1.3- Butadiene-2,3-dicarboxylic acid

The generation of variously substituted butadienes has been accomplished via the thermal rDA reaction of substituted cyciohexene derivatives. Derivatives of 1,3-butadiene-2,3-dicarboxylic acid, which are otherwise difficuit to prepare, have been obtained by the vapor-phase pyrolysis of cyciohexene-1,2-... 

HOOC-CH2-CH2-COOH), one with fumaric (trans-butadiene dicarboxylic) acid and one with maleic (cis-butadiene dicarboxylic) acid. 

G-20 Dicarboxylic Acids. These acids have been prepared from cyclohexanone via conversion to cyclohexanone peroxide foUowed by decomposition by ferrous ions in the presence of butadiene (84—87). Okamura Oil Mill (Japan) produces a series of commercial acids based on a modification of this reaction. For example, Okamura s modifications of the reaction results in the foUowing composition of the reaction product C-16 (Linear) 4—9%, C-16 (branched) 2—4%, C-20 (linear) 35—52%, and C-20 (branched) 30—40%. Unsaturated methyl esters are first formed that are hydrogenated and then hydrolyzed to obtain the mixed acids. Relatively pure fractions of C-16 and C-20, both linear and branched, are obtained after... 

Bromovinyl)trimethylsilanc, 58, 153, 157 Butadiene-2,3-dicarboxylic acid, derivatives,... 

Compared with the anodic oxidation of a 1,3-diene, the cathodic reduction of a 1,3-diene may be less interesting since the resulting simple transformation to monoolefin and alkane is more conveniently achieved by a chemical method than by the electrochemical method. So far, only few reactions which are synthetically interesting have been studied15. The typical pattern of the reaction is the formation of an anion radical from 1,3-diene followed by its reaction with two molecules of electrophile as exemplified by the formation of the dicarboxylic acid from butadiene (equation 22)16. 

Sebacic acid (1,8-octane dicarboxylic acid), which is used to make nylon-610, has been produced from 1,3-butadiene and by the dry distillation of castor oil (ricinolein). The cleavage of licinoleic acid gives 2-octanol and the salt of sebacic acid. 

Abbreviations coiX-V] = copolymers of X and Y colX-b-Yl = block copolymers of poly X and poly Y ST = styrene MA = methyl acrylate MMA = methyl methacrylate AN = acrylonitrile BD = butadiene LR (liquid rubbers) = a, cj-polybutadiene-diols and -dicarboxylic acids Cell-Ac = cellulose acetate Cell-N02 = cellulose nitrate. 

Pure crystalline 2,3-dicyanobutadiene has been prepared in high yield by gas-phase thermolysis of cyclobutene (2).2,8 Analogous thermolysis of derivatives of cyclobutene-1,2-dicarboxylic acid appears to represent general procedures for the synthesis of derivatives of butadiene-2,3-dicarboxylic acid of high purity.2,12 These... 

Butadiene-2,3-dicarboxylic acid Succinic acid, dimethylene- (8), Butanedioic acid, bis(methylene)- (9) (488-20-0)... 

C-20 Dicarboxylic Acids. These acids have been prepared front cyclohexanone via conversion to cyclohexanone peroxide followed by decomposition by ferrous ions in Ihe presence of butadiene, Okamura Oil Mill (Japan) produces a series of commercial acids based on a modification of this reaction. 

R1 = N3 R2 = OH) were useful compounds (see Section II,D). The starting materials 55 had been synthesized via Diels-Alder reaction of acetylene-dicarboxylic acid with 2,3-dialkyl-1,3-butadienes, followed by oxidation (85USP4532301 85USP4556512). Yoshida et al. condensed the doubly cross-conjugated cyclopentadiene 57 with hydrazine to obtain 1,2-diazocine 58 (84TL4223) (For structural studies of 58, see Section II,B.)... 

McBride and Hall (37,38) reported the first observation of a controlled catalytic reaction on alumina using IETS. They studied the catalytically induced transfer hydrogenation from water vapor to unsaturated hydrocarbon chains chemisorbed on alumina at both ends of the chain. They absorbed muconic acid ( trans-trans-1,3 butadiene 1,4 dicarboxylic acid, HOOC-CH=CH-CH=CH-COOH ) onto oxidized aluminum strips using the liquid doping technique. The samples were returned to the vacuum system, and in the presence of 0.3 torr of D2O vapor, heated to up to 400° C by passing current through a heater strip evaporated on the back of the glass slide. The films were then allowed to cool and the junctions completed by evaporation of the Pb counter electrode. 

Fig. 15.20. [4+2]-Cycloaddi-tion between l-(di methyl-amino)- , 3-butadiene and cis-dicyanoethene dicarboxylic acid diester II explanation of the inversion of configuration in the dienophile moiety.

Poly(isobutylene) dicarboxylic acid was prepared by oxidation of the copolymer of isobutylene with a diene 53,54). The most efficient oxidizing agent was the system KMn04-periodic acid. Oxidation of a copolymer of isobutylene and 2,3-dimethyl-butadiene afforded a polymeric bis-ketone54). 

The radical polymerization in aqueous solution of a series of monomers—e.g., vinyl esters, acrylic and methacrylic acids, amides, nitriles, and esters, dicarboxylic acids, and butadiene—have been studied in a flow system using ESR spectrometry. Monomer and polymer radicals have been identified from their ESR spectra. fi-Coupling constants of vinyl ester radicals are low (12-13 gauss) and independent of temperature, tentatively indicating that the /3-CH2 group is locked with respect to the a-carbon group. In copolymerization studies, the low reactivity of vinyl acetate has been confirmed, and increasing reactivity for maleic acid, acrylic acid, acrylonitrile, and fumaric acid in this order has been established by quantitative evaluation of the ESR spectra. This method offers a new approach to studies of free radical polymerization. 

Using hydroformylation and other catalytic or stoichiometric reactions, how could the following transformations be achieved in one or more steps (a) Ethylene to 2-methylpentanol (b) butadiene to 1,6-hexanediol (c) allyl alcohol to butane 1,4-dicarboxylic acid (d) allyl alcohol to 4-carboxylic butanal. 

The selective hydrogenation of 1,5-cyclooctadiene (1,5-COD) and 1,5,9-cyclodode-catriene (1,5,9-CDT), cyclic oligomers of 1,3-butadiene, to the corresponding monoenes has been the subject of considerable interest, since the hydrogenation may constitute one of the steps leading to the synthesis of C8 and C12 lactams, dicarboxylic acids, and their derivatives. 

C. 5 -Methoxycyclohexan- -one- > A -dicarboxylic acid anhydride. To 3.00 g (0.174 mol) of 1-methoxy-3-trimethylsiloxy- 1,3-butadiene at 0°C (ice bath) is added a total of 980 mg (0.01 mol) of freshly sublimed maleic anhydride in portions of 70-80 mg each over a period of 25 min. When the addition is complete, the ice bath is removed and the clear solution is stirred for 15 min at room temperature (Note 7). Three 5-mL portions of a solution of tetrahydrofuran (35 mL) and 0.1 N hydrochloric acid (15 mL) are added and the solution is stirred for 1 min. The remaining acid solution (35 mL) is added all at once and the resulting solution is poured into 100 mL of chloroform and treated with 25 mL of water. The organic layer is separated and the aqueous layer is extracted four times with 100-mL portions of chloroform. The extracts are combined and dried over anhydrous magnesium sulfate. The solvent is then removed under reduced pressure (Note 8) to provide 2.0 g of an oil which solidifies. Pentane (10 mL) is added to the oily solid and small portions... 

Ozonolysis as used below is the oxidation process involving addition of ozone to an alkene to form an ozonide intermediate which eventually leads to the final product. Beyond the initial reaction of ozone to form ozonides and other subsequent intermediates, it is important to recall that the reaction can be carried out under reductive and oxidative conditions. In a general sense, early use of ozonolysis in the oxidation of dienes and polyenes was as an aid for structural determination wherein partial oxidation was avoided. In further work both oxidative and reductive conditions have been applied . The use of such methods will be reviewed elsewhere in this book. Based on this analytical use it was often assumed that partial ozonolysis could only be carried out in conjugated dienes such as 1,3-cyclohexadiene, where the formation of the first ozonide inhibited reaction at the second double bond. Indeed, much of the more recent work in the ozonolysis of dienes has been on conjugated dienes such as 2,3-di-r-butyl-l,3-butadiene, 2,3-diphenyl-l,3-butadiene, cyclopentadiene and others. Polyethylene could be used as a support to allow ozonolysis for substrates that ordinarily failed, such as 2,3,4,5-tetramethyl-2,4-hexadiene, and allowed in addition isolation of the ozonide. Oxidation of nonconjugated substrates, such as 1,4-cyclohexadiene and 1,5,9-cyclododecatriene, gave only low yields of unsaturated dicarboxylic acids. In a recent specific example... 

The aromatization of bicyclo[4.1.0]hept-3-enes gives access to a wide variety of cycloproparenes the substrates are readily available via Diels — Alder reaction of butadienes w ith cyclopropcnes. 1,2-Dihalo- and tetrahalocyclopropenes have been used for this purpose. In the aromatization step, it is important that the halo substituents arc located at Cl and C6 of the bicyclo[4.1. OJhept-3-ene. Halogens at C2 and C5 result in ring enlargement rather than aromatization on reaction with base. Oxidative bis-decarboxylation of bicyclo[4.1.0]hept-3-ene-l, 6-dicarboxylic acid was investigated as an alternative route to cycloproparenes however, the products were derived from carbenium ion capture after monodecarboxylation. 

---