NO141851B - PROCEDURE FOR THE PREPARATION OF METHYL-3- (2-KINOXALINYLMETHYL) -CARBAZATE-N1.N4-DIOXYD - Google Patents
PROCEDURE FOR THE PREPARATION OF METHYL-3- (2-KINOXALINYLMETHYL) -CARBAZATE-N1.N4-DIOXYD Download PDFInfo
- Publication number
- NO141851B NO141851B NO741133A NO741133A NO141851B NO 141851 B NO141851 B NO 141851B NO 741133 A NO741133 A NO 741133A NO 741133 A NO741133 A NO 741133A NO 141851 B NO141851 B NO 141851B
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- Prior art keywords
- acid
- methyl
- carbazate
- dioxide
- kinoxalinylmethyl
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 8
- WFJRIDQGVSJLLH-UHFFFAOYSA-N methyl n-aminocarbamate Chemical compound COC(=O)NN WFJRIDQGVSJLLH-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003377 acid catalyst Substances 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000012442 inert solvent Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical compound ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 claims description 2
- 241001465754 Metazoa Species 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 244000144977 poultry Species 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 241000283690 Bos taurus Species 0.000 description 2
- 241000282472 Canis lupus familiaris Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241001494479 Pecora Species 0.000 description 2
- 241000700159 Rattus Species 0.000 description 2
- 241000282849 Ruminantia Species 0.000 description 2
- 241000282887 Suidae Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002924 anti-infective effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000003252 quinoxalines Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009885 systemic effect Effects 0.000 description 2
- 241000272517 Anseriformes Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000283707 Capra Species 0.000 description 1
- 208000014085 Chronic respiratory disease Diseases 0.000 description 1
- 241000283086 Equidae Species 0.000 description 1
- 241001331845 Equus asinus x caballus Species 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
- 241000699670 Mus sp. Species 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- SNIOPGDIGTZGOP-UHFFFAOYSA-N Nitroglycerin Chemical compound [O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O SNIOPGDIGTZGOP-UHFFFAOYSA-N 0.000 description 1
- 241000283973 Oryctolagus cuniculus Species 0.000 description 1
- 241000283903 Ovis aries Species 0.000 description 1
- 241000286209 Phasianidae Species 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000037396 body weight Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007952 growth promoter Substances 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000083 urinary anti-infective agent Substances 0.000 description 1
- 230000002485 urinary effect Effects 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Fodder In General (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Catalysts (AREA)
Description
Foreliggende oppfinnelse vedrører en ny fremgangsmåte The present invention relates to a new method
for fremstilling av mety1-3-(2-kinoksalinylmetylen)-karbazat-N 1 ,N 4-dioksyd. Forbindelsen fremstilt efter den nye fremgangsmåten er kjent som et urinveisantiseptikum, systemisk anti-infektiøst, vekstfremmende middel for dyr, som et middel for kontroll av kroniske åndedrettssykdommer i fjærkre og forbedring av for-utnyttelsen for dyr. [Australian Vet. J. 48, nr. 10 579 (1972) for the production of methyl 1-3-(2-quinoxalinylmethylene)-carbazate-N 1 ,N 4 -dioxide. The compound prepared according to the new method is known as a urinary antiseptic, systemic anti-infective, growth promoter for animals, as a means for controlling chronic respiratory diseases in poultry and improving the pre-utilization of animals. [Australian Vet. J. 48, No. 10,579 (1972)
og Ree. Med. Vet. ecole Alfort 148 nr. 3 365-73 (1972)]. and Ree. With. Know. ecole Alfort 148 no. 3 365-73 (1972)].
Ifølge foreliggende oppfinnelse tilveiebringes en fremgangsmåte for fremstilling av metyl-3-(2-kinoksalinylmetylen)-karbazat-N 1 ,N 4-dioksyd med formelen: According to the present invention, a method is provided for the production of methyl 3-(2-quinoxalinylmethylene)-carbazate-N 1 , N 4 -dioxide with the formula:
Fremgangsmåten karakteriseres ved at N-lavere-alkyl-2-(2-kinoksalinkarboksaldehyd-N 1 ,N 4-dioksyd)nitron med formelen hvor R er lavere alkyl, fortrinnsvis metyl, omsettes med minst en ekvimolar mengde av metylkarbazat i et reaksjonsinert oppløsningsmiddel i nærvær av en sterk syrekatalysator, valgt fra saltsyre, bromhydrogensyre, svovelsyre, fosforsyre, p-toluensulfonsyre og trifluoreddiksyre, ved en temperatur på The method is characterized in that N-lower-alkyl-2-(2-quinoxalinecarboxaldehyde-N 1 ,N 4-dioxide) nitrone with the formula where R is lower alkyl, preferably methyl, is reacted with at least an equimolar amount of methylcarbazate in a reaction-initiated solvent in presence of a strong acid catalyst selected from hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid and trifluoroacetic acid, at a temperature of
ca. 30 til 200°C. about. 30 to 200°C.
Den nye fremgangsmåten ifølge foreliggende oppfinnelse utføres i et reaksjonsinert løsningsmiddel. Et inert løsnings-middel for dette formål er ethvert løsningsmiddel som tillater oppløsning av reaksjonsmidlene og som ikke har noen uheldig innvirkning på reaksjonsmidlene og produktene under de anvendte betingelser. To foretrukne typer omfatter organiske syrer, The new method according to the present invention is carried out in a reaction-inert solvent. An inert solvent for this purpose is any solvent which allows dissolution of the reactants and which has no adverse effect on the reactants and products under the conditions used. Two preferred types include organic acids,
slik som eddiksyre, og lavere alkoholer og estere slik som etanol og etylacetat. Den nye fremgangsmåten ifølge foreliggende oppfinnelse krever tilstedeværelse av en sterk syrekatalysator valgt fra saltsyre, bromhydrogensyre, svovelsyre, fosforsyre, p-toluensulfonsyre og trifluoreddiksyre. Det er vanligvis tilfreds-stillende å anvende fra ca. 2-10 vekt%, beregnet på den totale reaksjonsblandingen av syrekatalysatoren. (Dersom det anvendes en sterk syre, f.eks. trifluoreddiksyre som løsningsmiddel, such as acetic acid, and lower alcohols and esters such as ethanol and ethyl acetate. The new method according to the present invention requires the presence of a strong acid catalyst selected from hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid and trifluoroacetic acid. It is usually satisfactory to use from approx. 2-10% by weight, calculated on the total reaction mixture of the acid catalyst. (If a strong acid is used, e.g. trifluoroacetic acid as solvent,
er det unødvendig med en syrekatalysator). Ofte er det ønskelig med tilstedeværelse av en liten mengde vann i reaksjonsblandingen, og denne kan passende tilsettes ved å anvende som en syrekatalysator slike syrer som konsentrert saltsyre eller bromhydrogensyre som inneholder vann. Imidlertid kan anvendes et hvilket som helst løsningsmiddel som har de ovenfor angitte egenskaper. Reaksjonstemperaturen kan variere fra 30°C til ca. 200°C, og som regel vil den optimale temperatur variere med valget av reagenser. Høyere temperatur kan kreve anvendelse av en autoklav eller høytrykkskar. an acid catalyst is unnecessary). It is often desirable to have a small amount of water present in the reaction mixture, and this can suitably be added by using as an acid catalyst such acids as concentrated hydrochloric acid or hydrobromic acid which contain water. However, any solvent which has the above-mentioned properties can be used. The reaction temperature can vary from 30°C to approx. 200°C, and as a rule the optimum temperature will vary with the choice of reagents. Higher temperatures may require the use of an autoclave or high-pressure vessel.
Avhengig av de anvendte reaksjonsmidler og temperatur Depending on the reagents used and temperature
kan reaksjonstiden variere fra noen få minutter til så meget som 24 timer. For å være sikker på at reaksjonen er avsluttet er det foretrukket å anvende relativt lang tid. Optimale reaksjons-betingelser bestemmes lett eksperimentelt. the reaction time can vary from a few minutes to as much as 24 hours. To be sure that the reaction has ended, it is preferred to use a relatively long time. Optimal reaction conditions are easily determined experimentally.
Forholdet mellom kinoksalinderivatet og metylkarbazatet kan variere meget, men for effektiv overføring er det nødvendig med minst én ekvivalent av. metylkarbazat pr. mol av kinoksalinderivatet og det er foretrukket med et molart overskudd på The ratio between the quinoxaline derivative and the methyl carbazate can vary widely, but for effective transfer at least one equivalent of is required. methylcarbazate per mol of the quinoxaline derivative and it is preferred with a molar excess of
50-100% av metylkarbazatet. 50-100% of the methylcarbazate.
Utgangsmaterialene fremstilles lett efter kjente The starting materials are easily produced according to known methods
metoder innenfor den organiske kjemi. methods within organic chemistry.
Nitronet fremstilles via den vei som er beskrevet Nitronet is produced via the route described
av H.K. Kim. U.S.-patent 3.644.363. Metylkarbazatet er tilgjengelig via den sekvensen som er beskrevet av N. Rabjohn og H.D. Barnstorff, J. Am. Chem. Soc, 75, 2259 (1953). by H.K. Kim. U.S. Patent 3,644,363. The methylcarbazate is available via the sequence described by N. Rabjohn and H.D. Barnstorff, J. Am. Chem. Soc, 75, 2259 (1953).
Produktet isoleres ved fortynning av reaksjonsblandingen med vann, avkjøling og derefter filtrering. Det faste stoffet oppsamles, vaskes med vann og tørkes, og man får det ønskede mety1-3-(2-kinoksalinylmetylen)karbazat-N 1 ,N 4-dioksyd. The product is isolated by diluting the reaction mixture with water, cooling and then filtering. The solid is collected, washed with water and dried, and the desired methyl 1-3-(2-quinoxalinylmethylene)carbazate-N 1 ,N 4 -dioxide is obtained.
Det verdifulle produkt som fremstilles ifølge foreliggende oppfinnelse, har urinveis, systemisk anti-infektiøs virkning på dyr, innbefattet mennesker, mot en rekke mikro-organismer som omfatter Gram-positive og Gram-negative bakterier. Det er spesielt verdifullt mot Gram-negative infeksjoner både The valuable product produced according to the present invention has a urinary, systemic anti-infective effect on animals, including humans, against a number of micro-organisms which include Gram-positive and Gram-negative bacteria. It is particularly valuable against Gram-negative infections as well
in vitro og in vivo. in vitro and in vivo.
Tilsetningen av en liten mengde av den beskrevne Schiffske base til dyrefåret, både til drøvtyggere og ikke-drøvtyggere, slik at disse dyrene får produktet i løpet av en forlenget tidsperiode i en mengde fra ca. 0,04 mg/kg til ca. 10 mg/kg legemsvekt pr. dag, spesielt i størstedelen av deres aktive vekstperiode, resulterer dessuten i en akselerasjon av veksthastigheten og forbedret fårutnyttelse. Disse to klassene av dyr omfatter fjærkre (kylling, ender, kalkuner), kyr, hunder, sauer, katter, rotter, svin, mus, hester, geiter, muldyr, The addition of a small amount of the described Schiffske base to the animal feed, both to ruminants and non-ruminants, so that these animals receive the product during an extended period of time in an amount from approx. 0.04 mg/kg to approx. 10 mg/kg body weight per day, especially during the majority of their active growth period, also results in an acceleration of growth rate and improved sheep utilization. These two classes of animals include poultry (chicken, ducks, turkeys), cows, dogs, sheep, cats, rats, pigs, mice, horses, goats, mules,
kaniner, mink etc. Den gunstige virkningen på veksthastighet og forutnyttelse ligger over den som man vannligvis oppnår ved fullverdig nærende for som inneholder alle næringsstoffer, vitaminer, mineraler og andre kjente faktorer som er nødvendig for maksimal og sunn vekst av slike dyr. Dyrene oppnår således markedsstørrelsen hurtigere og ved hjelp av mindre for. rabbits, mink, etc. The beneficial effect on growth rate and utilization is above that which is normally achieved with complete nutrition for which contains all nutrients, vitamins, minerals and other known factors that are necessary for maximum and healthy growth of such animals. The animals thus reach the market size faster and with the help of less feed.
Disse forblandinger har vist seg å være spesielt verdifulle og spesielt gode for slike dyr som fjærkre, rotter, hunder, svin, lam, kyr o.l. I noen tilfeller kan responsgraden variere med hensyn til kjønn av dyrene. Produktene kan selv-følgelig administreres i en del av foret eller de kan blandes jevnt gjennom et blandet for, alternativt kan de som nevnt ovenfor administreres som en ekvivalent mengde via drikkevannet til dyret. Det bør bemerkes at det kan anvendes en rekke for-komponenter i de næringsmessig avbalanserte forblandinger. These premixes have proven to be particularly valuable and especially good for such animals as poultry, rats, dogs, pigs, lambs, cows, etc. In some cases, the degree of response may vary with regard to the sex of the animals. The products can therefore be administered in part of the feed or they can be mixed evenly through a mixed feed, alternatively, as mentioned above, they can be administered as an equivalent amount via the animal's drinking water. It should be noted that a number of pre-components can be used in the nutritionally balanced pre-mixes.
De følgende eksempler illustrerer oppfinnelsen. The following examples illustrate the invention.
Eksempel I Example I
En løsning av 43,8 g (0,20 mol) N-metyl-2-(2-kinoksalinyl-N 1 ,N 4-dioksyd)-nitron og metylkarbazat (27 g, A solution of 43.8 g (0.20 mol) of N-methyl-2-(2-quinoxalinyl-N 1 ,N 4 -dioxide)-nitron and methylcarbazate (27 g,
0,30 mol) i eddiksyre (400 ml) tilsettes konsentrert svovelsyre (20 ml). Den resulterende blanding, oppvarmes ved ca. 90-100°C 0.30 mol) in acetic acid (400 ml) is added concentrated sulfuric acid (20 ml). The resulting mixture is heated at approx. 90-100°C
i ca. 20-24 timer. Efter avkjøling og fortynning med vann (1200 ml) oppsamles det utfelte faste stoff, tørres, og man får metyl-3-(2-kinoksalinyl-metylen)-karbazat-N 1 ,N 4-dioksyd. for about. 20-24 hours. After cooling and diluting with water (1200 ml), the precipitated solid is collected, dried, and methyl 3-(2-quinoxalinyl-methylene)-carbazate-N 1 ,N 4 -dioxide is obtained.
Eksempel II Example II
Til eddiksyre (20 ml) settes N-metyl-2-(2-kinoksalinyl-N 1 ,N 4-dioksyd)-nitron (2,19 g, 0,01 mol), metylkarbazat (1,35 g, 0,015 mol) og konsentrert svovelsyre (1 ml). Blandingen oppvarmes ved 90-100°C i 20 timer og avkjøles derefter og for- To acetic acid (20 ml) is added N-methyl-2-(2-quinoxalinyl-N 1 ,N 4-dioxide)-nitrone (2.19 g, 0.01 mol), methyl carbazate (1.35 g, 0.015 mol) and concentrated sulfuric acid (1 mL). The mixture is heated at 90-100°C for 20 hours and then cooled and pre-
tynnes med 60 ml vann og filtreres for å gi metyl-3-(2-kinoksalinyl-metylen)-karbazat-N 1 ,N 4-dioksyd (2,2 g, 84%) som et lysegult, fast stoff med smeltepunkt 248-250°C (spaltning). Massespektrogram, NMR og IR i overensstemmelse med antatt struktur. diluted with 60 mL of water and filtered to give methyl 3-(2-quinoxalinyl-methylene)-carbazate-N 1 ,N 4 -dioxide (2.2 g, 84%) as a pale yellow solid, mp 248- 250°C (decomposition). Mass spectrogram, NMR and IR in accordance with assumed structure.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US34980573A | 1973-04-10 | 1973-04-10 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO741133L NO741133L (en) | 1974-10-11 |
| NO141851B true NO141851B (en) | 1980-02-11 |
| NO141851C NO141851C (en) | 1980-06-04 |
Family
ID=23374042
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO741133A NO141851C (en) | 1973-04-10 | 1974-03-29 | PROCEDURE FOR THE PREPARATION OF METHYL-3- (2-KINOXALINYLMETHYL) -CARBAZATE-N1.N4-DIOXYD. |
Country Status (27)
| Country | Link |
|---|---|
| JP (1) | JPS5333596B2 (en) |
| AR (1) | AR210723A1 (en) |
| AU (1) | AU477279B2 (en) |
| CA (1) | CA1018977A (en) |
| CH (1) | CH603599A5 (en) |
| CS (1) | CS212276B2 (en) |
| DD (1) | DD110875A5 (en) |
| DK (1) | DK140756B (en) |
| ES (1) | ES424803A1 (en) |
| FI (1) | FI59405C (en) |
| FR (1) | FR2225429B1 (en) |
| GB (1) | GB1462424A (en) |
| HK (1) | HK48877A (en) |
| HU (1) | HU170050B (en) |
| IE (1) | IE39110B1 (en) |
| IL (1) | IL44434A (en) |
| IT (1) | IT1056058B (en) |
| MY (1) | MY7800014A (en) |
| NL (1) | NL7404044A (en) |
| NO (1) | NO141851C (en) |
| PH (1) | PH11135A (en) |
| PL (1) | PL94963B1 (en) |
| RO (1) | RO71311A (en) |
| SE (1) | SE407219B (en) |
| SU (1) | SU730302A3 (en) |
| YU (1) | YU39151B (en) |
| ZA (1) | ZA742052B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5135625Y2 (en) * | 1971-03-30 | 1976-09-02 | ||
| JPS4984830U (en) * | 1972-11-09 | 1974-07-23 | ||
| JPS49100338U (en) * | 1972-12-20 | 1974-08-29 | ||
| IT1078991B (en) * | 1977-05-26 | 1985-05-08 | Erregierre Ind Chim Spa | PROCESS FOR THE PREPARATION OF THE HYDRAZONE CARBOMETHOXY, OF THE 2-FORMYLKINOXALINE-1,4-DI-N-OXIDE |
| JPS5487994U (en) * | 1977-12-02 | 1979-06-21 | ||
| DK141708B (en) * | 1978-04-20 | 1980-05-27 | Rasmussen Holding As V Kann | Window maneuvering and locking grips. |
-
1974
- 1974-03-11 SE SE7403236A patent/SE407219B/en not_active IP Right Cessation
- 1974-03-15 GB GB1170674A patent/GB1462424A/en not_active Expired
- 1974-03-18 IL IL44434A patent/IL44434A/en unknown
- 1974-03-19 AU AU66828/74A patent/AU477279B2/en not_active Expired
- 1974-03-26 YU YU00834/74A patent/YU39151B/en unknown
- 1974-03-26 NL NL7404044A patent/NL7404044A/xx unknown
- 1974-03-27 IT IT49751/74A patent/IT1056058B/en active
- 1974-03-28 JP JP3402874A patent/JPS5333596B2/ja not_active Expired
- 1974-03-29 CH CH446274A patent/CH603599A5/xx not_active IP Right Cessation
- 1974-03-29 FR FR7411526A patent/FR2225429B1/fr not_active Expired
- 1974-03-29 FI FI978/74A patent/FI59405C/en active
- 1974-03-29 NO NO741133A patent/NO141851C/en unknown
- 1974-03-29 HU HUPI412A patent/HU170050B/hu unknown
- 1974-03-29 DK DK174874AA patent/DK140756B/en not_active IP Right Cessation
- 1974-03-29 SU SU742013770A patent/SU730302A3/en active
- 1974-03-29 IE IE00686/74A patent/IE39110B1/en unknown
- 1974-03-30 RO RO7478252A patent/RO71311A/en unknown
- 1974-03-30 ES ES424803A patent/ES424803A1/en not_active Expired
- 1974-04-01 CS CS742332A patent/CS212276B2/en unknown
- 1974-04-01 AR AR253076A patent/AR210723A1/en active
- 1974-04-01 CA CA196,545A patent/CA1018977A/en not_active Expired
- 1974-04-01 DD DD177605A patent/DD110875A5/xx unknown
- 1974-04-01 PL PL1974170010A patent/PL94963B1/pl unknown
- 1974-04-01 ZA ZA00742052A patent/ZA742052B/en unknown
-
1976
- 1976-03-23 PH PH18245A patent/PH11135A/en unknown
-
1977
- 1977-09-22 HK HK488/77A patent/HK48877A/en unknown
-
1978
- 1978-12-30 MY MY14/78A patent/MY7800014A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| HK48877A (en) | 1977-09-30 |
| AR210723A1 (en) | 1977-09-15 |
| GB1462424A (en) | 1977-01-26 |
| DD110875A5 (en) | 1975-01-12 |
| IL44434A (en) | 1977-08-31 |
| YU83474A (en) | 1982-08-31 |
| NO741133L (en) | 1974-10-11 |
| YU39151B (en) | 1984-06-30 |
| FR2225429B1 (en) | 1977-06-24 |
| DK140756C (en) | 1980-04-14 |
| CH603599A5 (en) | 1978-08-31 |
| DK140756B (en) | 1979-11-12 |
| JPS5333596B2 (en) | 1978-09-14 |
| AU477279B2 (en) | 1976-10-21 |
| SE407219B (en) | 1979-03-19 |
| IE39110L (en) | 1974-10-10 |
| JPS5030893A (en) | 1975-03-27 |
| CS212276B2 (en) | 1982-03-26 |
| IE39110B1 (en) | 1978-08-02 |
| AU6682874A (en) | 1975-09-25 |
| SU730302A3 (en) | 1980-04-25 |
| PL94963B1 (en) | 1977-09-30 |
| NL7404044A (en) | 1974-10-14 |
| ES424803A1 (en) | 1976-05-16 |
| IL44434A0 (en) | 1974-06-30 |
| FI59405C (en) | 1981-08-10 |
| NO141851C (en) | 1980-06-04 |
| MY7800014A (en) | 1978-12-31 |
| RO71311A (en) | 1981-08-30 |
| ZA742052B (en) | 1975-03-26 |
| HU170050B (en) | 1977-03-28 |
| PH11135A (en) | 1977-10-27 |
| FR2225429A1 (en) | 1974-11-08 |
| IT1056058B (en) | 1982-01-30 |
| FI59405B (en) | 1981-04-30 |
| CA1018977A (en) | 1977-10-11 |
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