GB596537A - Manufacture of substituted 5-amino-oxazole-4-carboxylic esters - Google Patents
Manufacture of substituted 5-amino-oxazole-4-carboxylic estersInfo
- Publication number
- GB596537A GB596537A GB1942245A GB1942245A GB596537A GB 596537 A GB596537 A GB 596537A GB 1942245 A GB1942245 A GB 1942245A GB 1942245 A GB1942245 A GB 1942245A GB 596537 A GB596537 A GB 596537A
- Authority
- GB
- United Kingdom
- Prior art keywords
- heating
- oxazole
- amino
- benzyl
- ethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- QPQATANMPQAAGP-UHFFFAOYSA-N 5-amino-1,3-oxazole-4-carboxylic acid Chemical class NC=1OC=NC=1C(O)=O QPQATANMPQAAGP-UHFFFAOYSA-N 0.000 title abstract 2
- 238000004519 manufacturing process Methods 0.000 title 1
- 238000010438 heat treatment Methods 0.000 abstract 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract 4
- 239000000243 solution Substances 0.000 abstract 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 abstract 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract 3
- 238000009738 saturating Methods 0.000 abstract 3
- 229910000761 Aluminium amalgam Inorganic materials 0.000 abstract 2
- ZOAUTDGCWCIUNX-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)NC(C(=O)OCC1=CC=CC=C1)C#N Chemical compound C(C1=CC=CC=C1)(=O)NC(C(=O)OCC1=CC=CC=C1)C#N ZOAUTDGCWCIUNX-UHFFFAOYSA-N 0.000 abstract 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M NaHCO3 Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 abstract 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N Phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 abstract 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N Phosphorus pentoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 abstract 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N Phosphoryl chloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 abstract 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M Sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 abstract 2
- 238000005917 acylation reaction Methods 0.000 abstract 2
- 125000000217 alkyl group Chemical group 0.000 abstract 2
- 125000003710 aryl alkyl group Chemical group 0.000 abstract 2
- 150000002148 esters Chemical class 0.000 abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 2
- -1 phenylacetyl Chemical group 0.000 abstract 2
- 229960000583 Acetic Acid Drugs 0.000 abstract 1
- PASDCCFISLVPSO-UHFFFAOYSA-N Benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 abstract 1
- VPUXOBKWJUQBAS-UHFFFAOYSA-N C(=CCCC)C=1OC(=C(N1)C(=O)OCC)N Chemical compound C(=CCCC)C=1OC(=C(N1)C(=O)OCC)N VPUXOBKWJUQBAS-UHFFFAOYSA-N 0.000 abstract 1
- UVECCHLSIFGSRO-UHFFFAOYSA-N C(C1=CC=CC=C1)C=1OC(=C(N1)C(=O)OCC)N Chemical compound C(C1=CC=CC=C1)C=1OC(=C(N1)C(=O)OCC)N UVECCHLSIFGSRO-UHFFFAOYSA-N 0.000 abstract 1
- KFSPHKGJKBYYKC-UHFFFAOYSA-N C1(=CC=CC=C1)C=1OC(=C(N1)C(=O)OCC1=CC=CC=C1)N Chemical compound C1(=CC=CC=C1)C=1OC(=C(N1)C(=O)OCC1=CC=CC=C1)N KFSPHKGJKBYYKC-UHFFFAOYSA-N 0.000 abstract 1
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 229910000564 Raney nickel Inorganic materials 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 230000002378 acidificating Effects 0.000 abstract 1
- 150000001263 acyl chlorides Chemical class 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 abstract 1
- RCUIWQWWDLZNMS-UHFFFAOYSA-N benzyl 2-cyanoacetate Chemical compound N#CCC(=O)OCC1=CC=CC=C1 RCUIWQWWDLZNMS-UHFFFAOYSA-N 0.000 abstract 1
- 235000019445 benzyl alcohol Nutrition 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 abstract 1
- CVCNAHPOWFVTKQ-UHFFFAOYSA-N ethyl 5-amino-2-phenyl-1,3-oxazole-4-carboxylate Chemical compound O1C(N)=C(C(=O)OCC)N=C1C1=CC=CC=C1 CVCNAHPOWFVTKQ-UHFFFAOYSA-N 0.000 abstract 1
- 238000005755 formation reaction Methods 0.000 abstract 1
- 239000012362 glacial acetic acid Substances 0.000 abstract 1
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 238000006317 isomerization reaction Methods 0.000 abstract 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 abstract 1
- 235000017557 sodium bicarbonate Nutrition 0.000 abstract 1
- 235000010288 sodium nitrite Nutrition 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
Alkyl and aralkyl esters of 5-amino-oxazole-4-carboxylic acids bearing a hydrocarbon substituent in the 2-position are manufactured by causing acylaminocyanacetic esters of the formula ROOC-CH(CN)-NHCO-R1 (wherein R represents alkyl or aralkyl and R1 a hydrocarbon radical) to isomerize by heating them or by subjecting them to contact with an acidic catalyst. The starting materials may be made from the appropriate isonitrosocyanacetic esters (e.g. ethyl isonitrosocyanacetate) by reduction, e.g. by means of aluminium amalgam or of hydrogen in the presence of a Raney nickel catalyst, followed by acylation, e.g. by treatment in the presence of a base (e.g. sodium bicarbonate) with an acyl chloride (e.g. phenylacetyl, benzoyl or hexen-2-oyl chloride), whereby isomerization may follow immediately unless the formation of any acid during acylation is prevented. Examples describe the conversion of ethyl a -phenylacetylaminocyanacetate to 2-benzyl-4-carbethoxy-5-amino-oxazole by (1) heating to 100 DEG C. with phosphorus pentachloride in chloroform; (2) heating on a steam bath with phosphorus oxychloride; (3) dissolving in ethanol and saturating the solution with dry hydrogen chloride at 0 DEG C.; and (10) simple heating to 160-170 DEG C.; of ethyl a -benzoylaminocyanacetate to 2-phenyl-4-carbethoxy-5-amino-oxazole by (4) simple heating to 140-150 DEG C.; (5) heating to 100 DEG C. with phosphorus pentachloride in chloroform; (6) heating similarly with phosphorus pentoxide; and (7) dissolving in ether and saturating the solution with dry hydrogen chloride at 0 DEG C.; (8) of ethyl a -hexen-2-oylaminocyanacetate to 2-penten-1-yl-4-carbethoxy-5-amino-oxazole by dissolving in ether and saturating the solution with dry hydrogen chloride in the cold; and (9) of benzyl benzoylaminocyanacetate to benzyl 2-phenyl-5-amino-oxazole-4-carboxylate by simple heating to 160 DEG C. Benzyl benzoylaminocyanacetate is obtainable by heating ethyl cyanacetate with benzyl alcohol, treating a solution of the resulting benzyl cyanacetate in glacial acetic acid with an aqueous solution of sodium nitrite, reducing the so formed oximino compound with aluminium amalgam, and acylating the product with benzoyl chloride.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB596537A true GB596537A (en) | 1948-01-06 |
Family
ID=1734728
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB1942245A Expired GB596537A (en) | 1945-07-30 | Manufacture of substituted 5-amino-oxazole-4-carboxylic esters |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB596537A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007017088A1 (en) * | 2005-07-25 | 2007-02-15 | Novartis Ag | Amidonitrile compounds |
-
1945
- 1945-07-30 GB GB1942245A patent/GB596537A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007017088A1 (en) * | 2005-07-25 | 2007-02-15 | Novartis Ag | Amidonitrile compounds |
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