NO147422B - N-METOXYCARBONYL-N`-SUBSTITUTED HYDRAZINE FOR USE AS INTERMEDIATE IN THE PREPARATION OF METHYL-3- (2-KINOXALINYL-METHYL) -CARBZATE - Google Patents
N-METOXYCARBONYL-N`-SUBSTITUTED HYDRAZINE FOR USE AS INTERMEDIATE IN THE PREPARATION OF METHYL-3- (2-KINOXALINYL-METHYL) -CARBZATE Download PDFInfo
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- NO147422B NO147422B NO813221A NO813221A NO147422B NO 147422 B NO147422 B NO 147422B NO 813221 A NO813221 A NO 813221A NO 813221 A NO813221 A NO 813221A NO 147422 B NO147422 B NO 147422B
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- substituted hydrazine
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- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical class NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 title description 5
- -1 N-methoxycarbonyl-N-substituted hydrazine Chemical class 0.000 claims abstract description 5
- SOEMFPLGOUBPJQ-NTUHNPAUSA-N methyl n-[(e)-quinoxalin-2-ylmethylideneamino]carbamate Chemical compound C1=CC=CC2=NC(/C=N/NC(=O)OC)=CN=C21 SOEMFPLGOUBPJQ-NTUHNPAUSA-N 0.000 claims abstract 2
- 239000013067 intermediate product Substances 0.000 claims 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 10
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- WFJRIDQGVSJLLH-UHFFFAOYSA-N methyl n-aminocarbamate Chemical compound COC(=O)NN WFJRIDQGVSJLLH-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Chemical group 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000012259 ether extract Substances 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 150000002429 hydrazines Chemical class 0.000 description 2
- OVGGLBAWFMIPPY-UHFFFAOYSA-N methyl N-[(1,4-dioxidoquinoxaline-1,4-diium-2-yl)methylideneamino]carbamate Chemical compound C1=CC=CC2=[N+]([O-])C(C=NNC(=O)OC)=C[N+]([O-])=C21 OVGGLBAWFMIPPY-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
- CXCHEKCRJQRVNG-UHFFFAOYSA-N 2,2,2-trifluoroethanesulfonyl chloride Chemical compound FC(F)(F)CS(Cl)(=O)=O CXCHEKCRJQRVNG-UHFFFAOYSA-N 0.000 description 1
- YBJFSDXUCGYJSK-UHFFFAOYSA-N 2-bromo-3-methylquinoxaline Chemical class C1=CC=C2N=C(Br)C(C)=NC2=C1 YBJFSDXUCGYJSK-UHFFFAOYSA-N 0.000 description 1
- PZUHHXFIMAEXGO-UHFFFAOYSA-N 3-methyl-4-oxidoquinoxalin-1-ium 1-oxide Chemical class C1=CC=C2N([O-])C(C)=C[N+](=O)C2=C1 PZUHHXFIMAEXGO-UHFFFAOYSA-N 0.000 description 1
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- CKIHZSGJPSDCNC-UHFFFAOYSA-N Quindoxin Chemical class C1=CC=C2N([O-])C=C[N+](=O)C2=C1 CKIHZSGJPSDCNC-UHFFFAOYSA-N 0.000 description 1
- 241000282887 Suidae Species 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- OWIUPIRUAQMTTK-UHFFFAOYSA-N carbazic acid Chemical compound NNC(O)=O OWIUPIRUAQMTTK-UHFFFAOYSA-N 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007952 growth promoter Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- BBNBSVPCCCCNDP-UHFFFAOYSA-N methyl n-(methanesulfonamido)carbamate Chemical compound COC(=O)NNS(C)(=O)=O BBNBSVPCCCCNDP-UHFFFAOYSA-N 0.000 description 1
- OWIUPIRUAQMTTK-UHFFFAOYSA-M n-aminocarbamate Chemical compound NNC([O-])=O OWIUPIRUAQMTTK-UHFFFAOYSA-M 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/50—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with hetero atoms directly attached to ring nitrogen atoms
- C07D241/52—Oxygen atoms
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P17/00—Drugs for dermatological disorders
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/04—Antibacterial agents
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P33/00—Antiparasitic agents
- A61P33/02—Antiprotozoals, e.g. for leishmaniasis, trichomoniasis, toxoplasmosis
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- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Veterinary Medicine (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Medicinal Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pharmacology & Pharmacy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Chemical & Material Sciences (AREA)
- Oncology (AREA)
- Communicable Diseases (AREA)
- Tropical Medicine & Parasitology (AREA)
- Engineering & Computer Science (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Dermatology (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Saccharide Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
N-metoksykarbonyl-Nsubstituert hydrazin for anvendelse som mellomprodukt ved fremstilling av metyl-3-(2-kinoksalinylmetylen)-karbazat.N-methoxycarbonyl-N-substituted hydrazine for use as an intermediate in the preparation of methyl 3- (2-quinoxalinylmethylene) -carbazate.
Description
Foreliggende oppfinnelse gjelder nye hydrazin-derivater The present invention relates to new hydrazine derivatives
som er nyttige som mellomprodukter ved fremstilling av metyl-3-(2-kinoksalinylmetylen)karbazat-N 1 ,N 4-dioksyd som er en kjent forbindelse med verdifulle antibakterielle og veterinær-egenskaper. which are useful as intermediates in the preparation of methyl 3-(2-quinoxalinylmethylene)carbazate-N 1 ,N 4 -dioxide which is a known compound with valuable antibacterial and veterinary properties.
Kontinuerlige synteseanstrengelser for å oppdage nye forbindelser som er aktive mot bakterier og protozoer og opptrer som vekstfremmende midler for svin og fjærfe, har i løpet av de år som er gått, ført til utvikling av forskjellige prototyper av organiske forbindelser, innbefattet en rekke analoger av kinoksalin-1,4-dioksyder: J. Chem. Soc., 2052 Continuous synthetic efforts to discover new compounds active against bacteria and protozoa and acting as growth promoters for pigs and poultry have led over the years to the development of various prototype organic compounds, including a number of analogues of quinoxaline -1,4-dioxides: J. Chem. Soc., 2052
(1956); Heiv. Chim. Acta., 29, 95 (1946); Tetrahedron Letters, (1956); Hooray. Chim. Acta., 29, 95 (1946); Tetrahedron Letters,
3253 (1965); J. Org. Chem., 31, 4067 (1966); Angew. Chem. Internat. Edit., 8, 596 (1969); US-patenter 3 679 679, 3 728 345, 3 753 987, 3 863 162, 3 767 657, 3 803 145, 3 818 007, 3 433 871, 3 371 090 og belgisk patent 721 728. 3253 (1965); J. Org. Chem., 31, 4067 (1966); Angew. Chem. Boarding school. Ed., 8, 596 (1969); US Patents 3,679,679, 3,728,345, 3,753,987, 3,863,162, 3,767,657, 3,803,145, 3,818,007, 3,433,871, 3,371,090 and Belgian Patent 721,728.
En fremgangsmåte for fremstilling av 3-substituerte (2-kinoksalinyl-metylen)karbazat-N 1 ,N 4-dioksyder er beskrevet i US-patent 3 389 326, hvor et 2-bis(halogen)metylkinoksalin-derivat omsettes med hydroksylamin eller en passende hydrazino-karbonsyreester i nærvær av et primært eller sekundært amin og vann. A method for the production of 3-substituted (2-quinoxalinyl-methylene)carbazate-N 1 ,N 4 -dioxides is described in US patent 3,389,326, where a 2-bis(halo)methylquinoxaline derivative is reacted with hydroxylamine or a appropriate hydrazino-carboxylic acid ester in the presence of a primary or secondary amine and water.
Patentansøkning 77.1903 beskriver en forbedret fremgangsmåte for fremstilling av metyl-3-(2-kinoksalinylmetylen)-karbazat-N 1 ,N 4-dioksyd med formelen: Patent application 77.1903 describes an improved method for the production of methyl 3-(2-quinoxalinylmethylene)carbazate-N 1 ,N 4 -dioxide with the formula:
karakterisert ved at et 2-halogenmetylkinoksalin-N 1 ,N 4-dioksyd med formelen: hvor X er klor eller brom, omsettes med fra én til to ekvivalenter av et alkalimetallkarbonat og fra én til to ekvivalenter av et hydrazin med formelen: hvor R" er CFoS0o, CF-CH_S0o, CH-.SO- eller CH,C,H.SO. i et 32 322 32 3642 reaksjonsinert løsningsmiddel ved en temperatur på fra 75 til 85 C, og derefter utvinnes karbazatet med formel I. characterized in that a 2-halomethylquinoxaline-N 1 , N 4 -dioxide with the formula: where X is chlorine or bromine, is reacted with from one to two equivalents of an alkali metal carbonate and from one to two equivalents of a hydrazine with the formula: where R" is CFoS00, CF-CH_S00, CH-.SO- or CH,C,H.SO., in a 32 322 32 3642 reaction inert solvent at a temperature of from 75 to 85 C, and then the carbazate of formula I is recovered.
Den ovenfor beskrevne fremgangsmåte, som omfatter om-setning av et 2-halogenmetyl-kinoksalin-N 1 ,N 4-dioksyd i et reaksjons-inert løsningsmiddel i nærvær av et alkalimetallkarbonat, f.eks. vannfritt kaliumkarbonat med et alkyl- eller aryl^sulfonyl-substituert hydrazin, f.eks. N-metoksykarbonyl-N'-trifylhydrazin, kan representeres av følgende reaksjons-skjema: The method described above, which comprises reaction of a 2-halomethyl-quinoxaline-N 1 , N 4 -dioxide in a reaction-inert solvent in the presence of an alkali metal carbonate, e.g. anhydrous potassium carbonate with an alkyl- or aryl-sulfonyl-substituted hydrazine, e.g. N-methoxycarbonyl-N'-triphylhydrazine, can be represented by the following reaction scheme:
I en foretrukket utførelsesform av fremgangsmåten oppvarmes et 2-halogenmetyl-kinoksalin-N 1 ,N 4-dioksyd, fortrinnsvis 2-brom-metylkinoksalinforbindelsen, til en temperatur på 75 til 85°C i et reaksjons-inert løsningsmiddel som f.eks. acetonitril, med én til to ekvivalenter N-metoksykarbonyl-N<1->trifylhydrazin i nærvær av én til to ekvivalenter vannfritt kaliumkarbonat inntil reaksjonen er i hovedsak fullstendig (ca. 1 til 2 timer). Fortrinnsvis utføres reaksjonen med en ekvimolar mengde kaliumkarbonat og N-metoksykarbonyl-N'-trifylhydrazin. In a preferred embodiment of the method, a 2-halomethyl-quinoxaline-N 1 , N 4 -dioxide, preferably the 2-bromo-methylquinoxaline compound, is heated to a temperature of 75 to 85°C in a reaction-inert solvent such as e.g. acetonitrile, with one to two equivalents of N-methoxycarbonyl-N<1->triphylhydrazine in the presence of one to two equivalents of anhydrous potassium carbonate until the reaction is substantially complete (about 1 to 2 hours). Preferably, the reaction is carried out with an equimolar amount of potassium carbonate and N-methoxycarbonyl-N'-triphylhydrazine.
2-halogenmetylkinoksalin-mellomproduktene som anvendes The 2-halomethylquinoxaline intermediates used
ved ovenstående fremgangsmåte, kan fremstilles ved hjelp av de generelle metoder som er beskrevet i US-patent 3 753 987, by the above method, can be produced using the general methods described in US patent 3 753 987,
J. Chem. Soc, 2052 (1956) og Chemistry of Heterocyclic Compounds, 940 (1967). Halogenet kan være klor eller brom. J. Chem. Soc, 2052 (1956) and Chemistry of Heterocyclic Compounds, 940 (1967). The halogen can be chlorine or bromine.
De foretrukne mellomprodukter er 2-brom-metylkinoksalin-for-bindelsene. Disse forbindelser fremstilles fra 2-metyl-kinoksalin-1,4-dioksydene ved hjelp av de metoder som er beskrevet i J. Chem. Soc, 322 (1943), US-patenter 3 474 097 , The preferred intermediates are the 2-bromo-methylquinoxaline compounds. These compounds are prepared from the 2-methyl-quinoxaline-1,4-dioxides using the methods described in J. Chem. Soc, 322 (1943), US Patents 3,474,097,
3 553 208 og 3 660 398 og britisk patent 1 215 815. N-metoksykarbonyl-N'-trifylhydrazin, N-metoksykarbonyl-N'-tresylhydrazin, N-metoksykarbonyl-N'-metansulfonylhydrazin og N-metoksykarbonyl-N<1->tosylhydrazin kan fremstilles ved den generelle metode som er beskrevet i J. Org. Chem. 40, 3450 (1975). N-metoksykarbonyl-N'-trifylhydrazin fremstilles eksempelvis ved å sette en løsning av triflinsyreanhydrid i metylenklorid dråpevis til en metylenkloridløsning inneholdende en ekvimolar mengde metylkarbazat og et lite moloverskudd trietylamin ved -78°C. Den resulterende blanding får varme seg opp til romtemperatur og omrøres i ca. 16 timer. Blandingen konsentreres under vakuum ved romtemperatur og residuet ekstra-heres så med flere porsjoner eter. Eterekstrakten konsentreres under vakuum ved romtemperatur til et voksaktig fast stoff som brukes direkte ved den efterfølgende reaksjon uten ytterligere rensing. Alternativt gir utelatelse av trietylamin og isteden bruk av to ekvivalenter metylkarbazat, det krystallinske produkt. N-metoksykarbonyl-N<1->trifylhydrazin og N-metoksykarbonyl-N<1->tresylhydrazin er nye forbindelser. Ifølge oppfinnelsen tilveiebringes et nytt N-metoksykarbonyl-N'-substituert hydrazin som er nyttig som mellomprodukt ved fremstilling av forbindelsen med formel I ovenfor, og de karakteriseres ved formelen 3,553,208 and 3,660,398 and British Patent 1,215,815. N-methoxycarbonyl-N'-triphylhydrazine, N-methoxycarbonyl-N'-tresylhydrazine, N-methoxycarbonyl-N'-methanesulfonylhydrazine and N-methoxycarbonyl-N<1-> tosylhydrazine can be prepared by the general method described in J. Org. Chem. 40, 3450 (1975). N-methoxycarbonyl-N'-triphylhydrazine is prepared, for example, by adding a solution of triflic anhydride in methylene chloride dropwise to a methylene chloride solution containing an equimolar amount of methylcarbazate and a small molar excess of triethylamine at -78°C. The resulting mixture is allowed to warm to room temperature and stirred for approx. 16 hours. The mixture is concentrated under vacuum at room temperature and the residue is then extracted with several portions of ether. The ether extract is concentrated under vacuum at room temperature to a waxy solid which is used directly in the subsequent reaction without further purification. Alternatively, omitting triethylamine and using two equivalents of methylcarbazate instead gives the crystalline product. N-methoxycarbonyl-N<1->triphylhydrazine and N-methoxycarbonyl-N<1->tresylhydrazine are new compounds. According to the invention, a new N-methoxycarbonyl-N'-substituted hydrazine is provided which is useful as an intermediate in the preparation of the compound of formula I above, and they are characterized by the formula
hvor R" er CF3S02 eller CF3CH2S02. where R" is CF 3 SO 2 or CF 3 CH 2 SO 2 .
Følgende eksempler illustrerer fremstillingen av de The following examples illustrate the production of them
nye mellomprodukter ifølge oppfinnelsen. new intermediates according to the invention.
Eksempel 1• Example 1•
N- metoksykarbonyl- N'- trifylhydrazin N-Methoxycarbonyl-N'-triphylhydrazine
Triflinsyreanhydrid (35,4 mmol) i metylenklorid (40 ml) ble tilsatt dråpevis til en løsning av metylkarbazat Triflic anhydride (35.4 mmol) in methylene chloride (40 mL) was added dropwise to a solution of methylcarbazate
(35,5 mmol) og trietylamin (38,9 mmol) i metylenklorid (200 ml) ved -78°C med omrøring. Den resulterende blanding fikk varme seg opp til romtemperatur og ble omrørt i 16 timer. Blandingen ble konsentrert ved romtemperatur under vakuum og residuet ble ekstrahert med tre 100 ml porsjoner tilbakeløps-eter. De kombinerte eterekstraktene ble konsentrert under vakuum ved romtemperatur for å gi et voksaktig faststoff (5,26 g, ca. 67%). NMR-spektrum for råproduktet stemte overens med det ventede produkt forurenset med trietylaminsaltet av triflinsyren. Råmaterialet ble brukt direkte uten videre rensing ved etter-følgende reaksjoner. (35.5 mmol) and triethylamine (38.9 mmol) in methylene chloride (200 ml) at -78°C with stirring. The resulting mixture was allowed to warm to room temperature and stirred for 16 hours. The mixture was concentrated at room temperature under vacuum and the residue was extracted with three 100 mL portions of refluxing ether. The combined ether extracts were concentrated under vacuum at room temperature to give a waxy solid (5.26 g, ca. 67%). NMR spectrum of the crude product was consistent with the expected product contaminated with the triethylamine salt of triflic acid. The raw material was used directly without further purification in subsequent reactions.
Metylkarbazat (336 mmol) ble tilsatt i løpet av en Methylcarbazate (336 mmol) was added over a
20 minutters periode med omrøring til en løsning av triflinsyreanhydrid (178 mmol) i metylenklorid (2000 ml) under nitrogen ved -78°C. Den resulterende løsning fikk varme seg opp til romtemperatur og ble omrørt i 20 timer. Den resulterende, tykke, hvite suspensjon ble konsentrert under vakuum ved romtemperatur for å gi et hvitt fast stoff. Dette materiale ble utgnidd med dietyleter (450 ml) og oppsamlet, for å gi metyl-karbazatsaltet av triflinsyre. Dietyleterfiltratet ble konsentrert under vakuum ved romtemperatur for å gi et hvitt, fast stoff som ble utgnidd med heksan, oppsamlet, vasket med heksan og tørket for å gi produktet som et hvitt, krystallinsk fast stoff (utbytte, 84%), sm.p. 107-109°C. 20 minute period with stirring to a solution of triflic anhydride (178 mmol) in methylene chloride (2000 ml) under nitrogen at -78°C. The resulting solution was allowed to warm to room temperature and stirred for 20 hours. The resulting thick white suspension was concentrated under vacuum at room temperature to give a white solid. This material was triturated with diethyl ether (450 mL) and collected to give the methylcarbazate salt of triflic acid. The diethyl ether filtrate was concentrated under vacuum at room temperature to give a white solid which was triturated with hexane, collected, washed with hexane and dried to give the product as a white crystalline solid (yield, 84%), m.p. 107-109°C.
Analyse: Analysis:
Beregnet for C^H^N^S: C 16,21, H 2,25, N 12,61 Calculated for C^H^N^S: C 16.21, H 2.25, N 12.61
Funnet: C 16,24, K 2,20, N 12,68. Found: C 16.24, K 2.20, N 12.68.
Eksempel 2 Example 2
N- metoksykarbonyl- N'- tresylhydrazin N-Methoxycarbonyl-N'-tresylhydrazine
Fremgangsmåten fra eksempel 1 ble gjentatt med anvendelse av tresylklorid istedenfor triflinsyreanhydrid. The procedure from example 1 was repeated using tresyl chloride instead of triflic anhydride.
Claims (3)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US69626376A | 1976-06-15 | 1976-06-15 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO813221L NO813221L (en) | 1977-12-16 |
| NO147422B true NO147422B (en) | 1982-12-27 |
| NO147422C NO147422C (en) | 1983-04-06 |
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Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO771903A NO146864C (en) | 1976-06-15 | 1977-05-31 | PROCEDURE FOR THE PREPARATION OF METHYL-3- (2-KINOXALINYLMETHYL) CARBZATE-N1, N4-DIOXYD |
| NO813221A NO147422C (en) | 1976-06-15 | 1981-09-22 | N-METOXYCARBONYL-N`-SUBSTITUTED HYDRAZINE FOR USE AS INTERMEDIATE IN THE PREPARATION OF METHYL-3- (2-KINOXALINYL-METHYL) -CARBZATE |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO771903A NO146864C (en) | 1976-06-15 | 1977-05-31 | PROCEDURE FOR THE PREPARATION OF METHYL-3- (2-KINOXALINYLMETHYL) CARBZATE-N1, N4-DIOXYD |
Country Status (31)
| Country | Link |
|---|---|
| JP (2) | JPS52153986A (en) |
| AR (1) | AR221207A1 (en) |
| AT (1) | AT357562B (en) |
| BG (1) | BG35595A3 (en) |
| CA (1) | CA1087616A (en) |
| CH (1) | CH620911A5 (en) |
| CS (1) | CS200218B2 (en) |
| DD (2) | DD135080A5 (en) |
| DE (1) | DE2725023A1 (en) |
| DK (1) | DK142497B (en) |
| ES (2) | ES459750A1 (en) |
| FI (1) | FI771742A (en) |
| GB (3) | GB1591874A (en) |
| GR (1) | GR72289B (en) |
| HK (3) | HK1883A (en) |
| IE (1) | IE44684B1 (en) |
| IL (1) | IL52166A0 (en) |
| IT (1) | IT1078874B (en) |
| LU (1) | LU77474A1 (en) |
| MY (2) | MY8300230A (en) |
| NL (2) | NL166685C (en) |
| NO (2) | NO146864C (en) |
| NZ (1) | NZ184167A (en) |
| PH (2) | PH14866A (en) |
| PL (1) | PL105555B1 (en) |
| PT (1) | PT66618B (en) |
| SE (2) | SE428925B (en) |
| SG (1) | SG49282G (en) |
| SU (1) | SU657746A3 (en) |
| YU (1) | YU39492B (en) |
| ZA (1) | ZA772979B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60164410A (en) * | 1984-02-08 | 1985-08-27 | 株式会社石井製作所 | Threshing and sorting apparatus |
-
1977
- 1977-05-16 SE SE7705744A patent/SE428925B/en not_active IP Right Cessation
- 1977-05-17 CA CA278,574A patent/CA1087616A/en not_active Expired
- 1977-05-18 GB GB765/80A patent/GB1591874A/en not_active Expired
- 1977-05-18 ZA ZA00772979A patent/ZA772979B/en unknown
- 1977-05-18 GB GB764/80A patent/GB1591873A/en not_active Expired
- 1977-05-18 GB GB20800/77A patent/GB1591872A/en not_active Expired
- 1977-05-20 NZ NZ184167A patent/NZ184167A/en unknown
- 1977-05-20 IE IE1040/77A patent/IE44684B1/en not_active IP Right Cessation
- 1977-05-20 GR GR53522A patent/GR72289B/el unknown
- 1977-05-25 IL IL52166A patent/IL52166A0/en unknown
- 1977-05-26 PH PH19820A patent/PH14866A/en unknown
- 1977-05-26 CH CH650777A patent/CH620911A5/en not_active IP Right Cessation
- 1977-05-27 YU YU1327/77A patent/YU39492B/en unknown
- 1977-05-30 JP JP6315177A patent/JPS52153986A/en active Granted
- 1977-05-31 NL NL7705938.A patent/NL166685C/en not_active IP Right Cessation
- 1977-05-31 DE DE19772725023 patent/DE2725023A1/en active Pending
- 1977-05-31 CS CS773581A patent/CS200218B2/en unknown
- 1977-05-31 PT PT66618A patent/PT66618B/en unknown
- 1977-05-31 NO NO771903A patent/NO146864C/en unknown
- 1977-05-31 IT IT49637/77A patent/IT1078874B/en active
- 1977-06-01 AT AT387077A patent/AT357562B/en not_active IP Right Cessation
- 1977-06-01 DK DK240777AA patent/DK142497B/en unknown
- 1977-06-01 FI FI771742A patent/FI771742A/fi not_active Application Discontinuation
- 1977-06-02 LU LU77474A patent/LU77474A1/xx unknown
- 1977-06-02 DD DD77204377A patent/DD135080A5/en not_active IP Right Cessation
- 1977-06-02 DD DD7700199261A patent/DD131371A5/en unknown
- 1977-06-02 AR AR267928A patent/AR221207A1/en active
- 1977-06-13 BG BG7736608A patent/BG35595A3/en unknown
- 1977-06-14 SU SU772494213A patent/SU657746A3/en active
- 1977-06-14 ES ES459750A patent/ES459750A1/en not_active Expired
- 1977-06-14 ES ES459745A patent/ES459745A1/en not_active Expired
- 1977-06-15 PL PL1977198873A patent/PL105555B1/en unknown
- 1977-11-09 PH PH20413A patent/PH14481A/en unknown
-
1979
- 1979-11-10 JP JP14596079A patent/JPS5589256A/en active Granted
-
1980
- 1980-05-06 SE SE8003393A patent/SE437985B/en not_active IP Right Cessation
- 1980-12-10 NL NL8006697A patent/NL8006697A/en not_active Application Discontinuation
-
1981
- 1981-09-22 NO NO813221A patent/NO147422C/en unknown
-
1982
- 1982-10-11 SG SG49282A patent/SG49282G/en unknown
-
1983
- 1983-01-13 HK HK18/83A patent/HK1883A/en unknown
- 1983-01-13 HK HK19/83A patent/HK1983A/en unknown
- 1983-01-13 HK HK20/83A patent/HK2083A/en unknown
- 1983-12-30 MY MY230/83A patent/MY8300230A/en unknown
- 1983-12-30 MY MY229/83A patent/MY8300229A/en unknown
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