NO760448L - - Google Patents
Info
- Publication number
- NO760448L NO760448L NO760448A NO760448A NO760448L NO 760448 L NO760448 L NO 760448L NO 760448 A NO760448 A NO 760448A NO 760448 A NO760448 A NO 760448A NO 760448 L NO760448 L NO 760448L
- Authority
- NO
- Norway
- Prior art keywords
- deutero
- fluoro
- alanine
- propionic acid
- isomer
- Prior art date
Links
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- UYTSRQMXRROFPU-LIIDHCAMSA-N (2s)-2-amino-2-deuterio-3-fluoropropanoic acid Chemical compound FC[C@](N)([2H])C(O)=O UYTSRQMXRROFPU-LIIDHCAMSA-N 0.000 claims description 10
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 10
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 235000010288 sodium nitrite Nutrition 0.000 claims description 4
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 3
- 229960003767 alanine Drugs 0.000 claims description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 2
- 125000005843 halogen group Chemical group 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- HBQYPTHLJXLQRI-LIIDHCAMSA-N (2S)-2-azido-2-deuterio-3-fluoropropanoic acid Chemical compound N(=[N+]=[N-])[C@@](C(=O)O)(CF)[2H] HBQYPTHLJXLQRI-LIIDHCAMSA-N 0.000 description 3
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- UYTSRQMXRROFPU-MYSWAXPFSA-N (2r)-2-amino-2-deuterio-3-fluoropropanoic acid Chemical compound FC[C@@](N)([2H])C(O)=O UYTSRQMXRROFPU-MYSWAXPFSA-N 0.000 description 1
- UYTSRQMXRROFPU-VMNATFBRSA-N 2-amino-2-deuterio-3-fluoropropanoic acid Chemical compound FCC(N)([2H])C(O)=O UYTSRQMXRROFPU-VMNATFBRSA-N 0.000 description 1
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C247/00—Compounds containing azido groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C265/00—Derivatives of isocyanic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/15—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen containing halogen
- C07C53/19—Acids containing three or more carbon atoms
- C07C53/21—Acids containing three or more carbon atoms containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/185—Saturated compounds having only one carboxyl group and containing keto groups
- C07C59/19—Pyruvic acid
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Fremgangsmåte ved fremstilling av 2-deutero-3-fluor-D-alanin. Procedure for the production of 2-deutero-3-fluoro-D-alanine.
Foreliggende oppfinnelse angår generelt fremstillingen av 2-deutero-3-fluor-D-alanin og dets farmakologisk godtagbare salter sorn er sterkt a nt ibakte r ielle midler som er nyttige til å inhibere vekst av patogene bakterier av både den grampositive The present invention generally relates to the preparation of 2-deutero-3-fluoro-D-alanine and its pharmacologically acceptable salts, which are highly antibacterial agents useful in inhibiting the growth of pathogenic bacteria of both the gram-positive
og gramnegative type. Mere spesielt angår oppfinnelsen en ny asymmetrisk.fremgangsmåte hvorved 2-deutero-3-f luor-L-alanin overføres til dets D-isomer. and gram-negative type. More particularly, the invention relates to a new asymmetric process by which 2-deutero-3-fluoro-L-alanine is transferred to its D-isomer.
2-deutero-3-fluor-L-alanin oppløses i sterk (6n) vandig hydrogenbromidsyre eller saltsyre, natriumnitrit tilsettes por-sjonsvis til oppløsningen, og den dannede oppløsning holdes ved ca. 0°C i ca. 3 timer for å danne L-2-brom-2-deutero-3-fluor-propionsyre, hhv. L-2-klor-2-deutero-3~fluor-propionsyre. 2-halogen-2-deutero-3-fluor-propionsyren utvinnes bekvemt fra den sure reaksjonsoppløsning ved ekst raksjon med et med vann ubland-bart organisk oppløsningsmiddel som methylenklorid, og inndamp-ning av ekstraktet i vakuum, idet den gjenværende L-2-halogen-2-deutero-3-fluor-propionsyre renses ved fraksjonert vakuumdestillasjon. L-2-brom-2-deutero-3-fluor-propionsyren og dens 2-kior-analog omsettes så med ammoniakk eller natriumazid.. Omsetningen av L-2-halogen-2-déutero-3-fluor-propionsyren med ammoniakk ut-føres fortrinnsvis i et trykkar under anvendelse av flytende ammoniakk'ved ca. værelsetemperatur, under hvilke betingelser reaksjonen i alminnelighet er fullstendig i løpet av ca. 5 dager. Fordampning av ammoniakken gir 2-deutero-3-fluor-3-alanin som bekvemt renses ved omkrystallisasjon fra isopropanol-vann.. 2-deutero-3-fluoro-L-alanine is dissolved in strong (6n) aqueous hydrobromic acid or hydrochloric acid, sodium nitrite is added portionwise to the solution, and the resulting solution is kept at approx. 0°C for approx. 3 hours to form L-2-bromo-2-deutero-3-fluoro-propionic acid, resp. L-2-chloro-2-deutero-3-fluoro-propionic acid. The 2-halo-2-deutero-3-fluoro-propionic acid is conveniently recovered from the acidic reaction solution by extraction with a water-immiscible organic solvent such as methylene chloride, and evaporation of the extract in vacuum, the remaining L-2- Halogen-2-deutero-3-fluoro-propionic acid is purified by fractional vacuum distillation. The L-2-bromo-2-deutero-3-fluoro-propionic acid and its 2-chior analogue are then reacted with ammonia or sodium azide. The reaction of the L-2-halo-2-deutero-3-fluoro-propionic acid with ammonia yields - is preferably conducted in a pressure vessel using liquid ammonia at approx. room temperature, under which conditions the reaction is generally complete within approx. 5 days. Evaporation of the ammonia gives 2-deutero-3-fluoro-3-alanine, which is conveniently purified by recrystallization from isopropanol-water.
Omsetningen av.L-2-klor- eller L-2-brom-mellomproduktet med natriumazid utføres fortrinnsvis ved å bringe reaktantene sammen i diméthylformamid, og omrøre reaksjonsblåndingen ved i det vesentlige værelsetemperatur, under hvilke betingelser reak sjonen er i det vesentlige fullstendig i løpet av en dag. Den således dannede D-2-azido-2-deutero-3-fluor-propionsyre under-kastes så katalytisk hydrogenering hvorved 2-azidogruppen reduseres til 2-amino og derved danner 2-deutero-3-fluor-D- The reaction of the L-2-chloro or L-2-bromo intermediate with sodium azide is preferably carried out by bringing the reactants together in dimethylformamide, and stirring the reaction mixture at substantially room temperature, under which conditions the reaction is substantially complete during of a day. The D-2-azido-2-deutero-3-fluoro-propionic acid thus formed is then subjected to catalytic hydrogenation whereby the 2-azido group is reduced to 2-amino and thereby forms 2-deutero-3-fluoro-D-
alanin. Denne fremgangsmåte gjør det mulig direkte å overføre L-isomeren av 2-deutero-3~fluoralanin til D-isomeren. alanine. This method makes it possible to directly transfer the L-isomer of 2-deutero-3-fluoroalanine to the D-isomer.
Som nevnt ovenfor, er 2-deutero-3~fluor-D-alanin et sterktAs mentioned above, 2-deutero-3-fluoro-D-alanine is a strong
og nyttig ant ibakterielt middel, mens det iso.mere 2-deutero-3-fluor-L-alanin (skjønt det har antibakteriell virkning) i.alminnelighet er en uønsket isomer. Istedenfor således å racemisere v L-isomeren erholdt ved spaltning av 2-deutero-3-fluor-DL-alanin, fulgt av ytterligere spaltning av den således dannede DL-bland-ing, kan L-isomerene, 2-deutero-3-fluor-L-alanin, overføres asymmetrisk direkte til 2-deutero-3-fluor-D-alanin. and useful antibacterial agent, while the isomeric 2-deutero-3-fluoro-L-alanine (although antibacterial) is generally an undesirable isomer. Instead of thus racemizing the L-isomer obtained by cleavage of 2-deutero-3-fluoro-DL-alanine, followed by further cleavage of the DL mixture thus formed, the L-isomers, 2-deutero-3-fluoro -L-alanine, is transferred asymmetrically directly to 2-deutero-3-fluoro-D-alanine.
De følgende eksempler belyser fremgangsmåtene for utfør-else av oppfinnelsen. The following examples illustrate the methods for carrying out the invention.
Eksempel 1Example 1
21,492-deutero-3-fluor-L-alanin oppløses i 250 ml 6 N vandig hydrogenbromidsyre. Oppløsningen avkjøles til 0°C, og 22 g natriumnitrit tilsettes i små porsjoner idet temperaturen holdes ved 0 - 5°C. Efter avslutning av tilsetningen holdes reaksjonsblandingen ved 0°C i 3 timer. Oppløsningen ekstraheres med methylenklorid som så tørres over magnesiumsulf at.. Methylenkloridet fordampes i vakuum. Den gjenværende L-2-brom-2-deutero-3-fluor-propionsyre renses så ved fraksjonert vakuumdestillasjon. 21,492-deutero-3-fluoro-L-alanine is dissolved in 250 ml of 6 N aqueous hydrobromic acid. The solution is cooled to 0°C, and 22 g of sodium nitrite are added in small portions, keeping the temperature at 0 - 5°C. After completion of the addition, the reaction mixture is kept at 0°C for 3 hours. The solution is extracted with methylene chloride, which is then dried over magnesium sulphate. The methylene chloride is evaporated in a vacuum. The remaining L-2-bromo-2-deutero-3-fluoro-propionic acid is then purified by fractional vacuum distillation.
3,0 g L-2-brom-2-deutero-3-fluor-propionsyre innføres i en stålbombe og 30 ml flytende ammoniakk tilsettes. Bomben lukkes og hensettes ved værelsetemperatur i 5 dager. Ammoniakken fordampes, og det rå 2-deutero-3-fluor-D-alanin renses ved omkrystallisasjon fra 50% isopropanol-vann. 3.0 g of L-2-bromo-2-deutero-3-fluoro-propionic acid are introduced into a steel bomb and 30 ml of liquid ammonia are added. The bomb is closed and left at room temperature for 5 days. The ammonia is evaporated, and the crude 2-deutero-3-fluoro-D-alanine is purified by recrystallization from 50% isopropanol-water.
Alternativt oppløses 2,0 g L-2-brom-2-deutero-3-fluor-propionsyre i 20 ml dimethylformamid. 1,0 g natriumazid tilsettes, og blandingen omrøres ved 2 5°C.i 24 timer. Blandingen helles i vann og ekstraheres med ether. Etherekstraktet vaskes med vann og tørres. Ca. 20 ml ethanol tilsettes til filt ratet, Alternatively, 2.0 g of L-2-bromo-2-deutero-3-fluoro-propionic acid are dissolved in 20 ml of dimethylformamide. 1.0 g of sodium azide is added, and the mixture is stirred at 25°C for 24 hours. The mixture is poured into water and extracted with ether. The ether extract is washed with water and dried. About. 20 ml of ethanol is added to the felt rate,
og den dannede oppløsning av D-2-azido-2-deutero-3-fluor-propionsyre omsettes med hydrogen i nærvær av 0,5 g 5% palladium-på- and the resulting solution of D-2-azido-2-deutero-3-fluoro-propionic acid is reacted with hydrogen in the presence of 0.5 g of 5% palladium-on-
carbon. Katalysatoren frafiltreres, og oppløsningsmidlet fordampes i vakuum hvorved man får rått 2-deutero-3-fluor-D-alanin som renses ved krystallisasjon fra vandig isopropanol. carbon. The catalyst is filtered off, and the solvent is evaporated in vacuo, whereby crude 2-deutero-3-fluoro-D-alanine is obtained, which is purified by crystallization from aqueous isopropanol.
Eksempel 2Example 2
21,492-deutero-3-fluor-L-alanin oppløses i 250 ml 6 N vandig saltsyre. Oppløsningen avkjøles til 0°C, og 22 g natriumnitrit tilsettes i små porsjoner mens temperaturen holdes ved 0 - 5°C. Efter avsluttet tilsetning holdes reaksjonsoppløsningen ved 0°C i 3 timer. Den erholdte oppløsning ekstraheres med methylenk-lorid, methylenkloridekst raktet tørres over magnesiumsulf at , og methylenkloridet fordampes i vakuum. Den gjenværende L-2-klor-2-deutero-3-fluor-propionsyre renses ved fraksjonert vakuumdestillasjon. 21,492-deutero-3-fluoro-L-alanine is dissolved in 250 ml of 6 N aqueous hydrochloric acid. The solution is cooled to 0°C, and 22 g of sodium nitrite are added in small portions while the temperature is maintained at 0 - 5°C. After the addition is finished, the reaction solution is kept at 0°C for 3 hours. The resulting solution is extracted with methylene chloride, the methylene chloride extract is dried over magnesium sulfate, and the methylene chloride is evaporated in a vacuum. The remaining L-2-chloro-2-deutero-3-fluoro-propionic acid is purified by fractional vacuum distillation.
3,0 g L-2-klor-2-deutero-3- fluor-propionsyre innføres i en stålbombe, og 30 ml flytende ammoniakk tilsettes. Bomben lukkes og hensettes ved værelsetemperatur i 5 dager. Ammoniakken fordampes, og det rå 2-deutero-3-fluor-D-alanin renses ved krystallisasjon fra 50% isopropanol-vann. 3.0 g of L-2-chloro-2-deutero-3-fluoro-propionic acid are introduced into a steel bomb, and 30 ml of liquid ammonia is added. The bomb is closed and left at room temperature for 5 days. The ammonia is evaporated, and the crude 2-deutero-3-fluoro-D-alanine is purified by crystallization from 50% isopropanol-water.
Alternativt oppløses 2,0 g L-2-klor-2-deutero-3-fluor-propionsyre i 20 ml diméthylf o.rmamid. 1,0 g natriumazid tilsettes, og blandingen omrøres ved 25°C i 24 timer.. Blandingen helles i vann, og D-2-azido-2-deutero-3-fluor-propionsyren hydrogeneres katalytisk, og produktet renses ved omkrystallisasjon fra 50%-ig vandig isopropanol, hvorved man får 2-deutero-3-fluor-D-alanin. Alternatively, 2.0 g of L-2-chloro-2-deutero-3-fluoro-propionic acid are dissolved in 20 ml of dimethylformamide. 1.0 g of sodium azide is added, and the mixture is stirred at 25°C for 24 hours. The mixture is poured into water, and the D-2-azido-2-deutero-3-fluoro-propionic acid is hydrogenated catalytically, and the product is purified by recrystallization from 50 % aqueous isopropanol, whereby 2-deutero-3-fluoro-D-alanine is obtained.
Claims (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/552,474 US3950411A (en) | 1972-02-03 | 1975-02-24 | Processes for asymmetric conversion of 3-fluoro-L-alanine and 2-deutero-3-fluoro-L-alanine to their D-isomers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO760448L true NO760448L (en) | 1976-08-25 |
Family
ID=24205490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO760448A NO760448L (en) | 1975-02-24 | 1976-02-12 |
Country Status (21)
| Country | Link |
|---|---|
| JP (1) | JPS51110513A (en) |
| AR (1) | AR207277A1 (en) |
| AU (1) | AU500536B2 (en) |
| CA (1) | CA1045157A (en) |
| CH (1) | CH620194A5 (en) |
| CS (1) | CS199274B2 (en) |
| DE (1) | DE2607252A1 (en) |
| DK (1) | DK55976A (en) |
| ES (1) | ES445381A1 (en) |
| FI (1) | FI760302A (en) |
| FR (1) | FR2301513A1 (en) |
| GB (1) | GB1488332A (en) |
| GR (1) | GR59306B (en) |
| HU (1) | HU173362B (en) |
| IE (1) | IE43351B1 (en) |
| NL (1) | NL7601511A (en) |
| NO (1) | NO760448L (en) |
| PT (1) | PT64805B (en) |
| SE (1) | SE7601423L (en) |
| YU (1) | YU41876A (en) |
| ZA (1) | ZA761045B (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3880922A (en) * | 1972-02-03 | 1975-04-29 | Merck & Co Inc | Process for preparing 3-fluoro-D-alanine by asymmetric rearrangement of 2-(azidocarbonyl)-3-fluoro-propionic ester or nitrile |
-
1976
- 1976-01-01 AR AR262279A patent/AR207277A1/en active
- 1976-02-09 FI FI760302A patent/FI760302A/fi not_active Application Discontinuation
- 1976-02-10 SE SE7601423A patent/SE7601423L/en unknown
- 1976-02-11 DK DK55976*#A patent/DK55976A/en unknown
- 1976-02-12 NO NO760448A patent/NO760448L/no unknown
- 1976-02-13 NL NL7601511A patent/NL7601511A/en not_active Application Discontinuation
- 1976-02-16 PT PT64805A patent/PT64805B/en unknown
- 1976-02-17 AU AU11178/76A patent/AU500536B2/en not_active Expired
- 1976-02-17 CH CH193076A patent/CH620194A5/en not_active IP Right Cessation
- 1976-02-17 GR GR50072A patent/GR59306B/en unknown
- 1976-02-18 CA CA246,060A patent/CA1045157A/en not_active Expired
- 1976-02-19 YU YU00418/76A patent/YU41876A/en unknown
- 1976-02-19 GB GB6655/76A patent/GB1488332A/en not_active Expired
- 1976-02-20 ES ES445381A patent/ES445381A1/en not_active Expired
- 1976-02-20 IE IE335/76A patent/IE43351B1/en unknown
- 1976-02-20 FR FR7604715A patent/FR2301513A1/en active Granted
- 1976-02-23 DE DE19762607252 patent/DE2607252A1/en not_active Withdrawn
- 1976-02-23 CS CS761182A patent/CS199274B2/en unknown
- 1976-02-23 ZA ZA761045A patent/ZA761045B/en unknown
- 1976-02-24 JP JP51018580A patent/JPS51110513A/ja active Pending
- 1976-02-24 HU HU76ME1954A patent/HU173362B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| PT64805A (en) | 1976-03-01 |
| CH620194A5 (en) | 1980-11-14 |
| GR59306B (en) | 1977-12-12 |
| HU173362B (en) | 1979-04-28 |
| PT64805B (en) | 1978-02-06 |
| IE43351L (en) | 1976-08-21 |
| AR207277A1 (en) | 1976-09-22 |
| AU500536B2 (en) | 1979-05-24 |
| DE2607252A1 (en) | 1976-09-02 |
| CA1045157A (en) | 1978-12-26 |
| NL7601511A (en) | 1976-08-26 |
| AU1117876A (en) | 1977-08-25 |
| IE43351B1 (en) | 1981-02-11 |
| FR2301513B1 (en) | 1979-02-02 |
| ES445381A1 (en) | 1977-06-01 |
| JPS51110513A (en) | 1976-09-30 |
| DK55976A (en) | 1976-08-25 |
| ZA761045B (en) | 1977-09-28 |
| CS199274B2 (en) | 1980-07-31 |
| GB1488332A (en) | 1977-10-12 |
| FI760302A (en) | 1976-08-25 |
| FR2301513A1 (en) | 1976-09-17 |
| SE7601423L (en) | 1976-08-25 |
| YU41876A (en) | 1982-02-28 |
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