CS208719B2 - Method of making the 2-oxopyrrolidin-(-alkylamides - Google Patents
Method of making the 2-oxopyrrolidin-(-alkylamides Download PDFInfo
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- CS208719B2 CS208719B2 CS7761A CS6177A CS208719B2 CS 208719 B2 CS208719 B2 CS 208719B2 CS 7761 A CS7761 A CS 7761A CS 6177 A CS6177 A CS 6177A CS 208719 B2 CS208719 B2 CS 208719B2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/24—Oxygen or sulfur atoms
- C07D207/26—2-Pyrrolidones
- C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
- C07D207/27—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with substituted hydrocarbon radicals directly attached to the ring nitrogen atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/36—Oxygen or sulfur atoms
- C07D207/40—2,5-Pyrrolidine-diones
- C07D207/404—2,5-Pyrrolidine-diones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. succinimide
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- Pyrrole Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
Vynález te týká způsobu výroby 2-oxooPrr°oidin-N-alkylmidů obecného vzorce I,Te invention relates to the preparation of 2-rr oxooP ° oidin N alkylmidů formula I
(X)(X)
X-CQNH2 kde X znamená ilkyliden t 1 iž 4 atomy Uilíku.X-CQNH 2 wherein X is C 1 -C 4 alkylidene.
Je známo, že te sloučeniny obecného vzorce I mohou získat redukcí 2-oxooprrroidinnalrii omeeaihalogeenlkylimidy podle britkkého patentového tpitu č. 1 039 113, jakož i působením amoniaku na estery nebo chloridy 2-oxoopyrolidinkarbooylových kystlin, rovněž podle britského patentového spisu δ. 1 039 113 nebo termický^ rozkaadem amorných tooí 2-oxoo1~hprrooidinh karboxylových kyseein podle britkkého patentového spisu č. 1 309 692. Dále je poptáno, že 2-oxo-1-pyroolidin-lmll-butyrεoid může vzniknout podle USA patentového spisu č. 3 250 784 působením kapalného amomiaku na ga□Olhutyr<n,lktnn při vyšších teplotách a za vysokého tlaku.It is known that the compounds of the formula I can be obtained by reduction of 2-oxo-propyroidalnalium omeeahalogenoalkylimides according to British Patent Specification No. 1,039,113 and by the action of ammonia on the esters or chlorides of 2-oxoopyrrolidine carbooyl kystines, also according to British patent specification δ. No. 1,039,113 or the thermal decomposition of the amorphous salts of 2-oxo-1-hydroxypropyl carboxylic acid according to British Patent Specification No. 1,309,692. It is further desirable that 2-oxo-1-pyrrolidine-1H-butyride can be formed according to U.S. Pat. No. 3,250,784 by the action of liquid amomiac on ga □ olhutyr <n, lktnn at higher temperatures and high pressure.
Některé sloučeniny, které je možné tímto způsobem vyrobit, vykazují terapeutický účinek při léčení mot^i^:i^ckých poruch, hyppetonie, hyperkinese a poruch panmět. Nejznáměší z těchto sloučenin je 2-oxo-1-pprrolidinacetemie, který je znám pod generickým názvem PIRACETAM.Certain of the compounds that can be produced in this manner exhibit a therapeutic effect in the treatment of motile disorders, hyppetonia, hyperkinesia and hinge disorders. The best known of these compounds is 2-oxo-1-proprolidinacetemia, known under the generic name PIRACETAM.
Z literatury je známo, že 2,5-diIxooyrooOidin, jakož i jeho N-mmeyldeelvát te mohou redukovat elektrolyticky na 2-oxonyrro0iein, popřípadě na jemu ^ppolídaící N-motyldeeivlt (viz Chem. Ber. 33) /1900// 2 22-4; Coi. Czech. Chem. Comm. 2 /1930/ 531; J. Am. Chem. Soc. 55 /1933/ 295).It is known in the literature that the 2,5-dioloyloylidine and its N-methyl allactate can be electrolytically reduced to 2-oxonyloxy or to its substituting N-motyl derivatives (see Chem. Ber. 33) / 1900 // 22. 4; Coi. Czech. Chem. Comm. 2/1930/531; J. Am. Chem. Soc. 55/1933/295).
WW
206719 (I)206720 (I)
Podstata způsobu výroby 2-oxopyrrolldln-N-alkylamldů obecného vzorce I,The process for the preparation of 2-oxopyrrolidine-N-alkylamides of the general formula I,
I x-conh2 kde X znamená alkyliden a 1 až 4 atomy uhlíku, podle vynálezu spočívá v tom, že se kondenzací natriůmsukcinimidu a omega-halogenalkylamidu obecného vzorce II,According to the invention, x-conh 2 wherein X is alkylidene and 1 to 4 carbon atoms is characterized by the condensation of the sodium succinimide and the omega-haloalkylamide of the formula II,
Hal-X-CONH2 (II) kde Hal znamená halogen а X má shora uvedený význam, získaný 2,5-dioxopyrrolidin-N-alkylamid obecného vzorce III,Hal-X-CONH 2 (II) wherein Hal is halogen and X is as defined above, the obtained 2,5-dioxopyrrolidine-N-alkylamide of formula III,
(III) x-conh2 kde X má shora uvedený význam, elektrolyticky redukuje.(III) x-conh 2 wherein X is as defined above, electrolytically reduces.
Uvedená reakce probíhá podle následujícího reakčního schématu:The reaction proceeds according to the following reaction scheme:
nJ L· + Hal-X-CONHn л | |> I | °Л/° 2 — O=kN>O el.red. ^>=0 i iinJ · L + Hal-X-CONHn л | |> I | ° Л / ° 2 - O = to N > O el. ^> = 0 i ii
Na X-CONH2 X-CONH2 To X-CONH 2 X-CONH 2
II IVIII IVI
Podle vynálezu se natriumsukcinimid obvykle vyrobí působením natrlumetylátu na sukcinizaid v nízkém alkoholu, například etanolu, a potom se převede reakcí s omega-halogenalkylamidy v etanolu, dimetylformamidu, toluenu nebo jiném vhodném rozpouštědla, při 80 až 150 °C na N-alkylamidy 2,5-oxopyrrolidinu. Tyto sloučeniny se potom podrobí elektrolytické redukci, s výhodou při 0 až 30 °C, v elektrolyzéru s kovovou katodou (například olověnou) za použití diafragmy, v kyselém prostředí a při konstantní hustotě proudu, s výhodou 5 až 8 ampérů. Jako anoda se mohou používat kovy jako platina nebo olovo. Průběh reakce se může sledovat pomocí chroraatografie na tenké vrstvě. Zpracování elektrolytu po provedené reakci neutralizací louhy při 0 až 5 °C, filtrací, jakož i odpařením filtrátu až do sucha ve vakuu poskytne krystalický surový produkt, z něhož se požadovaný produkt může extrahovat vhodným rozpouštědlem, jako například etanolem. Ze získaného roztoku se dá získat čistý produkt po odpaření známými metodami krystalizace.According to the invention, sodium succinimide is usually prepared by treating a succinizide in a low alcohol such as ethanol with sodium trimethylate and then converted to N-alkyl amides at 80 to 150 ° C by reaction with omega-haloalkylamides in ethanol, dimethylformamide, toluene or other suitable solvent. -oxopyrrolidine. These compounds are then subjected to an electrolytic reduction, preferably at 0 to 30 ° C, in a metal cathode (e.g. lead) electrolyzer using a diaphragm, in an acid medium and at a constant current density, preferably 5 to 8 amperes. As anode, metals such as platinum or lead can be used. The progress of the reaction can be monitored by thin layer chromatography. Treatment of the electrolyte after reaction by neutralizing the caustic at 0-5 ° C, filtering, and evaporating the filtrate to dryness under vacuum affords a crystalline crude product from which the desired product can be extracted with a suitable solvent such as ethanol. From the solution obtained, a pure product can be obtained after evaporation by known crystallization methods.
Tímto způsobem se optimálně zabrání hydrolytickému odbourání amidů, které by se dalo jinak očekávat.In this way, the hydrolytic degradation of the amides that would otherwise be expected is optimally avoided.
Přednost způsobu podle vynálezu oproti způsobům známým z literatury, které v podstatě spočívají v tom, že se jako výchozí produkt použije pyrrolidinnatrium, spočívá v tom, že se může při výrobě sukeinimidnatria upustit od použití kovového sodíku nebo natriumhydridu, že se meziprodukt pro elektrolýzu získá velmi jednoduchým způsobem v dobrých výtěžcích a s dobrou čistotou a že dále použití elektrolytické redukce pro výrobu sloučenin vede kvalitativně i kvantitativně к velmi dobrým výsledkům. Celý způsob je charakterizován jednoduchostí provedení, malým zatížením okolí, jakož i malými náklady na výchozí produkty.The advantage of the process according to the invention over methods known from the literature, which consists essentially in the use of pyrrolidine sodium as the starting product, is that the use of sodium metal or sodium hydride can be dispensed with in the production of succinimidatrium, in a simple manner in good yields and good purity, and that further the use of electrolytic reduction for the production of the compounds leads to very good results qualitatively and quantitatively. The whole process is characterized by simplicity of design, low environmental burden, as well as low initial product costs.
Vynález je dále popsán následujícími příklady, které jej však nemají nikterak omezovatThe invention is further described by the following non-limiting examples
Výroba 2,5-dioxopyrrolidin-N-alkylamidů:Production of 2,5-dioxopyrrolidine-N-alkylamides:
Příklad 1Example 1
2j5-Oioopprrrodidin-a-acetamid25-Oiooproprodidine-α-acetamide
13,78 g (0,155 molu) natrUmsukcinimOdu a 14,50 g (0,155 molu) chlvracetamidu se zahřívá a 500 ml etanolu pod opětným tokem 5 hodin k varu. Vyloučené krystaly chloridu sodného se odfiltrují· Z roztoku se během 48 hodin .vyloučí 9,4 g produktu.13.78 g (0.155 mol) of sodium succinimide and 14.50 g (0.155 mol) of chloroacetamide were heated and refluxed for 500 hours with 500 ml of ethanol. The precipitated sodium chloride crystals were filtered off. 9.4 g of product precipitated out of solution within 48 hours.
Teplota tání 140 až 143 °C.Melting point 140-143 ° C.
Po ii.tta^cO produktu a odp^a^ení etanolu ve vakuu až do sucha, krystalO-zaci o etanolu, se získá dalších 10,4 g produktu. Teplota tání 140 až 143 °C. Celkový výtěžek 19,8 g/81,8 %.After the product is evaporated and the ethanol is evaporated to dryness in vacuo until crystallization with ethanol, an additional 10.4 g of product is obtained. Melting point 140-143 ° C. Total yield 19.8 g / 81.8%.
Analýza: (156,14) vypočteno: 46,15 % C, 5,16 % H, 17,94 % П; nalezeno: 46,30 % C, 5,02 % H, 17,77 % П.Analysis: (156.14) calculated: 46.15% C, 5.16% H, 17.94% P; Found:% C, 46.30;% H, 5.02;% P, 17.77.
IR spektrum (KBr)IR spectrum (KBr)
-CO-N-CO-CO-N-CO
-CONH2 -CONH 2
-nh2 -nh 2
Msaneeické rezonanční spektrum (DMSO-dgMass Resonance Spectrum (DMSO-dg
•Příklad 2• Example 2
2,5-Vioχppyvrolndn-nj-aa-P“0Popn amadid2,5-Vioxypyrrolidine-nj-aa-P10Popn amadide
Analogicky jako v příkladu 1 se získá ze 4,84 g (0,04 molu) natrUumsukciniaidu a 6,07 g (0,04 molu) beta-propionamidu ve 120 ml dOaetplVoaajmidu při 118 až 120 °C vedle 1,14 g neorejnvaanéhv natruimsukcLnimOdu 2,96 g (61,3 %) požadovaného produktu. Teppota tání 110 až 111 °C. AneaytOcký čistý produkt teploty tání 112 až 113 °C se získá krystalO-zací ze směsi benzenu a etanolu.Analogously to Example 1, from 4.84 g (0.04 mole) of sodium succiniumide and 6.07 g (0.04 mole) of beta-propionamide in 120 ml of acetonitrile at 118-120 ° C are obtained in addition to 1.14 g of untreated sodium sulfide. 2.96 g (61.3%) of the desired product. Melting point 110-111 ° C. The pure pure product, m.p. 112 DEG-113 DEG C., is obtained by crystallization from a mixture of benzene and ethanol.
Analýza: ΟΗΗ,Ν2°3 (170,17) vypočteno: 49,40 % C, 5,92 % H, 16,46 % П; nalezeno: 49,67 % C. 5,64 % H. 16,19 % П.Analysis: Ο Η Η, Ν 2 ° 3 (170.17) calculated: 49.40% C, 5.92% H, 16.46% П; found: 49.67% C. 5.64% H. 16.19% П.
IR spektrum (KBr)IR spectrum (KBr)
Píkl a d 3Peak a d 3
2,5-Dioxppyrrolidin-N-beta-propionsmid2,5-Dioxppyrrolidine-N-beta-propionsmid
Aidlogicky jako v příkladu 2, avšak při teplotě 150 °C a době reakce tří hodin,.se získá 1,18 g nezreegováného sukcidimidu a 2,6 g (54,5 %) požadovaného produktu s teplotou tádí 109 až 111 °C.In an analogous manner to Example 2, but at a temperature of 150 ° C and a reaction time of three hours, 1.18 g of unregulated succinimide and 2.6 g (54.5%) of the desired product were obtained with a melting point of 109-111 ° C.
Příklad 4Example 4
2,5-Dloxppyioiodidin-N-giMnbubytyramid2,5-Dloxppyioiodidine-N-aminobubytyramide
Aidlogicky jako v příkladu 1 se získá ze 2,42 g (0,02 molu) datrimsukcidimidu a 2,43 g (0,02 molu) gamaachlorbutyremidu ve 30 ml dimetylformamidu, ké kterému se přidaly 0,2 g jodidu soddého, při teplotě reakce 118 až 120 °C po pěti hodidách 0,6 g dezreagovadého sukcidimidu a 0,92 < (35,8 %) požadovadého produktu. Teplota tádí 79 až 81 °C. A^aal^t-icky čistý produkt se získá krystal0zyc0 ze směsi bedzedu, etadolu a éteru. Teplota tádí 82 až 84 °C.Analogously to Example 1, 2.45 g (0.02 mole) of datrimsuccidimide and 2.43 g (0.02 mole) of gammaachlorobutyremide in 30 ml of dimethylformamide, to which 0.2 g of sodium iodide were added, were obtained at reaction temperature. 118 DEG-120 DEG C. after 5 hours 0.6 g of desulfurized succinimide and 0.92 <(35.8%) of the desired product. Mp 79-81 ° C. The product was crystallized from a mixture of bedzed, ethanol and ether. Mp 82-84 ° C.
Aidlýza: ΟθΗ^^ (184,19)Aidlyza: ΟθΗ ^^ (184,19)
680 (vs)680 (vs)
Magnetické rezonanční spektrum (DMSO-dg)Magnetic Resonance Spectrum (DMSO-dg)
Příklad 5Example 5
2,5-Oioxppyrrolidin-N-maiia-buryramid2,5-Oioxppyrrolidine-N-methyl-buryramide
Analogicky jako v příkladu 4 se reakce provede ve 100 rl absolutního toluenu. Získá se 0,8 g nezreegovaného sukciniridu a 0,667 (32,6 %) požadovaného produktu. Teplota bání 80 až 82 °C.Analogously to Example 4, the reaction was carried out in 100 µl of absolute toluene. 0.8 g of unregulated succiniride and 0.667 (32.6%) of the desired product are obtained. Mp 80-82 ° C.
Výroba 2-oioppprolidin--i-alUylmiidů elebrolptickou redukcí vhodných 2,5-dioiopyproli·din-N-alkyl amidů:Preparation of 2-oioppprolidine-i-allylmiids by elebrolptic reduction of suitable 2,5-dihydro-proline-N-alkyl amides:
Příklad 6Example 6
2-0ilpyprQlidin-N-acetιmid g (0,0064 rolu) 2,5-dioilyyгrllidln-N-ccetaridu se rozpustí při 0 až 5 °C v 80 rl 50% kyseliny sírové a redukuje se elektrolyticky v elektrolyzé™ o objemu asi 100 rl při tonetantoír proudu 8 arperů za požití olověró labldu s povrcher 5° cr2 a olověnou anodou při teplotě 0 až 5 °C. Elektrolyter anodového prostoru je 10% kyselina sírová. Prostor anody a prostor katody jsou navzájer odděleny syntetickou diafagrou. Prorísení roztoku elektrolytu v prostoru katody se dosáhne poHu^íí rí^gne-ického ríchadla. Průběh reakce se sleduje porod choo^ítb^lro^f:Lt na tenké vrstvě (chloroform : rrtanol = 9:1). Produkt se izoluje z rea^ního roztoku neuuralizací ^dr^idem sodným při 0 až 5 °C až do hodnoty pH 7 a potom fiirrací vzniklého síranu sodného. O^i^Ea^ení^r filOrátu ve vakuu až do sucha se získá surový produkt, který se čistí extrakcí a lrystaaizacC. Získá se 0,66 g (72,6 %) požadovaného produktu s teplotou tání 149 až 151 °C.2-Oilpyrrolidine-N-acetamide g (0.0064 roles) of 2,5-dioilyl-pyridine-N-cetaride is dissolved at 0 to 5 ° C in 80 ml of 50% sulfuric acid and reduced electrolytically in an electrolysis cell of about 100 ml. when tonetantoír stream 8 after ingestion ARPER olověró L and b in LD with p ovrcher 5 ° CR 2 and the lead anode at 0-5 ° C. The electrode of the anode compartment is 10% sulfuric acid. The anode space and the cathode space are separated from each other by a synthetic diaphragm. The solution of the electrolyte solution in the cathode space is obtained by using a thickened agitator. The progress of the reaction was monitored by the thin layer (chloroform: methanol = 9: 1). The product is isolated from the reaction solution by neuralization with sodium sulfate at 0-5 ° C to pH 7 and then by filtration of the resulting sodium sulfate. Purification of the filtrate in vacuo to dryness yielded a crude product which was purified by extraction and crystallization. 0.66 g (72.6%) of the desired product is obtained with a melting point of 149-151 ° C.
Příklad 7Example 7
2-Oxoopprolidin-N-actaerid2-Oxoopprolidine-N-actaeride
Analogicky jako v příkladu 6 se získá při provedení reakce při konstantním proudu 5 ampérů a reakční teplotě 30 °C 0,44 g (48,4 %) požadovaného produktu, teplota tání 148 až 150 °C.Analogously to Example 6, 0.44 g (48.4%) of the desired product is obtained at a constant current of 5 amperes and a reaction temperature of 30 ° C, m.p. 148-150 ° C.
PPíklad 8EXAMPLE 8
2-Oxoopyrolidin-i-attaypooplonarid2-Oxoopyrrolidine-1-attaypooplonaride
Analogicky jako v příkladu 6, se získá z 0,5 g (0,00294 rolu) 2,5-dililpypгolidin-i-beta-propoonímidu při 0 až 5 °C, 0,31 g (67,5 %) požadovaného produktu s teplotou tání 135 až 137 °C.Analogously to Example 6, from 0.5 g (0.00294 roles) of 2,5-dililpyrrolidine-1-beta-propoonimide at 0 to 5 ° C, 0.31 g (67.5%) of the desired product is obtained. mp 135-137 ° C.
Příklad 9Example 9
2-Oxopyrrolidin-N-gama-butyramid2-Oxopyrrolidine-N-gamma-butyramide
Analogicky jako v příkladu 6 se získá z 0,5 g (0,00272 molu) 2,5-dioxopyrrolidin-N-gama-butyгamidu 0,29 g (62,8 %) požadovaného produktu, teplota tání 95 až 97 °C.Analogously to Example 6, 0.29 g (62.8%) of the desired product is obtained from 0.5 g (0.00272 mol) of 2,5-dioxopyrrolidine-N-gamma-butylamide, m.p. 95-97 ° C.
Claims (4)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| YU78/76A YU39341B (en) | 1976-01-14 | 1976-01-14 | Process for obtaining n-alkylamide-2-oxopyrrolidines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS208719B2 true CS208719B2 (en) | 1981-09-15 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS7761A CS208719B2 (en) | 1976-01-14 | 1977-01-04 | Method of making the 2-oxopyrrolidin-(-alkylamides |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS52116463A (en) |
| AT (1) | AT355013B (en) |
| CH (1) | CH624671A5 (en) |
| CS (1) | CS208719B2 (en) |
| FI (1) | FI63750C (en) |
| HU (1) | HU172999B (en) |
| PL (1) | PL103074B1 (en) |
| SE (1) | SE416730B (en) |
| SU (1) | SU893131A3 (en) |
| YU (1) | YU39341B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5933068A (en) * | 1982-08-17 | 1984-02-22 | Nitsukuu Kogyo Kk | Vacuum impregnation method |
| JPS59152030A (en) * | 1983-02-15 | 1984-08-30 | Taiho Kogyo Co Ltd | Method and device for impregnation of die casting parts |
| JPS59150655A (en) * | 1983-04-14 | 1984-08-28 | Taiho Kogyo Co Ltd | Method and device for impregnation to die cast parts |
| JPS62218028A (en) * | 1986-03-20 | 1987-09-25 | Toyota Motor Corp | Impregnation treatment method |
| RU2629117C1 (en) * | 2016-06-14 | 2017-08-24 | Сизов Владимир Владимирович | Method of producing 4-substituted 2-[2-oxo-1-pyrrolidinyl] acetamide |
-
1976
- 1976-01-14 YU YU78/76A patent/YU39341B/en unknown
- 1976-12-29 CH CH1643376A patent/CH624671A5/en not_active IP Right Cessation
- 1976-12-30 AT AT980876A patent/AT355013B/en not_active IP Right Cessation
-
1977
- 1977-01-04 CS CS7761A patent/CS208719B2/en unknown
- 1977-01-10 SE SE7700172A patent/SE416730B/en not_active IP Right Cessation
- 1977-01-11 HU HU77PI00000559A patent/HU172999B/en unknown
- 1977-01-12 PL PL1977195267A patent/PL103074B1/en unknown
- 1977-01-12 FI FI770088A patent/FI63750C/en not_active IP Right Cessation
- 1977-01-12 SU SU772439826A patent/SU893131A3/en active
- 1977-01-14 JP JP255077A patent/JPS52116463A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| YU7876A (en) | 1982-02-28 |
| FI63750C (en) | 1983-08-10 |
| ATA980876A (en) | 1979-07-15 |
| SU893131A3 (en) | 1981-12-23 |
| JPS52116463A (en) | 1977-09-29 |
| PL195267A1 (en) | 1978-03-13 |
| SE7700172L (en) | 1977-07-15 |
| FI770088A (en) | 1977-07-15 |
| AT355013B (en) | 1980-02-11 |
| FI63750B (en) | 1983-04-29 |
| PL103074B1 (en) | 1979-05-31 |
| JPS5744667B2 (en) | 1982-09-22 |
| CH624671A5 (en) | 1981-08-14 |
| SE416730B (en) | 1981-02-02 |
| YU39341B (en) | 1984-10-31 |
| HU172999B (en) | 1979-01-28 |
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