DK153793B - METHOD FOR PREPARING 2- (2-THIENYL) - OR 2- (3-THIENYL) -ETHYLAMINES - Google Patents
METHOD FOR PREPARING 2- (2-THIENYL) - OR 2- (3-THIENYL) -ETHYLAMINES Download PDFInfo
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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
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- 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
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- 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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Description
o 1o 1
DK 153793 BDK 153793 B
Opfindelsen angår en særlig fremgangsmåde til-frem-stillingen af 2- (2-thienyl) -ethylaminer eller 2-(3-thienyl)= 5 ethylaminer, hvoraf et stort antal kendes og anvendes som mellemprodukter både i den kemiske og farmaceutiske industri -The invention relates to a particular process for the preparation of 2- (2-thienyl) ethylamines or 2- (3-thienyl) = 5 ethylamines, a large number of which are known and used as intermediates in both the chemical and pharmaceutical industries.
De ifølge den foreliggende opfindelse fremstillede for-10 bindeiser har formlen (I): 4 _3 15 CH2'<TH'NH2 (I> ' 20 hvori r2 betegner et hydrogenatom eller en ligekædet eller forgrenet alkylgruppe.The compounds of the present invention prepared according to the present invention have the formula (I): 4-3 CH2 '<TH'NH2 (I>' 20 wherein r2 represents a hydrogen atom or a straight or branched alkyl group.
Aminoethylkæden kan indtage en hvilken som helst stilling på thiophenkernen.The aminoethyl chain can occupy any position on the thiophene nucleus.
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Derivaterne af formlen (I) er allerede blevet fremstillet ifølge en række metoder:The derivatives of formula (I) have already been prepared by a number of methods:
Reduktion af β-2- eller -3-nitrovinylthiophener med lithium= 30 aluminiumhydrid [R.T. Gilsdorf & F.F. Nord, J. Org. Chem., 15, 807 (1950); E. Campaigne & W.C. Me. Carthy, J. Am. Chem. Soc., 76, 4466 (1954)], eller ved hjælp af en elektrokemisk proces [FR-patentskrift nr. 2.415.671]; 35 2Reduction of β-2- or -3-nitrovinylthiophenes with lithium = 30 aluminum hydride [R.T. Gilsdorf & F.F. Nord, J. Org. Chem., 15, 807 (1950); E. Campaigne & W.C. Me. Carthy, J. Am. Chem. Soc., 76, 4466 (1954)], or by means of an electrochemical process [U.S. Patent No. 2,415,671]; 35 2
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reduktion af 2- (2-thienyl) -eller - (3-thienyl) -acetonitriler med lithiumaluminiumhydrid [B.F. Crowe & F.F. Nord, J. Org. Chem., 15, 81 (1950); E. Campaigne & W.C. Mc Carthy, ref. cit] eller med natriumamalgam [F.F. Blicke & J.H. Burck= 5 halter, J. Am. Chem. Soc., 64, 477 (1942)];reduction of 2- (2-thienyl) or - (3-thienyl) acetonitriles with lithium aluminum hydride [B.F. Crowe & F.F. Nord, J. Org. Chem., 15, 81 (1950); E. Campaigne & W.C. Mc Carthy, ref. cit] or with sodium amalgam [F.F. Blicke & J.H. Burck = 5 halter, J. Am. Chem. Soc., 64, 477 (1942)];
Curtius nedbrydning på 3-(2—thienyl)- eller -(3-thienyl)-propionsyre [G. Barger & A.P.T. Eassou, J. Chem. Soc., 2100 (1938); E. Campaigne & W.C. Mc Carthy ref. cit]; ud fra 2- (2-thienyl) -éLler - (3-thienyl) ethanolderivater 10 (halogenider eller arylsulfonater) ved direkte aminering [F.F. Blicke & J.H. Burckhalter, ref.cit; FR-patentskrift nr. 2.299.332 eller via et phthalimid FR-patentskrift nr. 2.299.332.Curtius degradation of 3- (2-thienyl) or - (3-thienyl) propionic acid [G. Barger & A.P.T. Eassou, J. Chem. Soc., 2100 (1938); E. Campaigne & W.C. Mc Carthy ref. cit]; from 2- (2-thienyl) or - (3-thienyl) ethanol derivatives (halides or arylsulfonates) by direct amination [F.F. Blicke & J.H. Burckhalter, ref.cit; FR Patent No. 2,299,332 or via a phthalimide FR Patent No. 2,299,332.
De nævnte kendte processer er meget kostbare og giver meget lave udbytter. Desuden er de forbundet med stor risiko, idet der anvendes metalhydrider, såsom LiAlH^ og farlige opløsningsmidler, såsom ethere og THF.The known processes mentioned are very expensive and give very low yields. In addition, they are associated with high risk, using metal hydrides such as LiAlH 2 and hazardous solvents such as ethers and THF.
Formålet med den foreliggende opfindelse er derfor at tilvejebringe en enkel, billig fremgangsmåde til fremstillingen af forbindelserne af formlen (I).The object of the present invention is therefore to provide a simple, inexpensive process for the preparation of the compounds of formula (I).
Ved fremgangsmåden ifølge opfindelsen starter man med et de-20 rivat af formlen (IV)In the process according to the invention one starts with a derivative of formula (IV)
Jf -CH = C(R0) - NO- (IV), hvori R2 har den i forbindelse med formlen (I) definerede betydning, og som kan fremstilles ved hjælp af en række metoder,Jf -CH = C (R0) - NO- (IV), wherein R 2 has the meaning defined in formula (I) and which can be prepared by a variety of methods,
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3 som er velkendte for fagfolk på dette område, såsom f.eks. ved kondensation af en forbindelse af formlen (II): R2 - CH2 - N02 (II) 5 med et carbonylderivat af formlen (III): CHO (III), hvori R? har den i forbindelse med formlen (I) definerede betydning, under betingelser, som er velkendte for fagfolk på dette område, til opnåelse af et derivat af formlen 10 (IV) : ^ J^T'CH = C(R2} " N02 {IV) ·3 which are well known to those skilled in the art, such as e.g. by condensing a compound of formula (II): R2 - CH2 - NO2 (II) with a carbonyl derivative of formula (III): CHO (III) wherein R? has the meaning defined in formula (I), under conditions well known to those skilled in the art, to obtain a derivative of formula 10 (IV): IV) ·
Fremgangsmåden ifølge opfindelsen til -fremstillingen af forbindelserne af formlen (I) er ejendommelig ved det i krav l's kendetegnende del anførte.The process of the invention for the preparation of the compounds of formula (I) is characterized by the characterizing part of claim 1.
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Fremstillingen af forbindelser af arylethylaminotypen i overensstemmelse med følgende skema H2 5 Ar - CH = C - N0o --X Ar - CH0 - CH - NH0 , 9 , 2 Kat 2 , 2The preparation of compounds of the arylethylaminotype according to the following scheme H2 5 Ar - CH = C - NOO - X Ar - CH0 - CH - NH0, 9, 2 Cat 2, 2
R RR R
dvs. ved katalytisk hydrogenering af β-nitrovinylaryl, kendes allerede. Den har imidlertid aldrig været beskrevet 10 i de tilfælde, hvor' den aromatiske gruppe- er thiophengruppen.i.e. by catalytic hydrogenation of β-nitrovinylaryl is already known. However, it has never been described in cases where the aromatic group is the thiophene group.
En katalytisk hydrogenering af 2-(β-nitrovinyl)-thiophen er . imidlertid allerede blevet beskrevet. Denne er imidlertid begrænset til fremstillingen af 2-(2-thienyl)-acetaldehydoxim, gennemført i nærværelse af palladium 15 [L. Kh. Freidlin, E.F. Litvin & V.M. Chursina, Khimiya G.A catalytic hydrogenation of 2- (β-nitrovinyl) thiophene is. however, has already been described. However, this is limited to the preparation of 2- (2-thienyl) acetaldehyde oxime, carried out in the presence of palladium 15 [L. Kh. Freidlin, E.F. Litvin & V.M. Chursina, Khimiya G.
et Soed. 3, 22 (1967), Chem. Abst 67, 73 465 y], men de anvendte mængder af katalysator (0,200 g palladiummetal pr. 0,775 g substrat, der skal hydrogeneres) udelukker enhver rimelig industriel anvendelse: Den anvendte palla-20 diummængde er faktisk over 25% med hensyn til substratet.et Soed. 3, 22 (1967), Chem. Abst 67, 73,465 y], but the amounts of catalyst used (0.200 g of palladium metal per 0.775 g of substrate to be hydrogenated) preclude any reasonable industrial use: the amount of palladium used is actually above 25% with respect to the substrate.
I modsætning hertil giver fremgangsmåden ifølge opfindelsen 2-(2-thienyl)- eller -(3-thienyl)-ethylaminer under let anvendelige, billige betingelser, når henses til den ringe mængde 25 katalysator, der anvendes.In contrast, the process of the invention provides 2- (2-thienyl) - or - (3-thienyl) -ethylamines under readily available, inexpensive conditions, considering the small amount of catalyst used.
Et af de karakteristiske træk ved den foreliggende opfindelse er,at nævnte reduktion gennemføres i to trin.One of the features of the present invention is that said reduction is accomplished in two steps.
30 I det første trin hydrogeneres derivatet af formlen (IV) i et ikke-basisk medium.In the first step, the derivative of formula (IV) is hydrogenated in a non-basic medium.
7 fortrinsvis i et neutralt, organisk opløsningsmiddel, som kan være en alkohol, såsom f.eks. methanol, ethanol, isopropanol, eller 35 en organisk syre, såsom f.eks. myresyre, eddikesyre, propionsyre, eller endnu mere fordelagtigt i en blanding af to opløsningsmidler, der hver er valgt fra én af de nævnte grupper, såsom en blanding af methanol eller ethanol og eddikesyre,7 preferably in a neutral organic solvent which may be an alcohol such as e.g. methanol, ethanol, isopropanol, or an organic acid such as e.g. formic acid, acetic acid, propionic acid, or even more advantageously in a mixture of two solvents each selected from one of said groups, such as a mixture of methanol or ethanol and acetic acid;
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i nærværelse af en metalkatalysator, der er valgt blandt palladium, platin, ruthenium, rhodium, iridium i forbindelse med en inaktiv bærer, idet vægtforholdet mellem metalkomponenten og udgangsforbindelsen (IV) er 1/10.000 til 1/100.in the presence of a metal catalyst selected from palladium, platinum, ruthenium, rhodium, iridium in association with an inert carrier, the weight ratio of the metal component to the starting compound (IV) being 1 / 10,000 to 1/100.
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Metallet fortyndes hensigtsmæssigt med 10-100 gange sin vægt af bæreren såsom f.eks. trækul, aluminiumoxid eller bariumsulfat, og mængden af en således anvendt kombination er almindeligvis 1 - 10% af substratet, der skal hydrogeneres, hvilket svarer til det nævnte forhold for metalkomponenter pa 1/10.000 til 1/100 under et hydrogentryk, som ligger mellem 1 og 100 atmosfærer, fortrinsvis mellem 5 og 25 atmosfærer, 15 ved en temperatur, som ligger mellem 20 og 100°C, fortrinsvis mellem 30 og 60°C, fremgangsmåden tager almindeligvis fra 30 minutter til adskillige timer..The metal is conveniently diluted by 10-100 times its weight by the carrier such as e.g. charcoal, alumina or barium sulfate, and the amount of the combination thus used is generally 1 - 10% of the substrate to be hydrogenated, which corresponds to the mentioned ratio for metal components of 1 / 10,000 to 1/100 under a hydrogen pressure ranging from 1 and 100 atmospheres, preferably between 5 and 25 atmospheres, 15 at a temperature between 20 and 100 ° C, preferably between 30 and 60 ° C. The process generally takes from 30 minutes to several hours.
I det andet trin hydrogeneres derivatet af formlen (V), som isoleres fra reaktionsmediet på hensigtsmæssig måde, 25 fortrinsvis i et organisk opløsningsmiddel, som kan være en alkohol såsom f.eksV methanol, ethanol eller isopropanol, som hensigtsmæssigt, for at Hindre 'dannelsen af sekiindare aminer, vil indeholde opløst ammoniak, 30 i nærværelse af en nikkelkatalysator, enten en såkaldt Raney-nikkel eller understøttet nikkel på en inaktiv bærer såsom silica eller aluminiumoxid, idet det anvendte forhold.af metal 35 fortrinsvis er 1 - 10% med hensyn til substratet, der skal hydrogeneres underet hydrogentryk, mellem 1 og 100 atmosfærer, fortrinsvis mellem 5 og 25 atmosfærer-, * iIn the second step, the derivative of formula (V) which is isolated from the reaction medium is suitably hydrogenated, preferably in an organic solvent, which may be an alcohol such as, for example, methanol, ethanol or isopropanol, as appropriate, to prevent the formation of secondary amines will contain dissolved ammonia, 30 in the presence of a nickel catalyst, either a so-called Raney nickel or supported nickel on an inert carrier such as silica or alumina, the ratio of metal used being preferably 1 to 10% with respect to to the substrate to be hydrogenated under hydrogen pressure, between 1 and 100 atmospheres, preferably between 5 and 25 atmospheres,
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ved en temperatur mellem 20 og 100°C, fortrinsvis mellem 40 og 80°C, 5 fremgangsmåden tager almindeligvis fra 30 minutter til adskillelige timer.at a temperature between 20 and 100 ° C, preferably between 40 and 80 ° C, the process generally takes from 30 minutes to several hours.
De resulterende forbindelser af formlen (I) kan så isoleres og renses i overensstemmelse med sædvanlige frem-10 gangsmåder. Til dette formål kan det være fordelagtigt at omdanne de fri forbindelser af formlen (I) til deres salte, f.eks. til deres syreadditionssalte, ved reaktion med uorganiske eller organiske syre. Forbindelserne af formlen (I) kan frigives fra sådanne salte i overensstem-15 melse med kendte metoder.The resulting compounds of formula (I) can then be isolated and purified according to conventional methods. For this purpose, it may be advantageous to convert the free compounds of formula (I) into their salts, e.g. to their acid addition salts, by reaction with inorganic or organic acid. The compounds of formula (I) can be released from such salts according to known methods.
De følgende eksempler belyser nærmere fremgangsmåden ifølge den foreliggende opfindelse.The following examples further illustrate the process of the present invention.
20 Eksempel 1.Example 1.
Fremstilling af 2-(2-thienyl)-ethylaminhydrochlorid.Preparation of 2- (2-thienyl) ethylamine hydrochloride.
a) 2-thienylacetaldehydoximer 25 100 g (0,645 mol) 2-(2-thienyl)-nitroethylen opløst i 2 liter eddikesyre/ethanol (75:25) hydrogeneres i en trykbeholder ved 35°C under et tryk på 20 bar i nærværelse af 5 g 5% palladium-på-carbon, indtil absorptionen ophører ΑΛ (tid: ca. 2 timer). Katalysatoren filtreres derpå fra og skylles med ethanol, hvorefter den resulterende opløsning inddampes i vakuum ved 50°C. Den olieagtige rest optages i 500 ml methylenchlorid og opløsningen vaskes successivt med en omtrent N vandig natriumhydroxidopløsning og med 35 vand og inddampes derpå til opnåelse af 97 g 2-thienylacetaldehydoximer (syn + antiblanding) som en orangegula) 2-Thienyl acetaldehyde oxime 100 g (0.645 mol) of 2- (2-thienyl) nitroethylene dissolved in 2 liters of acetic acid / ethanol (75:25) is hydrogenated in a pressure vessel at 35 ° C under a pressure of 20 bar in the presence of 5 g of 5% palladium-on-carbon until absorption ceases ΑΛ (time: about 2 hours). The catalyst is then filtered off and rinsed with ethanol, then the resulting solution is evaporated in vacuo at 50 ° C. The oily residue is taken up in 500 ml of methylene chloride and the solution is washed successively with an approximately N aqueous sodium hydroxide solution and with 35 water and then evaporated to give 97 g of 2-thienyl acetaldehyde oxime (syn + antibody) as an orange yellow
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7 olie, der anvendes som sådan i det efterfølgende trin.7 oil used as such in the subsequent step.
b) Den ovenfor opnåede oximblanding, opløst i 2 liter methanol mættet med ammoniak, hydrogeneres i en trykbeholder ved 60°C under et tryk på 20 bar i nærværelse af 5 10 g Raney-nikkel indtil absorptionen ophører (tid: ca.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 a pressure of 20 bar in the presence of 5 10 g Raney nickel until absorption ceases (time: approx.
20 timer). Katalysatoren filtreres fra og skylles med methanol, og den resulterende opløsning inddampes. Toluen (500 ml) sættes til den olieagtige rest. Denne organiske fase ekstraheres med en vandig saltsyreopløsning (ca. N).20 hours). The catalyst is filtered off and rinsed 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 (about N).
10 Den sure vandige fase isoleres, gøres basisk med omtrentlig N vandig natriumhydroxid og ekstraheres derpå med toluen. Tilsætning til den isolerede organiske fase af en opløsning af hydrogenchloridgas i isopropylether fører til dannelsen af et bundfald, som filtreres fra og tørres 15 til opnåelse af 68 g (udbytte: 65% med hensyn til 2—(2— thienyl)nitroethylen) 2-(2-thienyl)ethylaminhydrochlorid, som hvide krystaller.The acidic aqueous phase is isolated, basified with approximately N 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 the formation of a precipitate which is filtered off and dried to give 68 g (yield: 65% with respect to 2- (2-thienyl) nitroethylene) 2- (2-thienyl) ethylamine hydrochloride, as white crystals.
Smeltepunkt = 202°C.Melting point = 202 ° C.
Analyse: Cgf^NS, HC1 = 163,67 20 Beregnet %: C 44,03, H 6,15, N 8,55Analysis: CgfH₂ NSN, HCl = 163.67 Calculated%: C 44.03, H 6.15, N 8.55
Fundet %: C 43,98, H 6,16, N 8,54.Found%: C 43.98, H 6.16, N 8.54.
Eksempel 2.Example 2.
2-(3-thienyl)ethylaminhydrochlorid.2- (3-thienyl) ethylamine hydrochloride.
Fremgangsmåden fra eksempel 1 anvendes, men de 5% Pd/C 25 erstattes med 5% Rh/C, hvilket giver hydrochloridet af forbindelsen et udbytte på 66%.The procedure of Example 1 is used, but the 5% Pd / C 25 is replaced by 5% Rh / C, giving the hydrochloride of the compound a 66% yield.
Smeltepunkt = 216°C.Melting point = 216 ° C.
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Analyse: CgHgNS, HC1 = 163,67Analysis: CgHgNS, HCl = 163.67
Beregnet %: C 44,03, H 6,15, N 8,55 Fundet %: C 43,92, H 6,18, N 8,50Calculated%: C 44.03, H 6.15, N 8.55 Found%: C 43.92, H 6.18, N 8.50
Eksempel 3.Example 3
5 l-methyl-2-(3-thienyl)-ethylaminhydrochlorid.5-Methyl-2- (3-thienyl) -ethylamine hydrochloride.
Under anvendelse af de i eksempel 1 beskrevne betingelser, men ved at erstatte de 5% Pd/C med 5% Pt/C og 2-(2-thienyl)-nitroethylen med l-methyl-2-(3-thienyl)-nitroethylen, fremstilles hydrochloridet af forbindelsen i et udbytte på 81%. Smeltepunkt = 138°C.Using the conditions described in Example 1, but replacing the 5% Pd / C with 5% Pt / C and 2- (2-thienyl) nitroethylene with 1-methyl-2- (3-thienyl) nitroethylene , the hydrochloride of the compound is prepared in a yield of 81%. Melting point = 138 ° C.
10 Analyse: C^H^NS, HCl = 177,69Analysis: C ^H ^NS, HCl = 177.69
Beregnet %: C 47,31, H 6,80, N 7,88 Fundet % : C 47,55, H 6,85, N 7,92Calculated%: C 47.31, H 6.80, N 7.88 Found%: C 47.55, H 6.85, N 7.92
Claims (4)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8113066A FR2508456A1 (en) | 1981-06-30 | 1981-06-30 | PROCESS FOR THE PREPARATION OF (THIENYL-2) -2 ETHYLAMINES AND (THIENYL-3) -2 ETHYLAMINES |
| FR8113066 | 1981-06-30 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK291782A DK291782A (en) | 1982-12-31 |
| DK153793B true DK153793B (en) | 1988-09-05 |
| DK153793C DK153793C (en) | 1989-01-23 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK291782A DK153793C (en) | 1981-06-30 | 1982-06-29 | METHOD FOR PREPARING 2- (2-THIENYL) - OR 2- (3-THIENYL) -ETHYLAMINES |
Country Status (24)
| Country | Link |
|---|---|
| EP (1) | EP0069002B1 (en) |
| JP (1) | JPS5810575A (en) |
| KR (1) | KR840000539A (en) |
| AR (1) | AR231444A1 (en) |
| AT (1) | ATE15369T1 (en) |
| AU (1) | AU556916B2 (en) |
| CA (1) | CA1205811A (en) |
| CS (1) | CS236482B2 (en) |
| DD (1) | DD202711A5 (en) |
| DE (1) | DE3266028D1 (en) |
| DK (1) | DK153793C (en) |
| ES (1) | ES514220A0 (en) |
| FI (1) | FI822318L (en) |
| FR (1) | FR2508456A1 (en) |
| GR (1) | GR77203B (en) |
| HU (1) | HU186867B (en) |
| IE (1) | IE53278B1 (en) |
| IL (1) | IL65984A (en) |
| NO (1) | NO155345C (en) |
| NZ (1) | NZ200856A (en) |
| PT (1) | PT75156B (en) |
| SU (1) | SU1148562A3 (en) |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| NZ223583A (en) * | 1987-02-26 | 1990-02-26 | Merrell Dow Pharma | 2- or 3-thienyl-or-furyl-2-propyn-1-amines and antihypertensive compositions |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2623174A1 (en) * | 1976-05-22 | 1977-12-01 | Basf Ag | Primary amine prepn. from oximes - by hydrogenation in presence of ammonia with catalysts contg. aluminium and nickel and/or cobalt |
-
1981
- 1981-06-30 FR FR8113066A patent/FR2508456A1/en active Granted
-
1982
- 1982-06-01 IE IE1314/82A patent/IE53278B1/en not_active IP Right Cessation
- 1982-06-04 NZ NZ200856A patent/NZ200856A/en unknown
- 1982-06-06 IL IL65984A patent/IL65984A/en not_active IP Right Cessation
- 1982-06-08 AR AR289630A patent/AR231444A1/en active
- 1982-06-09 ES ES514220A patent/ES514220A0/en active Granted
- 1982-06-09 GR GR68378A patent/GR77203B/el unknown
- 1982-06-10 AU AU84752/82A patent/AU556916B2/en not_active Expired
- 1982-06-21 EP EP82401132A patent/EP0069002B1/en not_active Expired
- 1982-06-21 DE DE8282401132T patent/DE3266028D1/en not_active Expired
- 1982-06-21 AT AT82401132T patent/ATE15369T1/en not_active IP Right Cessation
- 1982-06-25 SU SU823457191A patent/SU1148562A3/en active
- 1982-06-29 ZA ZA824618A patent/ZA824618B/en unknown
- 1982-06-29 FI FI822318A patent/FI822318L/en not_active Application Discontinuation
- 1982-06-29 PT PT75156A patent/PT75156B/en unknown
- 1982-06-29 DK DK291782A patent/DK153793C/en not_active IP Right Cessation
- 1982-06-29 CS CS824901A patent/CS236482B2/en unknown
- 1982-06-29 HU HU822110A patent/HU186867B/en unknown
- 1982-06-29 CA CA000406317A patent/CA1205811A/en not_active Expired
- 1982-06-29 NO NO822228A patent/NO155345C/en not_active IP Right Cessation
- 1982-06-30 DD DD82241258A patent/DD202711A5/en not_active IP Right Cessation
- 1982-06-30 YU YU01429/82A patent/YU142982A/en unknown
- 1982-06-30 JP JP57113845A patent/JPS5810575A/en active Granted
- 1982-06-30 KR KR1019820002916A patent/KR840000539A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CS236482B2 (en) | 1985-05-15 |
| IE821314L (en) | 1982-12-30 |
| DD202711A5 (en) | 1983-09-28 |
| DE3266028D1 (en) | 1985-10-10 |
| CA1205811A (en) | 1986-06-10 |
| IL65984A0 (en) | 1982-09-30 |
| FR2508456B1 (en) | 1983-09-09 |
| SU1148562A3 (en) | 1985-03-30 |
| EP0069002A1 (en) | 1983-01-05 |
| JPH039914B2 (en) | 1991-02-12 |
| PT75156B (en) | 1984-02-21 |
| KR840000539A (en) | 1984-02-25 |
| GR77203B (en) | 1984-09-11 |
| YU142982A (en) | 1984-12-31 |
| PT75156A (en) | 1982-07-01 |
| ATE15369T1 (en) | 1985-09-15 |
| FI822318L (en) | 1982-12-31 |
| ZA824618B (en) | 1983-04-27 |
| AU8475282A (en) | 1983-01-06 |
| AU556916B2 (en) | 1986-11-27 |
| NO155345B (en) | 1986-12-08 |
| EP0069002B1 (en) | 1985-09-04 |
| DK153793C (en) | 1989-01-23 |
| NO155345C (en) | 1987-03-18 |
| NZ200856A (en) | 1985-11-08 |
| FI822318A0 (en) | 1982-06-29 |
| IE53278B1 (en) | 1988-09-28 |
| HU186867B (en) | 1985-10-28 |
| AR231444A1 (en) | 1984-11-30 |
| FR2508456A1 (en) | 1982-12-31 |
| NO822228L (en) | 1983-01-03 |
| IL65984A (en) | 1985-09-29 |
| ES8305348A1 (en) | 1983-04-01 |
| ES514220A0 (en) | 1983-04-01 |
| JPS5810575A (en) | 1983-01-21 |
| DK291782A (en) | 1982-12-31 |
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| Date | Code | Title | Description |
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| PUP | Patent expired |