NO155345B - PROCEDURE FOR PREPARING 2- (2-THIENYL) -ETHYLAMINES AND 2- (3-THIENYL) -ETHYLAMINES. - Google Patents

PROCEDURE FOR PREPARING 2- (2-THIENYL) -ETHYLAMINES AND 2- (3-THIENYL) -ETHYLAMINES. Download PDF

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Publication number
NO155345B
NO155345B NO822228A NO822228A NO155345B NO 155345 B NO155345 B NO 155345B NO 822228 A NO822228 A NO 822228A NO 822228 A NO822228 A NO 822228A NO 155345 B NO155345 B NO 155345B
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compound
thienyl
hydrogenated
formula
ethylamines
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NO822228A
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NO822228L (en
NO155345C (en
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Gilles Anne-Archard
Alain Heymes
Gerard Valette
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Sanofi Sa
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
    • C07D333/20—Radicals substituted by singly bound hetero atoms other than halogen by nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Heterocyclic Compounds Containing Sulfur Atoms (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Description

Foreliggende oppfinnelse angår en ny fremgangsmåte ved fremstilling av 2-(2-thienyl)-ethylaminer og 2-(3-thienyl)-ethylaminer, hvorav et stort antall er kjente og anvendt som mellomprodukter både i den kjemiske og farma-søytiske industri. The present invention relates to a new process for the production of 2-(2-thienyl)-ethylamines and 2-(3-thienyl)-ethylamines, a large number of which are known and used as intermediates in both the chemical and pharmaceutical industries.

Forbindelsene fremstilt i henhold til foreliggende oppfinnelse, har formelen: The compounds produced according to the present invention have the formula:

hvor: where:

står i 2-, 3-, 4- eller 5-stillingen,og og R2, som kan være like eller forskjellige, er hydrogen, rettkjedet eller forgrenet alkyl eller en thienyl-, furyl-, pyridyl-, fenyl-eller nafthylgruppe som eventuelt er mono- eller flersubsti-tuert med halogen, nitro, cyano, amino, carboxy, alkyl, alkoxy eller fenyl. is in the 2-, 3-, 4- or 5-position, and and R2, which may be the same or different, is hydrogen, straight-chain or branched alkyl or a thienyl, furyl, pyridyl, phenyl or naphthyl group which optionally is mono- or poly-substituted with halogen, nitro, cyano, amino, carboxy, alkyl, alkoxy or phenyl.

Derivatene med formel (I) har allerede vært fremstilt ved en rekke metoder: reduksjon av 0-2- eller -3-nitrovinyl-thiofener med lithiumaluminiumhydrid [R. T. Gilsdorf & F. F. Nord, J. Org. Chem., 15, 807 (1950); E. Campaigne & W. C. Mc Carthy, The derivatives of formula (I) have already been prepared by a number of methods: reduction of 0-2- or -3-nitrovinyl-thiophenes with lithium aluminum hydride [R. T. Gilsdorf & F. F. Nord, J. Org. Chem., 15, 807 (1950); E. Campaigne & W. C. McCarthy,

J. Am. Chem. Soc, 76, 4466 (1954] eller ved en elektro-kjemisk fremgangsmåte [FR 78.01 992]; J. Am. Chem. Soc, 76, 4466 (1954) or by an electrochemical method [FR 78.01 992];

reduksjon av 2-(2-thienyl)- og - (3-thienyl-acetonitriler med lithiumaluminiumhydrid [B. F. Crowe & F. F. Nord, J. Org. Chem., 15, 81 (1950); E. Campaigne & W. C. Mc Carthy, reduction of 2-(2-thienyl)- and -(3-thienyl-acetonitrile with lithium aluminum hydride [B. F. Crowe & F. F. Nord, J. Org. Chem., 15, 81 (1950); E. Campaigne & W. C. Mc Carthy,

ref. angitt] eller med natriumamalgam [F. F. Blicke &ref indicated] or with sodium amalgam [F. F. Blicke &

J. H. Burckhalter, J. Am. Chem. Soc, 6_4 , 477 (1942)]; J.H. Burckhalter, J. Am. Chem. Soc, 6_4 , 477 (1942)];

Curtius-avbygning av 3-(2-thienyl)- og -(3-thienyl)-propion-syrer [G. Barger & A. P. T. Eassou, J. Chem. Soc, 2100 Curtius decomposition of 3-(2-thienyl)- and -(3-thienyl)-propionic acids [G. Barger & A.P.T. Eassou, J. Chem. Soc, 2100

(1938); E. Campaigne & W. C. Mc Carthy ref. angitt]; (1938); E. Campaigne & W. C. Mc Carthy ref indicated];

fra 2-(2-thienyl)- og -(3-thienyl)-ethanolderivater (halo-genider eller arylsulfonater) ved direkte aminering [F. F. Blicke & J. H. Burckhalter, ref. angitt; from 2-(2-thienyl)- and -(3-thienyl)-ethanol derivatives (halogenides or arylsulfonates) by direct amination [F. F. Blicke & J. H. Burckhalter, ref indicated;

FR 75 03 142] eller over et fthalimid (FR 75 03 142 ). FR 75 03 142] or over a phthalimide (FR 75 03 142 ).

Slike vanskelig anvendbare fremgangsmåter har imidlertid ikke gitt tilfredsstillende utbytter fra et industrielt syns-punkt . However, such difficult-to-use methods have not yielded satisfactory results from an industrial point of view.

Det er dessuten allerede kjent å fremstille forbindelser av arylethylaminotypen i henhold til følgende skjema: It is also already known to prepare compounds of the arylethylamino type according to the following scheme:

dvs. ved katalytisk hydrogenering av yQ-nitrovinyl-arylforbin-delser. Denne reaksjon har imidlertid aldri vært anvendt i de tilfeller hvor den aromatiske gruppe er thiofengruppen. Allikevel har en viss hydrogenering av 2-(£-nitrovinyl)-thio-fen allerede vært beskrevet, begrenset imidlertid til fremstilling av 2-(2-thienyl)-acetaldehyd-oxim i nærvær av palladium £l. Kh. Freidlin, E.F. Litvin & V.M. Chursina, Khimiya G. et Soed. 3 , 22 ( 1967 ), Chem. Abstr. 67_, 73 465 y] , men mengdene av katalysator anvendt (0,200 g palladiummetall pr. 0,775 g forbindelse som skal hydrogeneres) utelukker en rimelig industriell anvendelse: mengden av palladium utgjør jo mer enn 25% av mengden av forbindelsen som skal hydrogeneres. ie by catalytic hydrogenation of γ-nitrovinyl aryl compounds. However, this reaction has never been used in cases where the aromatic group is the thiophene group. Even so, some hydrogenation of 2-(£-nitrovinyl)-thiophene has already been described, however limited to the preparation of 2-(2-thienyl)-acetaldehyde oxime in the presence of palladium £1. Kh. Freidlin, E.F. Litvin & V.M. Chursina, Khimiya G. et Soed. 3, 22 (1967), Chem. Abstract 67_, 73 465 y] , but the amounts of catalyst used (0.200 g of palladium metal per 0.775 g of compound to be hydrogenated) preclude a reasonable industrial application: the amount of palladium constitutes more than 25% of the amount of the compound to be hydrogenated.

I motsetning hertil tillater den foreliggende oppfinnelse fremstilling av 2-(2-thienyl)- eller -(3-thienyl)-ethyl-aminer under meget akseptable og økonomisk rimelige betingelser, bl.a. fordi det benyttes små mengder katalyator. In contrast, the present invention allows the production of 2-(2-thienyl)- or -(3-thienyl)-ethylamines under very acceptable and economically reasonable conditions, i.a. because small amounts of catalyst are used.

Med oppfinnelsen tilveiebringes således en enkel og billig fremgangsmåte for fremstilling av forbindelser med den ovenstående formel (I). Ved fremgangsmåten bli en forbindelse med den generelle formel: hvor og R_ er som ovenfor angitt, hydrogenert katalytisk til en forbindelse med den generelle formel: The invention thus provides a simple and inexpensive method for producing compounds with the above formula (I). In the process, a compound of the general formula: where and R_ is as indicated above, hydrogenated catalytically to a compound of the general formula:

som isoleres, hvoretter forbindelsen med formel (V) som det karakteristisk nye ved fremgangsmåten hydrogeneres katalytisk under et hydrogentrykk på 1-100 atm, fortrinnsvis 5-25 atm, which is isolated, after which the compound of formula (V) which is characteristically new in the method is catalytically hydrogenated under a hydrogen pressure of 1-100 atm, preferably 5-25 atm,

og ved en temperatur på 20-100°C, fortrinnsvis 40-80°C.. and at a temperature of 20-100°C, preferably 40-80°C..

I det første trinn av fremgangsmåten ifølge oppfinnelsen hydrogeneres forbindelsen med formel (IV) i et ikke-alkalisk medium, i et oppløsningsmiddel som kan være en alkohol, som f.eks. methanol, ethanol eller isopropanol, eller en organisk syre som f.eks. maursyre, eddiksyre, propionsyre, eller fortrinnsvis i en blanding av to oppløsningsmidler, hvert valgt fra en av de nevnte grupper, f.eks. i en blanding av methanol eller ethanol og eddiksyre, i nærvær av en metallkatalysator som kan være valgt blant palladium, platina, ruthenium, rhodium og iridium. In the first step of the method according to the invention, the compound of formula (IV) is hydrogenated in a non-alkaline medium, in a solvent which can be an alcohol, such as e.g. methanol, ethanol or isopropanol, or an organic acid such as formic acid, acetic acid, propionic acid, or preferably in a mixture of two solvents, each selected from one of the aforementioned groups, e.g. in a mixture of methanol or ethanol and acetic acid, in the presence of a metal catalyst which may be selected from palladium, platinum, ruthenium, rhodium and iridium.

Metallet er med fordel fortynnet med 10-100 ganger The metal is advantageously diluted 10-100 times

sin vekt av en bærer som f.eks. trekull, aluminiumoxyd eller bariumsulfat, og i alminnelighet er mengden av en slik anvendt kombinasjon 1-10% av forbindelsen som skal hydrogeneres, hvil-ket svarer til et mengdeforhold på fra 1/10.000 til 1/100 mellom katalysatorkomponenten og forbindelsen som skal hydrogeneres. Hydrogeneringen utføres under et hydrogentrykk som i alminnelighet ligger mellom 1 og 100 atmosfærer, og som fortrinnsvis er mellom 5 og 25 atmosfærer, ved en temperatur som i alminnelighet ligger mellom 20° og 100°C, fortrinnsvis mellom 30° og 60°C. Hydrogeneringen tar i alminnelighet fra its weight by a carrier such as e.g. charcoal, aluminum oxide or barium sulphate, and in general the amount of such a combination used is 1-10% of the compound to be hydrogenated, which corresponds to a quantity ratio of from 1/10,000 to 1/100 between the catalyst component and the compound to be hydrogenated. The hydrogenation is carried out under a hydrogen pressure which is generally between 1 and 100 atmospheres, and which is preferably between 5 and 25 atmospheres, at a temperature which is generally between 20° and 100°C, preferably between 30° and 60°C. The hydrogenation generally starts from

30 minutter til noen timer. 30 minutes to a few hours.

Forut for det annet trinn blir derivatet med formel Prior to the second step, the derivative is given by formula

(V) isolert fra reaksjonsmediet på passende måte. Det blir (V) isolated from the reaction medium in a suitable manner. It will be

så hydrogenert i et oppløsningsmiddel som kan være en alkohol, som f.eks. methanol, ethanol eller isopropanol, som med fordel then hydrogenated in a solvent which may be an alcohol, such as e.g. methanol, ethanol or isopropanol, as with advantage

- for å forhindre dannelse av sekundære aminer - vil inneholde oppløst ammoniakk. Hydrogeneringen utføres i nærvær av en metallkatalysator, fortrinnsvis en nikkelkatalysator, enten såkalt Raney-nikkel eller nikkel anbragt på en bærer som sili- - to prevent the formation of secondary amines - will contain dissolved ammonia. The hydrogenation is carried out in the presence of a metal catalyst, preferably a nickel catalyst, either so-called Raney nickel or nickel placed on a support such as silicon

ciumoxyd eller aluminiumxyd, idet mengden av anvendt metall er 1-10% med hensyn på forbindelsen som skal hydrogeneres. Hydrogeneringen utføres under et hydrogentrykk mellom 1 og 100 atmosfærer, fortrinnsvis mellom 5 og 25 atmosfærer, ved en temperatur mellom 20° og 100°C, fortrinnsvis mellom 40° cium oxide or aluminum oxide, the amount of metal used being 1-10% with respect to the compound to be hydrogenated. The hydrogenation is carried out under a hydrogen pressure between 1 and 100 atmospheres, preferably between 5 and 25 atmospheres, at a temperature between 20° and 100°C, preferably between 40°

og 80°C, og den tar i alminnelighet fra 30 minutter til noen timer. and 80°C, and it generally takes from 30 minutes to a few hours.

De fremstilte forbindelser med formel (I) kan så isoleres og renses ved konvensjonelle metoder. Til dette for-mål kan det være fordelaktig å overføre de frie forbindelser med formel (I) til deres salter, f.eks. deres syreaddisjons-salter ved omsetning med,uorganiske eller organiske syrer. Forbindelsene med formel (i) kan så frigjøres fra sine salter ved kjente metoder. The prepared compounds of formula (I) can then be isolated and purified by conventional methods. For this purpose, it may be advantageous to transfer the free compounds of formula (I) to their salts, e.g. their acid addition salts by reaction with inorganic or organic acids. The compounds of formula (i) can then be freed from their salts by known methods.

Forbindelsene med formel (IV), som benyttes som utgangs-materialer, kan fremstilles ved en rekke metoder som er vel kjent i faget, som f.eks. ved kondensasjon av en forbindelse med formelen: The compounds of formula (IV), which are used as starting materials, can be prepared by a number of methods which are well known in the art, such as e.g. by condensation of a compound with the formula:

med et carbonylderivat med formelen: hvor er som ovenfor angitt, under velkjente betingelser, hvorved det fåes et derivat med formelen: with a carbonyl derivative of the formula: where is as indicated above, under well-known conditions, whereby a derivative of the formula is obtained:

De følgende eksempler illustrerer oppfinnelsen. The following examples illustrate the invention.

Eksempel 1 Example 1

Fremstilling av 2-( 2- thienyl)- ethylamin- hydroklorid Preparation of 2-(2-thienyl)-ethylamine hydrochloride

a) 2- thienyl- acetaldehyd- oximer a) 2-thienyl-acetaldehyde-oxime

100 g (0,645 mol) 2-(2-thienyl)-nitroethylen oppløst i 100 g (0.645 mol) 2-(2-thienyl)-nitroethylene dissolved in

2 liter eddiksyre:ethanol (75:25) hydrogeneres i et trykk-kar ved 35°C under et trykk, på 20 bar, i nærvær av 5 g 5%-ig palladium-på-trekull inntil absorpsjon opphører (tid: ca. 2 timer). Katalysatoren frafUtreres så og renses med ethanol, hvorefter den erholdte oppløsning inndampes i vakuum ved 50°C. Det oljeaktige residuum taes opp i 500 ml methylenklorid, og oppløsningen vaskes efter hverandre med en ca.IN vandig natriumhydroxydoppløsning og med vann og inndampes så, hvorved man får 97 g 2-thienyl-acetaldehyd-oximer (syn + anti blanding) som en orangegul olje som an-vendes som sådan i det påfølgende trinn, 2 liters of acetic acid:ethanol (75:25) are hydrogenated in a pressure vessel at 35°C under a pressure of 20 bar in the presence of 5 g of 5% palladium-on-charcoal until absorption ceases (time: approx. 2 hours). The catalyst is then filtered off and cleaned with ethanol, after which the resulting solution is evaporated in a vacuum at 50°C. The oily residue is taken up in 500 ml of methylene chloride, and the solution is washed successively with an approx. IN aqueous sodium hydroxide solution and with water and then evaporated, whereby 97 g of 2-thienyl-acetaldehyde-oxime (syn + anti mixture) is obtained as an orange-yellow oil which is used as such in the following step,

b) Oximblandingen erholdt ovenfor, oppløst i 2 liter methanol mettet med ammoniakk hydrogeneres i et trykkar ved b) The oxime mixture obtained above, dissolved in 2 liters of methanol saturated with ammonia, is hydrogenated in a pressure vessel at

60°C under et trykk på 20 bar i nærvær av 10 g Raney-nikkel inntil absorpsjonen opphører (tid: ca. 20 timer). Katalysatoren frafUtreres og renses med methanol, og den erholdte oppløsning inndampes. Toluen (500 ml) tilsettes til det oljeaktige residuum. Denne organiske fase ekstraheres med en vandig saltsyreoppløsning (ca.lN). Den erholdte sure vandige fase gjøres alkalisk med ca.IN vandig natriumhydroxyd og ekstraheres så med toluen. Tilsetning til den isolerte organiske fase av en oppløsning av hydrogenkloridgass i iso-propylether fører . til dannelsen av et bunnfall som fra-filtreres og tørres, hvorved man får 68 g (utbytte: 65% med hensyn på 2-(2-thienyl)-nitroethylenet) av 2-(2-thienyl)-ethylamin-hydroklorid, som hvite krystaller. 60°C under a pressure of 20 bar in the presence of 10 g of Raney nickel until absorption ceases (time: approx. 20 hours). The catalyst is filtered off and cleaned with methanol, and the resulting solution is evaporated. Toluene (500 ml) is added to the oily residue. This organic phase is extracted with an aqueous hydrochloric acid solution (approx. 1N). The obtained acidic aqueous phase is made alkaline with about 1N aqueous sodium hydroxide and then extracted with toluene. Addition to the isolated organic phase of a solution of hydrogen chloride gas in isopropyl ether leads to . to the formation of a precipitate which is filtered off and dried, thereby obtaining 68 g (yield: 65% with respect to 2-(2-thienyl)-nitroethylene) of 2-(2-thienyl)-ethylamine hydrochloride, as white crystals.

Smp. = 202°C Temp. = 202°C

Analyse: CgHgNS . HCl = 163,67 Analysis: CgHgNS . HCl = 163.67

Beregnet %: C 44,03; H 6,15; N 8,55 Calculated %: C 44.03; H 6.15; N 8.55

Funnet %: 43,98 6,16 8,54 Found %: 43.98 6.16 8.54

Eksempel 2 Example 2

2-( 3- thienyl)- ethylamin- hydroklorid 2-(3-thienyl)ethylamine hydrochloride

Når fremgangsmåten utføres som angitt i eksempel 1, men det 5%-ige Pd/C erstattes med 5%-ig Rh/C, fåes hydrokloridet av forbindelsen i et utbytte på 66%. When the method is carried out as stated in example 1, but the 5% Pd/C is replaced by 5% Rh/C, the hydrochloride of the compound is obtained in a yield of 66%.

Smp. = 216°C Temp. = 216°C

Analyse: CgHgNS . HCl = 163,67 Analysis: CgHgNS . HCl = 163.67

Beregnet %: C 44,03; H 6,15; N 8,55 Calculated %: C 44.03; H 6.15; N 8.55

Funnet %: 43,92 6,18 8,50 Found %: 43.92 6.18 8.50

Eksempel 3 Example 3

l- methyl- 2-( 3- thienyl)- ethylamin- hydroklorid 1-methyl-2-(3-thienyl)-ethylamine hydrochloride

Under anvendelse av betingelsene beskrevet i eksempel Under the conditions described in Example

1, idet det 5%-ige Pd/C erstattes med 5%-ig Pt/C, fremstilles hydrokloridet av forbindelsen i et utbytte på 81%. 1, with the 5% Pd/C being replaced by 5% Pt/C, the hydrochloride of the compound is produced in a yield of 81%.

Smp. = 138°C Temp. = 138°C

Analyse: C^-^NS . HCl = 177,69 Analysis: C^-^NS . HCl = 177.69

Beregnet %: C 47,31; H 6,80; N 7,88 Calculated %: C 47.31; H 6.80; N 7.88

Funnet %: 47,55 6,85 7,92 Found %: 47.55 6.85 7.92

Claims (3)

1. Fremgangsmåte ved fremstilling av 2-(2-thienyl)- og 2-(3-thienyl)-ethylaminer med den generelle formel: hvor: R^ står i 2-, 3-, 4- eller 5-st Ulingen, og R^ og R2 , som kan være like eller forskjellige, er hydrogen, rettkjedet eller forgrenet alkyl eller en thienyl-, furyl-, pyridyl-, fenyl- eller nafthylgruppe som eventuelt er mono- eller flersubsti- tuert med halogen, nitro, cyano, amino, carboxy, alkyl, alkoxy eller fenyl, ved hvilken en forbindelse med den generelle formel: hvor R1 og R2 er som ovenfor angitt, hydrogeneres katalytisk til en forbindelse med den generelle formel: som isoleres, karakterisert ved at forbindelsen med formel (V) hydrogeneres katalytisk under et hydrogentrykk på 1-100 atm, fortrinnsvis 5-25 atm, og ved en temperatur på 20-100°C, fortrinnsvis 40-80°C.1. Procedure for the production of 2-(2-thienyl)- and 2-(3-thienyl)-ethylamines with the general formula: where: R^ stands in 2-, 3-, 4- or 5-st Ulingen, and R^ and R2 , which can be the same or different, is hydrogen, straight chain or branched alkyl or a thienyl, furyl, pyridyl, phenyl or naphthyl group which is optionally mono- or polysubstitu- tuated with halogen, nitro, cyano, amino, carboxy, alkyl, alkoxy or phenyl, whereby a compound with the general formula: where R1 and R2 are as indicated above, is catalytically hydrogenated to a compound of the general formula: which is isolated, characterized in that the compound of formula (V) is catalytically hydrogenated under a hydrogen pressure of 1-100 atm, preferably 5-25 atm, and at a temperature of 20-100°C, preferably 40-80°C. 2. Fremgangsmåte ifølge krav 1 , karakterisert ved at de to katalytiske hydrogeneringstrinn utføres under ulike sett av betingelser.2. Method according to claim 1, characterized in that the two catalytic hydrogenation steps are carried out under different sets of conditions. 3. Fremgangsmåte ifølge krav 1 eller 2, ved hvilken det første hydrogeneringstrinn, hvor det foretas hydrogenering av forbindelsen med formel (IV), utføres i et ikke-alkalisk medium under et hydrogentrykk på 5-25 atm og ved en temperatur på 30-60°C, under anvendelse av en katalysator som inneholder en metallkomponent valgt blant palladium, platina og rhodium avsatt på en inert bærer, og som benyttes i en mengde svarende til et vektforhold på fra 1/10.000 til 1/100 mellom metallkom-ponenten og forbindelsen som skal hydrogeneres, karakterisert ved at det annet hydrogeneringstrinn, hvor forbindelsen med formel (V) hydrogeneres, utføres i et alkalisk medium, under anvendelse av en Raney-nikkel-katalysator i en mengde svarende til et vektforhold på fra 1/100 til 1/10 mellom katalysatorens metallkomponent og forbindelsen som skal hydrogeneres.3. Method according to claim 1 or 2, in which the first hydrogenation step, where the compound of formula (IV) is hydrogenated, is carried out in a non-alkaline medium under a hydrogen pressure of 5-25 atm and at a temperature of 30-60 °C, using a catalyst containing a metal component selected from palladium, platinum and rhodium deposited on an inert support, and which is used in an amount corresponding to a weight ratio of from 1/10,000 to 1/100 between the metal component and the compound which is to be hydrogenated, characterized in that the second hydrogenation step, where the compound of formula (V) is hydrogenated, is carried out in an alkaline medium, using a Raney nickel catalyst in an amount corresponding to a weight ratio of from 1/100 to 1/ 10 between the metal component of the catalyst and the compound to be hydrogenated.
NO822228A 1981-06-30 1982-06-29 PROCEDURE FOR PREPARING 2- (2-THIENYL) -ETHYLAMINES AND 2- (3-THIENYL) -ETHYLAMINES. NO155345C (en)

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FR8113066A FR2508456A1 (en) 1981-06-30 1981-06-30 PROCESS FOR THE PREPARATION OF (THIENYL-2) -2 ETHYLAMINES AND (THIENYL-3) -2 ETHYLAMINES

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NO822228L NO822228L (en) 1983-01-03
NO155345B true NO155345B (en) 1986-12-08
NO155345C NO155345C (en) 1987-03-18

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NZ214698A (en) * 1984-12-31 1988-08-30 Merrell Dow Pharma Thiophene derivatives and pharmaceutical compositions containing such
FR2608607B1 (en) * 1986-12-23 1989-04-28 Sanofi Sa PROCESS FOR THE PREPARATION OF THIENYLETHYLAMINES AND DITHIENYLETHYLAMINES THUS OBTAINED
CA1309719C (en) * 1987-02-26 1992-11-03 Thomas M. Bargar Heterocycly1-2-propyn-1-amines
FR2622191B1 (en) * 1987-10-22 1991-06-21 Sanofi Sa PROCESS FOR THE PREPARATION OF N- (2-CHLORO-BENZYL) -2 ETHYLAMINE AND INTERMEDIATE PRODUCTS IN THIS PREPARATION
US4906756A (en) * 1988-05-10 1990-03-06 Syntex (U.S.A.) Inc. 2-(2-nitrovinyl)thiophene reduction and synthesis of thieno[3,2-c]pyridine derivatives
US5191090A (en) * 1990-01-25 1993-03-02 Syntex (U.S.A.) Inc. Preparation of 2-(2'-thienyl)ethylamine derivatives and synthesis of thieno[3,2-c]pyridine derivatives therefrom
FR2664276B1 (en) * 1990-07-04 1992-10-23 Sanofi Sa GLYCIDIC THIENYL-2 DERIVATIVE, ITS PREPARATION METHOD AND ITS USE AS A SYNTHESIS INTERMEDIATE.
US5208252A (en) * 1992-07-24 1993-05-04 Ortho Pharmaceutical Corporation Aminoethylthiophene derivatives
GB201818117D0 (en) * 2018-11-06 2018-12-19 Syngenta Participations Ag Enantioselective process

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GR77203B (en) 1984-09-11
DK291782A (en) 1982-12-31
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CA1205811A (en) 1986-06-10
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FR2508456A1 (en) 1982-12-31
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IE821314L (en) 1982-12-30
FR2508456B1 (en) 1983-09-09
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FI822318A0 (en) 1982-06-29
NZ200856A (en) 1985-11-08
SU1148562A3 (en) 1985-03-30
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FI822318L (en) 1982-12-31
DK153793C (en) 1989-01-23
DK153793B (en) 1988-09-05
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PT75156A (en) 1982-07-01
NO155345C (en) 1987-03-18

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