Cyclohexene dicarboxylate

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

A three-component free radical reaction leading to a cyclohexene-dicarboxylic ester is also quite useful. 

Figure 11.30 Reaction scheme for the oxidation of cyclohexene dicarboxylate (after [122]).

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). 

Cyclohexanone oxime, 32, 15 Cyclohexene, 31, 66 1-Cyclohexene-l-acetonitrile, 31, 25, 26 4-Cyclohexene-1,2-dicarboxylic... 

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

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... 

Cyclopentenone annelation. The reaction of the dilithio derivative (2) of dimethyl 4-cyclohexene-1,2-dicarboxylate (LDA, THF/HMPT) with 1 at -45 -> 0° results in the bicyclic enone 3 in 72% yield. The reaction may involve conjugate addition of 2 to 1 to give a ketene (a) with loss of lithium phenoxide. Several other... 

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... 

The catalyst was prepared from the corresponding chiral diol and TiCl2(OPr-/)2 at room temperature in the presence of 4 A molecular sieves. Without molecular sieves, stoichiometric amounts of the titanium complex were required to obtain an equally high enantioselectivity. A remarkable solvent effect was observed. Various cycloadducts were only obtained with high optical yields when non-polar solvents were employed252,253. For example, 4-substituted 4-cyclohexene-1,2-dicarboxylate derivatives 408 were obtained with ee values ranging from 91 to 94% in the reactions of 91a, 399 and 407 with 17b in toluene/... 

To improve the processability of PI and to alleviate or eliminate volatiles, work began in the late 1960 s under NASA Lewis sponsorship (23), to end-cap oligomers with reactive groups. The first report involved the use of 3,6-endomethylene-l,2,3,6-tetrahy-drophthalic anhydride (5-norbornene-2,3-dicarbo ylic anhydride, nadic anhydride) and alkyl derivatives thereof (e.g. citraconic anhydride) and 1,2,3,4-tetrahydrophthalic anhydride (4-cyclohexene-1, 2-dicarboxylic anhydride) as the reactive end group on imide oligomers (23-25). This initial effort led to the development of P13N [with T for polyimide, 13 for Mn of 1300g/mole and N for nadic end cap] whose structure is shown below. 

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... 

Diastereoselective ring opening of mono- and bicyclic anhydrides with sodium (S)-4-isopropyl-2-thioxothiazolidinide is an attractive alternative 10°. Aminolyses are carried out in tetrahydrofuran at low temperatures in a 1 1 molar ratio in the absence or presence of additives such as HMPA, TMEDA or DMSO. High yield and diastereoselectivity are recorded in the case of 4-cyclohexene-1,2-dicarboxylic anhydride. /... 

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... 

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