4- CYCLOHEXENE-l ,2-DICARBOXYLIC

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). 

Cyclohexene-l,2-dicarboxylic acid, diethyl ester, cis-, and 1,2-Cyclohexanedicarboxylic acid, diethyl ester, cis-)... 

TRIMETHYLSILYLOXY-l,3-BUTADIENE AS A REACTIVE DIENE DIETHYL traits-4-TRIMETHYLSILYLOXY-4-CYCLOHEXENE-l,2-DICARBOXYLATE... 

Cyclohexanone cyanohydrin, hi 10 ds-4-Cyclohexene-1,2-dicarboximide, t75 ds-4-Cyclohexene-l,2-dicarboxylic anhydride, t74... 

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... 

HEXAHYDRO - 4a,5 - DIMETHYL - 2(3H) - NAPHTHALE-NONE and 2-TRIMETHYLSILYLOXY-1,3-BUTADIENE AS A REACTIVE DIENE DIETHYL trans -4-TRIMETHYL-SILYLOXY-4-CYCLOHEXENE-l,2-DICARBOXYLATE. Sulfur substitution also continues to be of high interest, and three preparations on sulfide synthesis are included BENZYL SULFIDE DIALKYL AND ALKYL ARYL SULFIDES NEOPENTYL PHENYL SULFIDE and UNSYMMETRICAL DIALKYL DISULFIDES sec-BUTYL ISOPROPYL DISULFIDE. 

This adduct, 3-frimethyl,silyl-4-cyclohexene-l,2-dicarboxylic acid anhydride, and derived allylsilancs (5) and (d) wore roiiiul U> undergo some inleresting... 

In order to prepare products with improved properties, we tried to epoxidize first the double bond in diglycidyl 4-cyclohexene-1,2-dicarboxylates. Attempts to epoxidize diglycidyl 4-methyl-4-cyclohexene-l,2-dicarboxylate failed, presumably because of steric hindrance by the methyl group at the double bond. On the other hand, the epoxidation occurs easily in the case of the -CH=C(CH3)-groups in an aliphatic chain [24]. 

UP-650T diglycidyl ether of l,l-di(hydroxymethyl)-3,4-epoxycyclohexane UP-650 diglycidyl ether of l,l-di(hydroxymethyl)-3-cyclohexene UP-656 glycidyl ether of 3,4-epoxy-l-hydroxymethyl-cyclohexane UP-640 diglycidyl ester of 3(4)-methyl-4-cyclohexene-l,2-dicarboxylic acid UP-640T di ycidyl ester of 4,5-epoxy-3(4)-methyl-cyclohexane-1,2-dicarboxylic acid... 

Fig. 11), through intermediates of type 291 readily obtainable from cis 4-cyclohexene-l,2-dicarboxylic acid 292 have also been described [114]. 

In contrast with the results obtained with simple allqfl halides, benzyl bromide leads to the formation of 77 and the ketone 78 in variable ratios (Scheme 26). A similar result has been reported in the reactions between the oxidative addition product of Ni(COD)bpy or Ni(COD)TMEDA with cw-4-cyclohexen-l,2-dicarboxylic anhydride and alkyl iodidesWith allyl bromide as the electrophile, ketone 79 is the only product isolated. However, when the reaction is performed with isolated nickelacycle 66 in the absence of Ni(CO)2Me2Phen, allylated alanine 80 is formed exclusively (60% yield) (Scheme 26). These results show that the carbonyl nickel complex is not inert because with certain reagents it transfers CO to the nickeMactone 66. Alternatively, the formation of ketones in these reactions could be explained by alkylation of the primary oxidative addition product or by carbonylation of allyl or benzyl bromide to give acyl bromides which react with 66 to give the observed products. However, this last reaction pathway seems unlikely because acetyl or benzoyl chloride do not react with in situ generated nickelacycle 66. 

In general, on going from the unsaturated fuUy conjugated anhydrides to the saturated systems, the two C—O stretching modes begin to coalesce, and in many cases only a single band is observed. In maleic anhydride, these modes occur at 1060 and 899 cm whUe in ds-4-cyclohexene-l,2-dicarboxylic acid anhydride they are found at 998 and 935 cm . Explain this observation. 

Graft copolymers between unsatnrated acids, especially acrylic acid and maleic anhydride (MA), and polyolefins (PE and PP) are widely used as surface modifiers and compatibilisers, sometimes in combination with bi-functional coupling agents [46], for talc, calcium carbonate and calcined clays. Such polymer coatings include polypropylene-maleic anhydride [47], polypropylene c/s-4-cyclohexene-l,2 dicarboxylic acid [48], polystearyl or polylauryl acrylate [49], polypropylene-acrylic acid, partially oxidised poly(butane diol) [50] and ethylene-vinyl acetate copolymers [51]. Acid-containing products can react with basic fillers. With most other types, they will simply adsorb on to the mineral surface, but they can form esters with some non-basic metal hydroxyls, notably silanols. 

Such regioselectivity is not observed in cw-20 and franj-4-cyclohexene-l,2-dicarboxylates because the participation of oxygen functions in the TS is not significant in the stability of the TS. 

As a consequence of the concerted mechanism, the Diels-Alder reaction is stereospecific. For example, reaction of 1,3-butadiene with dimethyl cw-2-butenedioate (dimethyl maleate, a cis aUcene) gives dimethyl cw-4-cyclohexene-l,2-dicarboxylate. The stereochemistry at the original double bond of the dienophile is retained in the product. In the complementary... 

Cordycepic acid 6678 4-Cyclohexene-l,2-dicarboxylic acid. Decanoic acid glycerol triester 5568... 

---