4-Cyclohexene-1 ,2-dicarboxylic anhydride, cis

Cyclohexene-1,2-dicarboxylic ANHYDRIDE, cis-, 30, 93 Cyclohexene oxide, 32, 39, 40 Cyclohexene sulfide, 32, 39... 

Cyclohexanedicarboxylic acid, diethyl ester, CIS-, 29 Cyclohexanone, 90 4-Cyclohexene-I, 2-dicarboxylic ACID, diethyl ester, CIS-, 29 4-Cyclohexene-1,2-dicarboxylic anhydride, CIS-, 93... 

Cyclohexene-1-acetonitrile, 31, 25, 26 4-Cyclohexene-1, 2-dicarboxylic ACID, DIETHYL ester, cis-, 30, 29 4-Cyclohexene-1,2-dicarboxylic ANHYDRIDE, cis-, 30, 93 Cyclohexene oxide, 32, 39, 40 Cyclohexene sulfide, 32, 39... 

Synonyms 4-Cyclohexene-1,2-dicarboxylic acid Maleic anhydride adduct of butadiene 3a,4,7,7a-Tetrahydro-1,3-isobenzofurandione Tetrahydrophthalic acid anhydride 1,2,3,6-Tetrahydrophthalic anhydride [gD] Tetrahydrophthalic anhydride THPA Definition Commercial prod, is the cis-isomer Empirical CsHsOs Formula C,iH8(C0)20... 

Tetrahydrobenzyl alcohol (( )3-cyclohexenene-l-methanol) and 30% aqueous hydrogen peroxide were purchased from Fluka, AG. 3-Cyclohexene-1-carboxylic acid and cis-4-cyclohexene-l,2-dicarboxylic acid were used as purchased from Lancaster Chemical Co. Methyl iodide, acetic anhydride, Oxone (potassium peroxymonosulfate), Aliquot 336 (methyl tri-n-octylammonium chloride), sodium tungstate dihydrate and N,N-dimethylaminopyridine (DMAP) were purchased from Aldrich Chemical Co. and used as received. 3,4-Epoxycyclohexylmethyl 3, 4 -epoxycyclohexane carboxylate (ERL 4221) and 4-vinylcyclohexene dioxide were used as purchased from the Union Carbide Corp. (4-n-Octyloxyphenyl)phenyliodonium hexafluoroantimonate used as a photoinitiator was prepared by a procedure described previously (4). 

When 1,2,3,6-tetrahydrophthalic anhydride (4-cyclohexene-l,2-dicarboxylic acid anhydride) (36) is heated with a mixture of hydrogen sulfide and hydrogen in the presence of cobalt sulfide, it gives octahydrobenzo[c]thiophene (53%) and a trace of 4,5,6,7-tetra-hydrobenzo[c]thiophene.48 Similar treatment of hexahydrophthalic anhydride gives a mixture (69%) of cis- and (rcww-octahydrobenzo[c]-thiophene, which may be separated by VPC.48... 

The experiment that follows involves the conversion of 4-cyclohexene-cis-1,2-dicarboxylic acid (3) to cyclohexane-cis-l,2-dicarboxylic acid (4), as shown in Equation 17.8. The catalytic hydrogenation of 3 is considered to be selective because the carboxylic acid groups, -CO2H, are not reduced under the reaction conditions. The starting material for this reduction may be readily prepared by the hydrolysis of 4-cyclohexene-czs-l,2-dicarboxylic acid anhydride, which is the product of the Diels-Alder reaction between butadiene and maleic anhydride, according to the procedure outlined in Section 12.3, Part Cl. 

Diels-Alder Reaction 4-Cyclohexene-cis-1,2-dicarboxylic Acid Anhydride... 

Interestingly, with hindered cyclic anhydrides, such as the cyclohexene derivative (cK-l-methyl-3-oxa-2,4-dioxobicyclo[4.3.0]-7-nonene, cis-l-methylcyclohex-4-ene-1,3-dicarboxylic add anhydride) shown in Scheme 9.113, only one of the two (the most hindered) carbonyl groups is reduced and the lactone (cyclic ester) cis- -methyl-3-oxa-4-oxobicyclo[4.3.0]-7-nonene(cis-l-methyl-l-hydroxymethylcyclohex-4-ene carboxylic acid y-lactone) is produced. As shown in the scheme, it is argued that the initial lithium aluminum hydride (LiAUlt) attack is on the less hindered carbonyl and intramolecular transfer of hydride (H ) to the more hindered carbonyl follows later. 

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