DK169669B1 - Process for the synthesis of N-amino-3-azabicyclo [3.3.0] octane - Google Patents
Process for the synthesis of N-amino-3-azabicyclo [3.3.0] octane Download PDFInfo
- Publication number
- DK169669B1 DK169669B1 DK303987A DK303987A DK169669B1 DK 169669 B1 DK169669 B1 DK 169669B1 DK 303987 A DK303987 A DK 303987A DK 303987 A DK303987 A DK 303987A DK 169669 B1 DK169669 B1 DK 169669B1
- Authority
- DK
- Denmark
- Prior art keywords
- octane
- azabicyclo
- amino
- monochloramine
- reaction
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/52—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring condensed with a ring other than six-membered
Description
DK 169669 B1DK 169669 B1
Den foreliggende opfindelse angår en hidtil ukendt fremgangsmåde til syntese af N-amino-3-azabicyklo[3, 3,0] octan.The present invention relates to a novel process for the synthesis of N-amino-3-azabicyclo [3, 3,0] octane.
N-amino-3-azabicyklo[3,3,0]octan eller N-amino-octahydrocyklo-penta[c]pyrrol er en forbindelse som meget ofte anvendes som 5 et mellemprodukt til syntese af medicinske produkter (GB-pa-tentskrift nr. 1.153.982) På nuværende tidspunkt er den eneste metode, der er beskrevet i litteraturen til fremstilling af denne forbindelse, fremgangsmåden beskrevet af J.B. Wright og R.E. Willette (J. Med.N-amino-3-azabicyclo [3,3,0] octane or N-amino-octahydrocyclopenta [c] pyrrole is a compound which is very often used as an intermediate for the synthesis of medical products (GB patent no. 1.153.982) At present, the only method described in the literature for the preparation of this compound is the method described by JB. Wright and R.E. Willette (J. Med.
10 and Pharm. Chem. 1962,5,819), hvilken fremgangsmåde består i nitrosering af 3-azabicyklo[3,3,0]octan efterfulgt af reduktion af det opnåede N-nitrosoderivat. Denne syntese fører til rimeligt gode udbytter. Den kræver imidlertid to adskilte trin, og produktet, der hidrører fra det første trin, må be-15 handles med stor omhu på grund af dets potentielle toksicitet og forårsager derved problemer, når fremgangsmåden udføres på industrielt niveau.And Pharm. Chem. 1962,5,819), which consists in the nitrosation of 3-azabicyclo [3,3,0] octane followed by reduction of the N-nitrosone derivative obtained. This synthesis leads to reasonably good yields. However, it requires two separate steps, and the product resulting from the first step must be treated with great care due to its potential toxicity, thereby causing problems when the process is carried out at the industrial level.
På den anden side er det kendt, at der til fremstillingen af forskellige hydraziner ofte anvendes den såkaldte "Raschig"-20 reaktion, som består i, at man syntetiserer monochloramin ved omsætning af ammoniak med natriumhypochloritopløsning og derefter omsætter det dannede monochloramin med en amin til opnåelse af den tilsvarende hydrazin. Denne fremgangsmåde er ganske besværlig at udføre, da den kræver to adskilte trin, 25 hvor syntesen af monochloramin i det første trin udføres i kulden, og det andet trin, hvorunder den faktiske syntese af hydrazin opnås, udføres under opvarmning.On the other hand, it is known that for the preparation of various hydrazines, the so-called "Raschig" reaction, which consists of synthesizing monochloramine by reaction of ammonia with sodium hypochlorite solution and then reacting the formed monochloramine with an amine, is often used. obtaining the corresponding hydrazine. This process is quite cumbersome as it requires two separate steps, wherein the synthesis of monochloramine in the first step is carried out in the cold, and the second step, during which the actual synthesis of hydrazine is obtained, is carried out under heating.
Derudover må monochloraminen være i kontakt med et tilstrækkeligt overskud af amin i de mellemliggende opløsninger for at 30 undgå nedbrydende sidereaktioner, og fremgangsmåden kræver derfor altid meget store mængder af opløsninger til behandling.In addition, the monochloramine must be in contact with a sufficient excess of amine in the intermediate solutions to avoid degrading side reactions, and therefore the process always requires very large amounts of solutions for treatment.
DK 169669 B1 2 I fransk patentansøgning nr. 76/34.692 beskrives en kontinuert fremgangsmåde til syntese af Ν,Ν-dimethylhydrazin udført under anvendelse af ammoniak, natriumhypochlorit og dimethylamin i vandigt medium.DK 169669 B1 2 French patent application No. 76 / 34,692 discloses a continuous process for the synthesis of Ν, Ν-dimethylhydrazine performed using ammonia, sodium hypochlorite and dimethylamine in aqueous medium.
5 Denne fremgangsmåde kan imidlertid ikke anvendes til fremstillingen af alle alkylhydraziner og især ikke til fremstilling af N-amino-3-azabicyklo[3,3,0]octan på grund af den kendsgerning, at udgangsmaterialet, der kræves for syntese deraf, 3-azabicyklo[3,3,0]octan, har specielle fysisk-kemiske egen-10 skaber, som er meget forskellige fra dimethylamins. På den ene side er denne bicykliske amin opløselig i alkaliske, vandige opløsninger ved moderate koncentrationer og især i kulde. På den anden side kan den kun omsættes med mono chl or amin ved høje temperaturer, ved hvilke vand/3-azabicyklo[3,3,0]octan-blan-15 dinger undergår separation til deres bestanddele.However, this process cannot be used for the preparation of all alkyl hydrazines and especially not for the preparation of N-amino-3-azabicyclo [3,3,0] octane due to the fact that the starting material required for its synthesis is 3- azabicyclo [3,3,0] octane, has special physicochemical properties very different from dimethylamine. On the one hand, this bicyclic amine is soluble in alkaline aqueous solutions at moderate concentrations and especially in cold. On the other hand, it can only be reacted with mono chlorine or amine at high temperatures at which water / 3-azabicyclo [3.3.0] octane mixtures undergo separation to their constituents.
Der er nu udviklet en ny fremgangsmåde til syntese af N-ami-no-3-azabicyklo[3,3,0]octan. Denne fremgangsmåde, der udføres på en kontinuert måde, er delvis baseret på brugen af Raschig-fremgangsmåden. Den består principielt i, at man fremstiller 20 chloramin ved indvirkning af natriumhypochlorit på ammoniak ved lav temperatur og derefter, hvilket er det originale, omsætter den derved dannede chloramin med 3-azabicyklo[3,3,0] -octan i et to-fasemedium efterfulgt af ekstraktion af det dannede hydrazin og genindvinding og recirkulering af udgangs-25 aminen direkte i form af en vandig opløsning uden noget yderligere trin.A new process for the synthesis of N-ami-no-3-azabicyclo [3.3.0] octane has now been developed. This process, performed in a continuous manner, is based in part on the use of the Raschig method. It consists principally of producing 20 chloramine by the action of sodium hypochlorite on low temperature ammonia and then, which is the original, reacting the resulting chloramine with 3-azabicyclo [3,3,0] -octane in a two-phase medium followed by extraction of the formed hydrazine and recovery and recycling of the starting amine directly in the form of an aqueous solution without any further steps.
Den foreliggende opfindelses formål er nærmere bestemt en kontinuert fremgangsmåde til syntese af N-amino-3-azabicyklo [3, 3,0]octan, hvilken fremgangsmåde er ejendommelig ved, at en 30 opløsning af ammoniumhydroxid og ammoniumchlorid omsættes med en vandig opløsning af natriumhypochlorit ved en temperatur mellem -15°C og -7°C i alkalisk medium, at den derved dannede monochloramin derefter omsættes med DK 169669 B1 3 3-azabicyklo [3,3,0] octan i et to-fasemedium i en egnet reaktor, der er udstyret med en coaksial omrører af bladtypen (eng. : vane type) ved en temperatur mellem 30°C og 90°C og i alkalisk medium, 5 at ammoniakken derefter fjernes fra reaktionsmediet ved afgasning og den uomsatte 3-azabicyklo[3,3,0]octan derefter fraskilles ved destillation til recirkulation deraf, at en koncentreret opløsning af N-amino-3-azabicyklo[3,3,0]-octan derefter isoleres ved adskillelse af bestanddelene ved 10 tilsætning af natriumhydroxid til reaktionsmediet, og at den derved opnåede hydrazin, om ønsket, oprenses ved destillation.More particularly, the object of the present invention is a continuous process for the synthesis of N-amino-3-azabicyclo [3,3] octane, characterized in that a solution of ammonium hydroxide and ammonium chloride is reacted with an aqueous solution of sodium hypochlorite. at a temperature between -15 ° C and -7 ° C in alkaline medium, the monochloramine thus formed is then reacted with DK 169669 B1 3 3-azabicyclo [3.3.0] octane in a two-phase medium in a suitable reactor, equipped with a blade type coaxial stirrer (eng: habit type) at a temperature between 30 ° C and 90 ° C and in alkaline medium, the ammonia is then removed from the reaction medium by degassing and the unreacted 3-azabicyclo [3, 3,0] octane is then separated by distillation to recycle, then a concentrated solution of N-amino-3-azabicyclo [3,3,0] -octane is then isolated by separation of the constituents by addition of sodium hydroxide to the reaction medium and thereby obtaining it Steamed hydrazine, if desired, is purified by distillation.
Til dannelse af mono chl or aminen blandes en vandig opløsning af natriumhypochlorit under omrøring med en opløsning af ammoniumhydroxid og ammoniumchlorid. Omsætningen udføres i alkalisk 15 medium, der har en pH-værdi på 9,2 til 10 i nærværelse af et overskud af ammoniumhydroxid og ammoniumchlorid. Forholdet mellem de molære koncentrationer af ammoniumhydroxid og ammoniumchlorid og natriumhypochlorit er ca. 2,5 til 3, og forholdet mellem de molære koncentrationer af ammoniumchlorid og 20 ammoniumhydroxid er ca. 0,50 til 0,80.To form the mono chlorine or amine, an aqueous solution of sodium hypochlorite is mixed with stirring with a solution of ammonium hydroxide and ammonium chloride. The reaction is carried out in alkaline medium having a pH of 9.2 to 10 in the presence of an excess of ammonium hydroxide and ammonium chloride. The ratio of the molar concentrations of ammonium hydroxide to ammonium chloride to sodium hypochlorite is approx. 2.5 to 3, and the ratio of the molar concentrations of ammonium chloride to 20 ammonium hydroxide is approx. 0.50 to 0.80.
Omsætning af monochloraminen med 3-azabicyklo [3,3,0] octan udføres i nærværelse af vandig natriumhydroxidopløsning ved 30-90°C. Forholdet mellem de molære koncentrationer af 3-azabicyklo [3,3,0] octan og monochloramin bør være større end 4 og 25 mindre end 8. Reaktionstiden er variabel og afhænger af temperaturen, ved hvilken reaktionen udføres og forholdet mellem koncentrationerne af reagenserne og er i størrelsesordenen 20-40 sekunder.Reaction of the monochloramine with 3-azabicyclo [3.3.0] octane is carried out in the presence of aqueous sodium hydroxide solution at 30-90 ° C. The ratio of the molar concentrations of 3-azabicyclo [3.3.0] octane to monochloramine should be greater than 4 and 25 less than 8. The reaction time is variable and depends on the temperature at which the reaction is carried out and the ratio of the concentrations of the reagents and is in the order of 20-40 seconds.
Efter dannelsen af N-amino-3-azabicyklo [3,3,0] octan og afkø-30 ling undergår reaktionsopløsningen afgasning til fjernelse af ammoniak, og det uomsatte 3-aminobicyklo[3,3,0]octan fraskilles fra reaktionsmediet ved simpel destillation under atmosfæ- DK 169669 B1 4 risk tryk og ved en temperatur fra ca. 90° til 100°C. Under disse betingelser opnås aminen i form af en vandig opløsning med en koncentration på 30% med hensyn til 3-azabicyklo- [3.3.0] octan. Denne opløsning recirkuleres øjeblikkeligt.After the formation of N-amino-3-azabicyclo [3.3.0] octane and cooling, the reaction solution undergoes degassing to remove ammonia and the unreacted 3-aminobicyclo [3.3.0] octane is separated from the reaction medium by simple reaction. distillation under atmospheric pressure and at a temperature of approx. 90 ° to 100 ° C. Under these conditions, the amine is obtained in the form of an aqueous solution with a concentration of 30% with respect to 3-azabicyclo [3.3.0] octane. This solution is immediately recycled.
5 Reaktionsopløsningen, der indeholder hydrazinet, behandles derefter med natriumhydroxid. Denne operation udføres i to trin, hvilket gør det muligt at N-amino-3-azabicyklo[3,3,0]-octan bliver fraskilt i en organisk fase med en koncentration på 92% med hensyn til hydrazinet. Den koncentrerede opløsning, 10 der derved opnås, kan anvendes direkte eller destilleres under reduceret tryk.The reaction solution containing the hydrazine is then treated with sodium hydroxide. This operation is performed in two steps, allowing N-amino-3-azabicyclo [3,3,0] -octane to be separated in an organic phase with a concentration of 92% with respect to the hydrazine. The concentrated solution thus obtained can be used directly or distilled under reduced pressure.
Således muliggør fremgangsmåden ifølge den foreliggende opfindelse ikke kun at N-amino-3-azabicyklo[3,3,0]octan syntetiseres på en kontinuert måde uden dannelsen af eventuelt toksisk 15 mellemprodukt, men muliggør også at hydrazinen fremstilles med lav omkostning.Thus, not only does the process of the present invention enable N-amino-3-azabicyclo [3,3,0] octane to be synthesized in a continuous manner without the formation of any toxic intermediate, but also allows the hydrazine to be produced at low cost.
Det er således, at den klassiske Raschig-syntese generelt kræver et stort overskud af amin, og dette repræsenterer en betragtelig ulempe, når de aminer, der anvendes som et ud-20 gangsmateriale til fremstillingen af de tilsvarende hydraziner, er meget dyre. Dette er tilfældet med 3-azabicyklo[3,3,0]-octan.Thus, the classical Raschig synthesis generally requires a large excess of amine, and this represents a considerable disadvantage when the amines used as a starting material for the preparation of the corresponding hydrazines are very expensive. This is the case with 3-azabicyclo [3,3,0] -octane.
Fremgangsmåden ifølge den foreliggende opfindelse (omsætning i et to-fasemedium, geometri af reaktorerne) muliggør, at dette 25 overskud af 3-azabicyklo[3,3,0]octan begrænses til mindre end 5 gange mængden af monochloramin. Som et resultat af genindvinding og recirkuleringen af uomsat 3-azabicyklo[3,3,0]octan muliggør fremgangsmåden derudover at N-amino-3-azabicyklo- [3.3.0] octan opnås med en meget lav omkostning sammenlignet 30 med de andre kendte fremgangsmåder. Isoleringen af 3-azabicyk- lo[3,3,0]octanen i form af en vandig opløsning ved relativ lav temperatur repræsenterer også et andet meget ejendommeligt træk såvel som en betragtelig økonomisk fordel ved fremgangs- DK 169669 B1 5 måden ifølge opfindelsen. Det er kendt at 3-azabicyklo[3,3,0]-octan er et varmenedbrydeligt produkt, som koger under atmosfærisk tryk ved kun 184°C. Fremgangsmåden ifølge den foreliggende opfindelse muliggør at 3-azabicyklo[3,3,0]octan kan 5 isoleres i heteroazeotropisk form ved en lavere temperatur.The process of the present invention (reaction in a two-phase medium, geometry of the reactors) allows this excess of 3-azabicyclo [3.3.0] octane to be limited to less than 5 times the amount of monochloramine. In addition, as a result of recovery and the recycling of unreacted 3-azabicyclo [3.3.0] octane, the process enables N-amino-3-azabicyclo [3.3.0] octane to be obtained at a very low cost compared to the other known methods. The isolation of the 3-azabicyclo [3.3.0] octane in the form of an aqueous solution at relatively low temperature also represents another very peculiar feature as well as a considerable economic advantage in the method of the invention. It is known that 3-azabicyclo [3,3,0] -octane is a heat-degradable product which boils under atmospheric pressure at only 184 ° C. The process of the present invention enables 3-azabicyclo [3,3,0] octane to be isolated in a heteroazeotropic form at a lower temperature.
En anden fordel ved den foreliggende opfindelse er et resultat af den lette fraskillelse fra de andre bestanddele af N-amino-3-azabicyklo[3,3,0]octan i form af en koncentreret opløsning (92% N-amino-3-azabicyklo[3,3,0]octan) ved simpelt hen at til-10 sætte natriumhydroxid til reaktionsmediet, fra hvilket ammoniak og 3-azabicyklo[3,3,0]octan tidligere er blevet fjernet.Another advantage of the present invention is the result of the ease of separation from the other constituents of N-amino-3-azabicyclo [3,3,0] octane in the form of a concentrated solution (92% N-amino-3-azabicyclo [3,3,0] octane) by simply adding sodium hydroxide to the reaction medium from which ammonia and 3-azabicyclo [3,3,0] octane have been previously removed.
En detaljeret beskrivelse af gennemførelsen af fremgangsmåden ifølge opfindelsen, for hvilken fremgangsmåde rute-diagrammet er vist på tegningen, er anført nedenfor.A detailed description of the implementation of the method according to the invention, for which the method of the route diagram is shown in the drawing, is given below.
15 EksempelExample
Fremstilling af N-amino-3-azabicyklo[3,3,0]octan.Preparation of N-amino-3-azabicyclo [3.3.0] octane.
Alle de anførte mængder svarer til en driftsenhed og er refereret til 1 liter hypochlorit injiceret.All the quantities listed correspond to one operating unit and are referenced to 1 liter of hypochlorite injected.
1 liter natriumhypochloritopløsning, (chlorometrisk titer 48°) 20 og 1 liter af en opløsning, der har en ammoniakkoncentration på 3,60 mol/liter og en ammoniumchloridkoncentration på 2,37 mol/liter indføres på kontinuert måde i en omrørt reaktor (R^ ved en hastighed på 3,1 ml/minut.1 liter of sodium hypochlorite solution, (chlorometric titer 48 °) 20 and 1 liter of a solution having an ammonia concentration of 3.60 mol / liter and an ammonium chloride concentration of 2.37 mol / liter are fed continuously into a stirred reactor (R at a rate of 3.1 ml / minute.
Temperaturen inden i reaktoren holdes på mellem -8° og -10°C, 25 og reaktionsblandingens pH-værdi er omkring 10. Ved udløbet fra R1 opnås en monochloraminopløsning, med en styrke på over 1 mol/liter, og dette svarer til et udbytte omkring 100% i forhold til natriumhypochlorittet.The temperature inside the reactor is kept between -8 ° and -10 ° C, 25 and the pH of the reaction mixture is about 10. At the outlet of R1, a monochloramine solution, with a strength of more than 1 mol / liter, is obtained, which corresponds to a yield. about 100% relative to the sodium hypochlorite.
Syntesen af N-amino-3-azabicyklo[3,3,0]octan udføres i et to- DK 169669 B1 6 fasemedium i en cylindrisk reaktor (R2), omrørt kraftigt ved hjælp af en coaksial omrører af bladtypen, således at blandingen holdes emulgeret. Reaktorens højde er ca. 25 cm og reaktorens volumen 31,6 ml.The synthesis of N-amino-3-azabicyclo [3.3.0] octane is carried out in a two-phase medium in a cylindrical reactor (R2), vigorously stirred by a blade-type coaxial stirrer, so that the mixture is kept emulsified. The height of the reactor is approx. 25 cm and the volume of the reactor 31.6 ml.
5 Den ovenfor opnåede chloraminopløsning (2 liter) , den vandige opløsning af 3-azabicyklo[3,3,0]octan (3,8 liter, 30% styrke) og natriumhydroxid (0,5 liter, 6 mol/liter) indføres samtidigt på kontinuert måde i reaktoren R2 ved en tilstrækkelig strømningshastighed til at der er et molforhold mellem 3-azabicy-10 klo [3,3,0] octan og monochloramin på ca. 5,2 og en pH-værdi fast ved 13,4. Reaktionsblandingens temperatur holdes ved ca.The chloramine solution (2 liters) obtained above, the aqueous solution of 3-azabicyclo [3.3.0] octane (3.8 liters, 30% strength) and sodium hydroxide (0.5 liter, 6 mol / liter) are introduced simultaneously in a continuous manner in the reactor R2 at a sufficient flow rate that there is a molar ratio of 3-azabicy-10klo [3,3,0] octane to monochloramine of approx. 5.2 and a pH value fixed at 13.4. The temperature of the reaction mixture is maintained at ca.
50°C. Efter 30 sekunders omsætning afkøles reaktionsblandingen i en udveksler til 16°C og bliver enkelfase igen. En blanding med en koncentration omkring 0,26 mol/liter med hensyn til hy-15 drazinet opnås. Reaktionsblandingen undergår derefter en af-gasningsoperation til fjernelse af det tilstedeværende ammoniak i opløsningen. Reaktionsopløsningen, fri for ammoniak, destilleres ved 98,4°C under atmosfærisk tryk (destillationskolonne DC-j_) til fjernelse af uomsat 3-azabicyklo [3,3,0] octan.50 ° C. After 30 seconds of reaction, the reaction mixture is cooled in an exchanger to 16 ° C and becomes single phase again. A mixture having a concentration of about 0.26 mol / liter with respect to the hydrazine is obtained. The reaction mixture then undergoes a degassing operation to remove the ammonia present in the solution. The reaction solution, free of ammonia, is distilled at 98.4 ° C under atmospheric pressure (DC-J distillation column) to remove unreacted 3-azabicyclo [3.3.0] octane.
20 Aminen opnås efter destillation i form af en vandig opløsning med en sammensætning på ca. 30% med hensyn til aminen. Denne opløsning recirkuleres derefter og anvendes øjeblikkelig.The amine is obtained after distillation in the form of an aqueous solution having a composition of approx. 30% with respect to the amine. This solution is then recycled and used immediately.
Efter fraskillelse af 3-azabicyklo[3,3,0] octan behandles reaktionsopløsningen, der indeholder hydrazinet, ved at tilsætte 25 fast natriumhydroxid for at separere N-amino-3-azabicyklo- [3.3.0] octanen fra i en organisk fase, styrkebestemt til næsten 92% med hensyn til hydrazinet. Afhængig af anvendelsesspecifikationerne kan den koncentrerede opløsning af hydrazinet derefter anvendes direkte eller destilleres under reduce- 30 ret tryk (destillationskolonne DC2)-After separation of 3-azabicyclo [3.3.0] octane, the reaction solution containing the hydrazine is treated by adding 25 solid sodium hydroxide to separate the N-amino-3-azabicyclo [3.3.0] octane from an organic phase. strength-determined to almost 92% with respect to the hydrazine. Depending on the application specifications, the concentrated solution of the hydrazine can then be used directly or distilled under reduced pressure (distillation column DC2) -
Hydrazinudbyttet i forhold til den forbrugte 3-azabicyklo- [3.3.0] octan er mellem 88 og 92%.The hydrazine yield relative to the 3-azabicyclo [3.3.0] octane consumed is between 88 and 92%.
Claims (4)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8701334 | 1987-02-04 | ||
| FR8701334A FR2610321B1 (en) | 1987-02-04 | 1987-02-04 | NEW PROCESS FOR THE SYNTHESIS OF N-AMINO AZA-3 BICYCLO (3, 3, 0) OCTANE |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK303987D0 DK303987D0 (en) | 1987-06-15 |
| DK303987A DK303987A (en) | 1988-08-05 |
| DK169669B1 true DK169669B1 (en) | 1995-01-09 |
Family
ID=9347573
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK303987A DK169669B1 (en) | 1987-02-04 | 1987-06-15 | Process for the synthesis of N-amino-3-azabicyclo [3.3.0] octane |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0277267B1 (en) |
| JP (1) | JPS63196565A (en) |
| AR (1) | AR243160A1 (en) |
| AT (1) | ATE57914T1 (en) |
| AU (1) | AU591784B2 (en) |
| CA (1) | CA1283420C (en) |
| DE (1) | DE3765925D1 (en) |
| DK (1) | DK169669B1 (en) |
| ES (1) | ES2005012A6 (en) |
| FR (1) | FR2610321B1 (en) |
| IE (1) | IE59681B1 (en) |
| PT (1) | PT85211B (en) |
| ZA (1) | ZA874526B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2769016B1 (en) * | 1997-09-30 | 1999-10-29 | Adir | HIGH-CONTENT CHLORAMINE SYNTHESIS PROCESS |
| FR2864081B1 (en) * | 2003-12-17 | 2006-04-28 | Isochem Sa | PROCESS FOR THE SYNTHESIS OF EXOCYCLIC CYCLOALKYL HYDRAZINE DERIVATIVES AND EXOCYCLIC HETEROCYCLOALKYL HYDRAZINE DERIVATIVES |
| FR2864078B1 (en) | 2003-12-17 | 2006-02-10 | Isochem Sa | PROCESS FOR THE CONTINUOUS SYNTHESIS OF MONOALKYL HYDRAZINES WITH FUNCTIONALIZED ALKYL GROUP |
| US20080156740A1 (en) * | 2006-12-29 | 2008-07-03 | Amit Gupta | Method for producing a stable oxidizing biocide |
| CN101307019B (en) * | 2008-04-28 | 2010-10-27 | 宁波九胜创新医药科技有限公司 | Method for preparing N-amino-3-azabicyclo[3,3,0]octane hydrochloride |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1449404A (en) * | 1973-03-30 | 1976-09-15 | Science Union & Cie | N-arylsulphonyl urea derivatives |
| YU40105B (en) * | 1973-07-04 | 1985-08-31 | Science Union & Cie | Process for the manufacture of n-arylsulfonyl-n'-(aza-3-bicycloalyl)-carbamides |
| FR2540110B1 (en) * | 1983-02-02 | 1985-07-05 | Adir | NEW INDUSTRIAL MANUFACTURING PROCESS OF N-NITROSO AZABICYCLOALCANES |
-
1987
- 1987-02-04 FR FR8701334A patent/FR2610321B1/en not_active Expired
- 1987-06-05 IE IE148887A patent/IE59681B1/en not_active IP Right Cessation
- 1987-06-12 EP EP87108477A patent/EP0277267B1/en not_active Expired - Lifetime
- 1987-06-12 DE DE8787108477T patent/DE3765925D1/en not_active Expired - Lifetime
- 1987-06-12 AT AT87108477T patent/ATE57914T1/en not_active IP Right Cessation
- 1987-06-15 CA CA000539646A patent/CA1283420C/en not_active Expired - Lifetime
- 1987-06-15 AR AR87307860A patent/AR243160A1/en active
- 1987-06-15 DK DK303987A patent/DK169669B1/en not_active IP Right Cessation
- 1987-06-16 AU AU74260/87A patent/AU591784B2/en not_active Expired
- 1987-06-23 ZA ZA874526A patent/ZA874526B/en unknown
- 1987-06-30 PT PT85211A patent/PT85211B/en unknown
- 1987-07-06 JP JP62167147A patent/JPS63196565A/en active Granted
- 1987-09-14 ES ES8702644A patent/ES2005012A6/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| AU7426087A (en) | 1988-08-11 |
| AR243160A1 (en) | 1993-07-30 |
| PT85211B (en) | 1990-11-20 |
| DE3765925D1 (en) | 1990-12-06 |
| ES2005012A6 (en) | 1989-02-16 |
| JPH0427233B2 (en) | 1992-05-11 |
| EP0277267B1 (en) | 1990-10-31 |
| ZA874526B (en) | 1987-12-29 |
| FR2610321B1 (en) | 1989-04-07 |
| PT85211A (en) | 1987-07-01 |
| IE59681B1 (en) | 1994-03-23 |
| DK303987A (en) | 1988-08-05 |
| EP0277267A1 (en) | 1988-08-10 |
| CA1283420C (en) | 1991-04-23 |
| IE871488L (en) | 1988-08-04 |
| ATE57914T1 (en) | 1990-11-15 |
| AU591784B2 (en) | 1989-12-14 |
| FR2610321A1 (en) | 1988-08-05 |
| JPS63196565A (en) | 1988-08-15 |
| DK303987D0 (en) | 1987-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101654402A (en) | Process for prepariing 1,3-dibromoacetone, 1-3-dichloroacetone and epichlorohydrin | |
| US4963232A (en) | Process for producing a purified hydrazine hydrate | |
| DK169669B1 (en) | Process for the synthesis of N-amino-3-azabicyclo [3.3.0] octane | |
| Sharts | N,-N-Difluoroalkylamines by direct fluorination of alkylamines | |
| JPS63192750A (en) | Improved manufacture of alkane sulfonamide | |
| US5166431A (en) | Preparation of alkanesulfonamides | |
| JP4926718B2 (en) | Method for producing exocyclic derivative of cycloalkyl-hydrazine and exocyclic derivative of heterocycloalkyl-hydrazine | |
| US4789539A (en) | Process for the preparation of chloramine | |
| KR101141473B1 (en) | Method for the continuous synthesis of monoalkyl-hydrazines with a functionalized alkyl group | |
| JPS58157751A (en) | Recovery of monomethylhydrazine | |
| US3875231A (en) | Recovery of reaction products of hydrazine and carbonyl compounds | |
| US4424385A (en) | Synthesis of nitromethane | |
| EP0027645A1 (en) | Process for preparing hydrazines | |
| US3755439A (en) | Method of preparing alkanesulfonamides from alkanesulfonyl chlorides | |
| US4469884A (en) | Preparation of n-methoxy-n-methylurethanes | |
| US4677227A (en) | Process for preparing hydrazines | |
| US4508695A (en) | Process for preparing hydrazines | |
| RU2187489C2 (en) | Method of synthesis of chloroform | |
| GB2092137A (en) | Tertiary alkyl hypohalite production | |
| JPH06316404A (en) | Preparation of chloramine | |
| EP0134259B1 (en) | Improved process for preparing hydrazines | |
| US3442612A (en) | Process for manufacture of hydrazine and alkyl substituted hydrazines | |
| CA2024796C (en) | Process for producing chlorosulfonyl isocyanate | |
| JPH06321882A (en) | Preparation of hydrocarbyl-substituted chloramine | |
| JPH0469086B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| B1 | Patent granted (law 1993) | ||
| PUP | Patent expired |