STEREOCHEMISTRY OF THERMOLYTIC BASE-CATALYZED DECARBOXYLATION TO FORM CONJUGATED DIENE-ACIDS - SYNTHESIS USING ETHYLIDENEMALONIC ESTER CONDENSATION

被引:12
作者
CROMBIE, L
CROMBIE, WML
机构
[1] Department of Chemistry, University of Nottingham
来源
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1 | 1994年 / 10期
关键词
D O I
10.1039/p19940001267
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The condensation of aromatic aldehydes with ethylidenemalonic ester in the presence of benzyltrimethylammonium hydroxide leads to 2(E),4(E)-half-esters. which are decarboxylated in refluxing pyridine to 2(E),4(E)-esters. When decarboxylated by thermolysis in quinoline at 130 degrees C cinnamyl-idenemalonic acid gives almost pure 5-phenylpenta-2(Z),4(E)-dienoic acid which slowly stereo-mutates, but on continued heating at 170 degrees C it passes over to give almost pure 2(E),4(E)-acid. In pyridine near its boiling point, however, the malonic acid is converted into a 64:36 mixture of 2(Z),4(E)-:2(E),4(E)-acids, the composition of wh ich does not change on continued refluxing. The use of carboxy-labelled dideuteriomalonic acid in the pyridine reaction leads to 5-phenylpenta-2(Z),4(E)-dienoic acid and its 2(E),4(E)-stereoisomer, each having similar similar to 2:1 alpha/gamma deuterium labelling. The latter stereoisomer does not arise by stereomutation, and a dual pathway originating from a common deuteriated lactone is proposed. Decarboxylation of the deuteriomalonic acid in quinoline at 130 degrees C, giving almost pure 2(Z),4(E)-dienoic acid with similar to 2:1 alpha/gamma labelling, involves only one of the pathways. The ethylidenemalonic acid method is suitable for the preparation of 2(E),4(E)-half-esters and 5-phenylpenta-2(Z),4(E)-dienoic acids having both electron-withdrawing as well as electron-releasing aryl substituents. 2(Z),4(E)-Sorbic acid can also be made from the corresponding malonic acid by quinoline-catalysed decarboxylation, whereas the classical pyridine-catalysed Doebner reaction forms almost entirely 2(E),4(E)-sorbic acid.
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页码:1267 / 1274
页数:8
相关论文
共 23 条
[1]   THE EXISTENCE OF A 1,2-ADDITION, 1,2-ELIMINATION MECHANISM FOR DECARBOXYLATION [J].
COREY, EJ ;
FRAENKEL, G .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1953, 75 (05) :1168-1172
[4]   SYNTHESIS OF CANNABINOIDS CARRYING OMEGA-CARBOXY SUBSTITUENTS - THE CANNABIDIOLS, CANNABINOL AND DELTA-1-TETRAHYDROCANNABINOLS AND DELTA-6-TETRAHYDROCANNABINOLS OF THIS SERIES [J].
CROMBIE, L ;
CROMBIE, WML ;
TUCHINDA, P .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1988, (05) :1255-1262
[5]   BIOSYNTHESIS OF PARASORBIC ACID (HEX-2-EN-5-OLIDE) BY ROWAN BERRY (SORBUS AUCUPARIA L) [J].
CROMBIE, L ;
FIRTH, PA .
JOURNAL OF THE CHEMICAL SOCIETY C-ORGANIC, 1968, (22) :2852-&
[6]  
CROMBIE L, 1979, TETRAHEDRON LETT, P4773
[7]   About the unsaturated acids of sorbin acid series and its transformation in cyclic hydrogen substances. [J].
Doebner, O .
BERICHTE DER DEUTSCHEN CHEMISCHEN GESELLSCHAFT, 1902, 35 :2129-2138
[8]   POLYENE ACIDS .6. A NEW (CIS-TRANS-)ISOMER OF SORBIC ACID AND ITS RELATION TO HEXENOLACTONES [J].
EISNER, U ;
ELVIDGE, JA ;
LINSTEAD, RP .
JOURNAL OF THE CHEMICAL SOCIETY, 1953, (MAY) :1372-1379
[9]   POLYENE ACIDS .11. PREPARATION OF ALPHA-TRITIATED (OR DEUTERIATED) CONJUGATED ENOIC AND DIENOIC ACIDS AND THEIR EXAMINATION BY TRITON MAGNETIC-RESONANCE SPECTROSCOPY [J].
ELVIDGE, JA ;
JONES, JR ;
MANE, RB ;
SALJOUGHIAN, M .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1978, (10) :1191-1194
[10]   POLYENE ACIDS .X. CONFORMATION OF HEXENOLACTONE AND CONFIGURATION OF DERIVED SORBIC ACID AS INDICATED BY PROTON MAGNETIC RESONANCE SPECTROSCOPY [J].
ELVIDGE, JA ;
RALPH, PD .
JOURNAL OF THE CHEMICAL SOCIETY B-PHYSICAL ORGANIC, 1966, (03) :243-&