Cyclohexene-4,5-dicarboxylic acid

A parallel electrooxidation of cis- or trans-cyclohexene-4,5-dicarboxylic acids would thus be expected to produce 1,4-cyclohexadiene, eqn 7. 

For example, cyclohexene dicarboxylic acid exists in cis and trans forms XII and XIII. 

The epoxidation method developed by Noyori was subsequently applied to the direct formation of dicarboxylic acids from olefins [55], Cyclohexene was oxidized to adipic acid in 93% yield with the tungstate/ammonium bisulfate system and 4 equivalents of hydrogen peroxide. The selectivity problem associated with the Noyori method was circumvented to a certain degree by the improvements introduced by Jacobs and coworkers [56]. Additional amounts of (aminomethyl)phos-phonic acid and Na2W04 were introduced into the standard catalytic mixture, and the pH of the reaction media was adjusted to 4.2-5 with aqueous NaOH. These changes allowed for the formation of epoxides from ot-pinene, 1 -phenyl- 1-cyclohex-ene, and indene, with high levels of conversion and good selectivity (Scheme 6.3). 

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). 

In the case of 1,3-cyclohexadiene with Me2Zn, the dicarboxylation afforded the /rdicarboxylic acid 96 (Scheme 33). In contrast, when Ph2Zn was used instead of Me2Zn as a transmetallation agent, the phenylative carboxylation occurred in high regio- and stereoselectivity to give the l,4-m-substituted-2-cyclohexene 97, as a result of reductive elimination from the phenyl-7r-allylnickel intermediate, prior to the second carboxylation reaction (Scheme 33).47... 

Cyclohexanone, 2-hydroxymethyl-ene-, preparation of, 54, 38 reaction with alkylenedithio-tosylates, 54, 37 Cyclohexanone, 2,2-trimethy1-enedithio-, 54, 39 4-CYCLOHEXENE—1,2-DICARBOXYLIC ACID, DIETHYL ESTER, trans-, 50, 43... 

In recent studies, Friberg and co-workers (J, 2) showed that the 21 carbon dicarboxylic acid 5(6)-carboxyl-4-hexyl-2-cyclohexene-1-yl octanoic acid (C21-DA, see Figure 1) exhibited hydrotropic or solubilizing properties in the multicomponent system(s) sodium octanoate (decanoate)/n-octanol/C2i-DA aqueous disodium salt solutions. Hydrotropic action was observed in dilute solutions even at concentrations below the critical micelle concentration (CMC) of the alkanoate. Such action was also observed in concentrates containing pure nonionic and anionic surfactants and C21-DA salt. The function of the hydrotrope was to retard formation of a more ordered structure or mesophase (liquid crystalline phase). 

Figure 1. Structure of the dicarboxylic acid 5-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid (C21-DA).

Eevulinic acid, see Aniline Malaoxon, see Malathion Malathion diacid, see Malathion Malathion dicarboxylic acid, see Malathion Malathion monoacid, see Malathion Malathion a-monoacid, see Malathion Malathion p-monoacid, see Malathion 2-Nitrophenol p-Malathion monoacid, see Malathion Malathion monocarboxylic acid, see Malathion Maleic acid, see 2-Chlorophenol, Maleic anhydride. Maleic hvdrazide. 4-Nitrophenol, Phenol Malonic acid, see Cyclohexene, 1,4-Dioxane Malonic acid semialdehyde, see irans-1,3-Dichloropropylene... 

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

Triethylamine (8) Ethanamine, N,N-diethyl- (9) (121-44-8) Diethyl trans-4-trimethylsiIyloxy-4-cycIohexene-1,2-dicarboxylate 4-Cyclohexene-1,2-dicarboxylic acid, 4-(trimethylsilyloxy)-, diethyl ester (8,9) (-)... 

Protons present in aqueous acid also act as reasonably efficient electron acceptors. If the reduced hydrogen atoms are formed on metallized suspensions, catalytic hydrogenation can result. For example, in contrast to the oxidative chemistry reported earlier for cyclohexene-4,5-bis-dicarboxylic acid (Eq. 28), if the reaction is conducted in the absence of oxygen in aqueous nitric acid, catalytic hydrogenation of the double bond becomes a major pathway, Eq. (34). ... 

C-21 Dicarboxylic Acids. C-21 dicarboxylic acids arc a mixture of predominately 5 dicarboxylic acids are produced by Westvaco Corporation in Charleston, South Carolina in mullimillion-kg quantities. The process involves reaction of tall oil fatty acids (TOFA) (containing about 50% oleic acid and 50% linolcic acid) with acrylic acid and iodine at 220-250°C for about 2 h. 

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... 

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... 

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