SE190894C1 - - Google Patents
Info
- Publication number
- SE190894C1 SE190894C1 SE190894DA SE190894C1 SE 190894 C1 SE190894 C1 SE 190894C1 SE 190894D A SE190894D A SE 190894DA SE 190894 C1 SE190894 C1 SE 190894C1
- Authority
- SE
- Sweden
- Prior art keywords
- chlorine
- oxidizing agent
- oxazine
- hydantoin
- pyrido
- Prior art date
Links
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 11
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 229940091173 hydantoin Drugs 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- PAOWOJRQGBFDQG-UHFFFAOYSA-N pyrido[2,3-e][1,3]oxazine-2,4-dione Chemical compound C1=CC=C2OC(=O)NC(=O)C2=N1 PAOWOJRQGBFDQG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HORQAOAYAYGIBM-UHFFFAOYSA-N 2,4-dinitrophenylhydrazine Chemical compound NNC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O HORQAOAYAYGIBM-UHFFFAOYSA-N 0.000 description 1
- DXMYTBSZYATUTO-UHFFFAOYSA-N 2H-1,3-oxazine hydrochloride Chemical compound Cl.O1CN=CC=C1 DXMYTBSZYATUTO-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- GEFUOUGNUMYCBB-UHFFFAOYSA-N Cl.O=C1OC2=C(C(N1)=O)N=CC=C2 Chemical compound Cl.O=C1OC2=C(C(N1)=O)N=CC=C2 GEFUOUGNUMYCBB-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000004893 oxazines Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Uppfinnare: NKFW Clauson-Kaas, R Denss, F Ostermayer och E Renk Prioritet begiird Iran den 14. november 1961 (Schweiz) FOreliggande uppfinning avser ett nytt fOrfaramie fir framstallning av 3,4-dihydro-2,4-dioxo2H-pyrido [2,3-e] [1, 3] oxazin. Inventors: NKFW Clauson-Kaas, R. Denss, F. Ostermayer and E. Renk Priority given to Iran on November 14, 1961 (Switzerland). The present invention relates to a novel pharmaceutical for the preparation of 3,4-dihydro-2,4-dioxo2H-pyrido [2 , 3-e] [1,3] oxazine.
Det har overraskande nog visat sig, att man kan framstalla 3,4-dihydro-2,4-clioxo-2H-pyrido[2,3-e][1,31oxazin med formeln om ett oxidationsmedel bringas att inverka pa 5-(2'-fury1)-hydantoin med formeln —CH—CO IIN NH \ / C 0 II Denna omvandling av furylhydantoin till namnda oxazinderivat med tillhj alp av ett oxidationsmedel utgor en ovdntad, hittills icke nagonstans beskriven reaktion. It has surprisingly been found that 3,4-dihydro-2,4-clioxo-2H-pyrido [2,3-e] [1,31-oxazine] can be prepared by the formula if an oxidizing agent is reacted with 5- (2 This conversion of furylhydantoin to said oxazine derivative by means of an oxidizing agent constitutes an unexpected, hitherto nowhere described reaction.
Som oxidationsmedel ifragakommer speciellt halogen. SpecieLlt väl lampar sig harfor klor, antingen som gas eller i form av nagot amne, som under reaktionsbetingelserna avger klor. Vid sistnamnda variant anvandes exempelvis natriumhypoklorit som klor-avgivande dmne. Halogen is especially used as an oxidizing agent. Chlorine is particularly well-suited for chlorine, either as a gas or in the form of a substance which emits chlorine under the reaction conditions. In the latter variant, for example, sodium hypochlorite was used as the chlorine-releasing substance.
Reaktionen utfores foretrddesvis i ett 16sningseller utspadningsmedel, exempelvis vatten, som kan forsattas med na.got vattenlosligt, polart, organiskt losningsmedel t. ex. en lagmolekylar alkanol eller etylenglykol etc., eller vidare aven i vattenhaltig attiksyra. The reaction is preferably carried out in a solvent or diluent, for example water, which can be continued with some water-soluble, polar, organic solvent, e.g. a low molecular weight alkanol or ethylene glycol, etc., or furthermore also in aqueous acetic acid.
Speciellt lampligt är utforandet av omsattningen enligt uppfinningen vid anvandning av klor som oxidationsmedel, cm reaktionen utfOres i surt, t. ex. saltsyrat, vattenhaltigt eller vattenhaltigt-organiskt medium, i vilket den furylhydantoin, som skall omsattas, foreligger i suspension eller losning. I stand for klor kan emellertid aven brom anvandas. Particularly suitable is the practice of the reaction according to the invention in the use of chlorine as oxidizing agent, if the reaction is carried out in acid, e.g. hydrochloric acid, aqueous or aqueous-organic medium in which the furylhydantoin to be reacted is present in suspension or solution. However, in the case of chlorine, bromine can also be used.
Framstallningen av den som utgangsforening anvanda 5-(2'-fury1)-hydantoinen med den ovan angivna formeln II ar kand; jamfor t. ex. Henze & Speer, J. amer. Chem. Soc. 64, 522 (1942) samt Harvill & Herbst, J. Org. Chem. 9, 21 (1944). The preparation of the starting compound using the 5- (2'-furyl) -hydantoin of the above formula II is known; compared to e.g. Henze & Speer, J. amer. Chem. Soc. 64, 522 (1942) and Harvill & Herbst, J. Org. Chem. 9, 21 (1944).
FOljande exempel askadliggora narmare fOrfarandet enligt uppfinningen. Temperaturerna aro angivna i celsiusgrader. The following examples further illustrate the process of the invention. The temperatures are given in degrees Celsius.
Exempel 1. I en suspension av 184 g pulveriserad 5-(2'-fury1)-hydantoin i 420 ml 2-n saltsyra inledas under forloppet av 1 1/2-2 timmar 114 g klor vid 15° under kraftig omrOring. Darefter filtreras suspensionen genast, aterstoden °mitres med 300 ml aceton och filtreras Ater. Den erhallna 3,4- dihydro -2,4- dioxo - 2H - pyrido [2,3-e] [1,3] oxazin-hydrokloriden kan overforas till has genom tvattning med vatten, tills filtratet avgar neutrait. Basen erhalles aven genom losning av hydrokloriden 12-n natronlut och darpa foljande neutralisation med utspadd saltsyra. Basen omkristalliseras ur kokande vatten, isattika eller pyridin under tillsats av kol och smaller darefter vid 280°. Foreningen ger icke flagon jarnklorid-reaktion (i metanol) och ingen fallning med en losning av 2,4-dinitrofenylhydrazin i 2-n saltsyra. Utbyte 25-35 %. Example 1. In a suspension of 184 g of powdered 5- (2'-furyl) -hydantoin in 420 ml of 2-n hydrochloric acid, 114 g of chlorine are initiated in the course of 1 1 / 2-2 hours at 15 ° with vigorous stirring. The suspension is then filtered immediately, the residue is metered in with 300 ml of acetone and filtered again. The resulting 3,4-dihydro-2,4-dioxo-2H-pyrido [2,3-e] [1,3] oxazine hydrochloride can be transferred to hash by washing with water until the filtrate gives off a neutral. The base is also obtained by dissolving the hydrochloride 12-n sodium hydroxide solution and dropping the following neutralization with dilute hydrochloric acid. The base is recrystallized from boiling water, glacial acetic acid or pyridine with the addition of carbon and then narrower at 280 °. The compound does not give a flake iron chloride reaction (in methanol) and no precipitation with a solution of 2,4-dinitrophenylhydrazine in 2-n hydrochloric acid. Yield 25-35%.
Exempel 2. I en llisning av 8,3 g 5-(2'-fury1)- hydantoin i 23 ml 6-n saltsyra och 25 ml metanol inledes under forloppet av 60 minuter vid 11-15° gasformigt klor rnotsvarande en flytande mangd 2— av 3,5 ml vid — 80°. Darefter avfiltreras den bildade 3,4-dihydro-2,4-dioxo-2H-pyrido [2,3-el[1,3]oxazin-hydrokloriden, tvattas med 99-procentig etanol och torkas. Utbyte 25-35 %. Example 2. In a solution of 8.3 g of 5- (2'-furyl) -hydantoin in 23 ml of 6-hydrochloric acid and 25 ml of methanol are initiated in the course of 60 minutes at 11-15 ° gaseous chlorine corresponding to a liquid amount of 2 Of 3.5 ml at - 80 °. The 3,4-dihydro-2,4-dioxo-2H-pyrido [2,3-el [1,3] oxazine hydrochloride formed is then filtered off, washed with 99% ethanol and dried. Yield 25-35%.
Exempel 3. 5,52 g 5-(2`-fury1)-hydantoinhydrat losas i 15 ml attiksyra och 15 ml vatten. mom forloppet av 15 minuter inledes vid 19° gasformig klor motsvarande 1,5 ml flytande klor vid — 80°. Efter avkylning till — 20° tillsattas 30 ml 99-procentig etanol, 10 ml eter och 10 ml konc. saltsyra. Sedan det hela lamnats att sta 10 minuter vid — 20° avfiltreras den utfallda 3,4-dihydro2,4-dioxo-2H-pyrido [2,3-e} [1,3]oxazin-hydrokloriden, tvattas med 99-procentig etanol och torkas. Utbyte 25-30 %. Example 3. 5.52 g of 5- (2 '-furyl) -hydantoin hydrate are dissolved in 15 ml of acetic acid and 15 ml of water. The course of 15 minutes begins at 19 ° gaseous chlorine corresponding to 1.5 ml of liquid chlorine at -80 °. After cooling to -20 °, 30 ml of 99% ethanol, 10 ml of ether and 10 ml of conc. hydrochloric acid. After leaving for 10 minutes at -20 ° C, the precipitated 3,4-dihydro-2,4-dioxo-2H-pyrido [2,3-e} [1,3] oxazine hydrochloride is filtered off, washed with 99% ethanol and dried. Yield 25-30%.
Exempel 4. 92 g 5-(2'-fury1)-hydantoin suspenderas i 210 ml 2-n saltsyra och forsattes droppvis under kraftig omroring under fiirloppet av 1 timme med 120 g brom. Reaktionsblandningen filtreras omedelbart efter bromtillsatsen och filteraterstoden tvattas med aceton och darefter med vatten. Den erhallna 3,4-dihydro-2,4-dioxo-2Hpyrido-[2,3-e][1,3]oxazinen smalter efter omkristallisation ur isattika vid 280°. Den är identisk med den genom behandling av 5-(2'-fury1)-hydantoin med klor framstallda substansen. Utbyte 7-10 %. Example 4. 92 g of 5- (2'-furyl) -hydantoin are suspended in 210 ml of 2-n hydrochloric acid and continued dropwise with vigorous stirring over the course of 1 hour with 120 g of bromine. The reaction mixture is filtered immediately after the bromine addition and the filter residue is washed with acetone and then with water. The resulting 3,4-dihydro-2,4-dioxo-2H-pyrido [2,3-e] [1,3] oxazine melts after recrystallization from glacial acetic acid at 280 °. It is identical to the substance produced by the treatment of 5- (2'-fury1) -hydantoin with chlorine. Yield 7-10%.
Claims (4)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE190894T |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| SE190894C1 true SE190894C1 (en) | 1964-01-01 |
Family
ID=41977461
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SE190894D SE190894C1 (en) |
Country Status (1)
| Country | Link |
|---|---|
| SE (1) | SE190894C1 (en) |
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0
- SE SE190894D patent/SE190894C1/sv unknown
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