 2-Nitro-4-chlorphenol methyüert, das gebildete 2-Nitro-4-chloranisol reduziert und acetyliert, das dabei gebildete 2-Acetylamino-4-chloranisol nitriert und das so gebildete 2-Acetylamino-4-chlor-5-nitroanisol hydrolysiert.The starting product, 2-amino-4-chloro-5-nitroanisole, can be obtained by adding p-chlorophenol nitrated, methylated the 2-nitro-4-chlorophenol formed, reduced the 2-nitro-4-chloroanisole formed and acetylated, the 2-acetylamino-4-chloroanisole thus formed nitrated and hydrolyzed the 2-acetylamino-4-chloro-5-nitroanisole thus formed.

Das Verfahren der Erfindung wird im folgenden an Hand eines Ausführungsbeispiels näher erläutert.The method of the invention is explained in more detail below using an exemplary embodiment.

Herstellung von 2-Methoxy-4-nitro-5-chlorbenzonitril Preparation of 2-methoxy-4-nitro-5-chlorobenzonitrile

a) In ein Gefäß von 250 ml Fassungsvermögen bringt man 10,1 g 2-Amino-4-nitro-5-chloranisol und 11,5 ml konzentrierte Salzsäure. Man rührt 4 Stunden und läßt bis zum folgenden Tag stehen. Am folgenden Tag fügt man tropfenweise eine Lösung von 3,6 g Natriumnitrit in 7 ml Wasser hinzu, wobei man die Temperatur zwischen 0 und 5° C hält. Nach Beendigung der Zugabe, welche ungefähr 1 Stunde dauert, rührt man bei 0 bis 5° C. Die Lösung wird so schnell wie möglich für die Überführung in das Nitril nach der bekannten Methode von Sandmeyer verwendet. a) 10.1 g of 2-amino-4-nitro-5-chloroanisole are placed in a vessel with a capacity of 250 ml and 11.5 ml of concentrated hydrochloric acid. The mixture is stirred for 4 hours and left until the following Day stand. The following day, a solution of 3.6 g of sodium nitrite is added dropwise in 7 ml of water, keeping the temperature between 0 and 5 ° C. When the addition is complete, which takes about 1 hour, the mixture is stirred at 0 to 5 ° C. The solution is as soon as possible for conversion to the nitrile after the well-known method used by Sandmeyer.

b) Dazu gibt man in einen 500 ml-Kolben, welcher 30 g Kupfer(I)-cyanid enthält, 10 g Natriumcarbonat. Man bringt die Temperatur auf 60° C und führt die in der Stufe A) hergestellte Diazotierungslösung mittels eines Tropftrichters ein, wobei man die Temperatur bei 60° C hält. Nach Beendigung der Zugabe· erwärmt man noch 1 Stunde auf 60° C, läßt auf Raumtemperatur abkühlen und trocknet das erhaltene 2-Methoxy-4-nitro-5-chlorbenzonitril (8,3 g : Fp = 135° C).b) Put in a 500 ml flask, which Contains 30 g copper (I) cyanide, 10 g sodium carbonate. The temperature is brought to 60 ° C. and the one prepared in stage A) is carried out Diazotization solution using a dropping funnel, keeping the temperature at 60 ° C. After the addition the mixture is heated to 60 ° C. for a further hour, allowed to cool to room temperature and dry the 2-methoxy-4-nitro-5-chlorobenzonitrile obtained (8.3 g: mp = 135 ° C.).

Stufe B:Level B:

Herstellung von 2-Methoxy-4-nitro-5-chlorbenzoesäuremethylester Preparation of methyl 2-methoxy-4-nitro-5-chlorobenzoate

In einen 250 ml-Kolben bringt man 45 ml Methanol und 5 ml Wasser. Mittels eines Tropftrichters gibt man tropfenweise 10,4 g rauchende Schwefelsäure zu diesem Gemisch. Darauf fügt man 10,4 g 2-Methoxy-4-nitro-5-chlorbenzonitril hinzu. Das Gemisch wird 7 Stunden unter Rühren am Rückfluß gehalten. Man läßt erkalten und gießt das Gemisch in 160 ml kaltes Wasser. Dann wird gepulvertes Natriumcarbonat in kleinen Portionen hinzugefügt, um den pH-Wert auf 8 zu bringen. Man schüttelt 1 Stunde, trocknet und wäscht auf dem Filter bis zur Neutralität. 45 ml of methanol and 5 ml of water are placed in a 250 ml flask. Using a dropping funnel 10.4 g of fuming sulfuric acid are added dropwise to this mixture. 10.4 g are then added Add 2-methoxy-4-nitro-5-chlorobenzonitrile. The mixture is refluxed with stirring for 7 hours held. It is allowed to cool and the mixture is poured into 160 ml of cold water. Then powdered sodium carbonate added in small portions to bring the pH to 8. Shake for 1 hour dries and washes on the filter until neutral.

Man erhält 9,2 g 2-Methoxy-4-nitro-5-chlorbenzoesäuremethylester (Fp. = 160° C).9.2 g of methyl 2-methoxy-4-nitro-5-chlorobenzoate are obtained (melting point = 160 ° C.).

Stufe C:Level C:

Herstellung von N-(Diäthylaminoäthyl)-2-methoxy^-nitro-S-chlorbenzamid Production of N- (diethylaminoethyl) -2-methoxy ^ -nitro-S-chlorobenzamide

Man bringt 42 ml Äthylenglykol und 18,9 g Diäthylaminoäthylamin in einen 250 ml-Kolben und fügt unter Stickstoff und unter Rühren 13,5 g 2-Methoxy-4-nitro-5-chlorbenzoesäuremethylester hinzu. Das Gemisch wird unter Stickstoff und unter Rühren 3 Stunden auf HO0C erhitzt. Wenn die Reaktion beendet ist, gibt man langsam 42 ml einer 1On-Natronlauge hinzu. Dann wird das Gemisch am Rückfluß erhitzt und beim Abkühlen mit 42 ml Wasser versetzt. Das erhaltene Produkt kristallisiert. Man trocknet und wäscht es auf dem Filter bis zur Neutralität. 42 ml of ethylene glycol and 18.9 g of diethylaminoethylamine are placed in a 250 ml flask and 13.5 g of methyl 2-methoxy-4-nitro-5-chlorobenzoate are added under nitrogen and with stirring. The mixture is heated to HO 0 C for 3 hours under nitrogen and with stirring. When the reaction has ended, 42 ml of 1On sodium hydroxide solution are slowly added. The mixture is then heated to reflux and, on cooling, 42 ml of water are added. The product obtained crystallizes. It is dried and washed on the filter until neutral.

Man erhält 12 g N-(Diäthylaminoäthyl)-2-methoxy-4-nitro-5-ch!orbenzamid (Fp. = 85;· C).12 g of N- (diethylaminoethyl) -2-methoxy-4-nitro-5-chlorobenzamide (melting point = 85 ; · C) are obtained.

Stufe D:Level D:

Herstellung von N-(Diäthylaminoäthyl)-2-methoxy^-amino-S-chlorbenzamid Production of N- (diethylaminoethyl) -2-methoxy ^ -amino-S-chlorobenzamide

Man gibt 8 g N-(Diäthylaminoäthyl)-2-methoxy-4-nitro-5-chlorbenzamid, 13 ml Wasser und 2,2 ml konzentrierte Chlorwasserstoffsäure in einen 250 ml-Kolben. Man schüttelt bis zur Auflösung und gibt dann schnell 4,8 g Zinnpulver hinzu. Das Gemisch wird unter Bewegung auf 80 bis 90° C erhitzt. Mit Hilfe eines Tropftrichters fügt man dann 20,4 ml konzentrierte Salzsäure hinzu. Die Zugabe dauert ungefähr 1 Stunde. Nach Beendigung der Zugabe erhitzt man 3 Stunden auf 90 bis 95° C. Das Gemisch wird dann in eine Lösung von 18,8 g Soda in 50 ml Wasser gegossen. Man rührt 15 Minuten, wobei der Niederschlag auskristallisiert und wäscht ihn auf dem Filter bis zur Neutralität.8 g of N- (diethylaminoethyl) -2-methoxy-4-nitro-5-chlorobenzamide are added, Place 13 ml of water and 2.2 ml of concentrated hydrochloric acid in a 250 ml flask. Shake until dissolved and then quickly add 4.8 g of tin powder. The mixture is heated to 80 to 90 ° C with agitation. 20.4 ml are then added using a dropping funnel concentrated hydrochloric acid added. The addition takes about 1 hour. Heated after the addition was complete one for 3 hours at 90 to 95 ° C. The mixture is then poured into a solution of 18.8 g of soda in 50 ml Poured water. The mixture is stirred for 15 minutes, during which the precipitate crystallizes out and washes it on the Filter up to neutrality.

Man erhält 5 g N-(Diäthylaminoäthyl)-2-methoxy-4-amino-5-chlorbenzamid (das Produkt kann aus Alkohol umkristallisiert werden. Es schmilzt dann konstant bei 148° C).5 g of N- (diethylaminoethyl) -2-methoxy-4-amino-5-chlorobenzamide are obtained (The product can be recrystallized from alcohol. It then melts constantly at 148 ° C).

Claims (1)

Patentanspruch:Claim: Verfahren zur Herstellung von N-(Diäthylamirioäthyi)-2-methoxy-4-amino-5-chIorbenzainid aus l-Amino^-chlor-S-nitroanisol, dadurch gekennzeichnet, daß man aus der Diazoniumverbindung des Ausgangsprodukts mit Kupfer(I)-cyanid in an sich bekannter Weise nach der Sandmeyerreaktion 2-Cyan-4-chlor-5-nitroanisol herstellt, dieses mit Methanol in Gegenwart von rauchender Schwefelsäure zum Methylester der Z-Methoxy^-nitro-S-chlorbenzoesäure hydrolysiert, der dann in an sich bekannter Weise mit Diäthylaminoäthylamin zum N-(Diäthylaminoäthyl)-2-methoxy-4-nitro-5-chlorbenz- amid umgesetzt wird, und man die so erhaltene Verbindung in an sich bekannter Weise zum N-(Diäthylaminoäthyl)-2 - rnethoxy^-amino-S-chlorbenzamid reduziert.Process for the preparation of N- (Diethylamirioäthyi) -2-methoxy-4-amino-5-chlorobenzainide from l-amino ^ -chloro-S-nitroanisole, thereby characterized in that one from the diazonium compound of the starting product with copper (I) cyanide in a manner known per se according to the Sandmeyer reaction 2-cyano-4-chloro-5-nitroanisole produces this with methanol in the presence of fuming sulfuric acid to the methyl ester Z-methoxy ^ -nitro-S-chlorobenzoic acid hydrolyzed, which then in a known manner with diethylaminoethylamine to N- (diethylaminoethyl) -2-methoxy-4-nitro-5-chlorobenz- amide is reacted, and the compound thus obtained is converted to N- (diethylaminoethyl) -2 in a manner known per se - Methoxy ^ -amino-S-chlorobenzamide reduced. B e i s ρ i eB e i s ρ i e Stufe A:Level A:
DE1543893A 1965-12-27 1966-12-16 Process for the preparation of N- (diethylaminoethyl) -2-methoxy-4-amino-5-chlorobenzamide Expired DE1543893C3 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE19661793772 DE1793772B2 (en) 1965-12-27 1966-12-16 N- (diethylaminoethyl) -2-methoxy-4amino-5-chlorobenzamide monohydrochloride, process for its preparation and medicinal products containing this compound excreted from: 1543893

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR43874A FR1513226A (en) 1965-12-27 1965-12-27 New process for the preparation of substituted benzamides

Publications (3)

Publication Number Publication Date
DE1543893A1 DE1543893A1 (en) 1970-02-05
DE1543893B2 DE1543893B2 (en) 1974-10-10
DE1543893C3 true DE1543893C3 (en) 1975-05-22

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Application Number Title Priority Date Filing Date
DE1543893A Expired DE1543893C3 (en) 1965-12-27 1966-12-16 Process for the preparation of N- (diethylaminoethyl) -2-methoxy-4-amino-5-chlorobenzamide

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Country Link
JP (1) JPS546539B1 (en)
BE (1) BE688790A (en)
CH (1) CH475949A (en)
DE (1) DE1543893C3 (en)
ES (1) ES333713A1 (en)
FR (1) FR1513226A (en)
GB (1) GB1153796A (en)
IL (1) IL26895A (en)
OA (1) OA02159A (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54148743A (en) * 1978-05-12 1979-11-21 Asahi Chem Ind Co Ltd Production of methoclopramide
JPS6058224B2 (en) 1978-07-31 1985-12-19 旭化成株式会社 Method for producing metoclopramide
FR2460923A1 (en) * 1979-07-06 1981-01-30 Ile De France Prepn. of psychotropic drug intermediates - from 3-nitro-4-amino:anisole by five-stage process to 2-methoxy-4-amino-5-alkyl sulphonyl:benzoic acids
CN111349052B (en) * 2020-04-07 2021-02-12 福建海西新药创制有限公司 Synthesis method of mosapride citrate

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Publication number Publication date
ES333713A1 (en) 1967-10-01
OA02159A (en) 1970-05-05
IL26895A (en) 1971-08-25
DE1543893B2 (en) 1974-10-10
CH475949A (en) 1969-07-31
DE1543893A1 (en) 1970-02-05
BE688790A (en) 1967-04-24
FR1513226A (en) 1968-02-16
JPS546539B1 (en) 1979-03-29
GB1153796A (en) 1969-05-29

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C3 Grant after two publication steps (3rd publication)
E77 Valid patent as to the heymanns-index 1977