Cycloalkane-carboxylates

Attention has also been directed to the degradation of cycloalkane carboxylic acids ... 

Wang ZY, Han XY, Wang LS. Quantitative correlation of chromatographic retention and acute toxicity for alkyl(l-phenylsulfonyl) cycloalkane carboxylates and their structural parameters by DFT. Chin J Struct Chem 2005 24(7) 851-7. 

He YB, Wang LS, Liu ZT, Zhang Z. Acute toxicity of alkyl (1-phenylsulfonyl) cycloalkane-carboxylates to Daphnia magna and quantitative structure-activity relationships. Chemosphere 1995 31 2739-46. 

Chen, J., Feng, L., Liao, Y., Han, S., Wang, L.-S. and Hu, H. (1996) Using AMI Hamiltonian in quantitative structure-properties relationship studies of alkyl(l-phenylsulfonyl) cycloalkane-carboxylates. Chemosphere, 33, 537-546. 

PERKIN Carboxylic Acid (Ester) Synthesis Synthesis of cycloalkane carboxylic acids from a,t -dihaloalkanes and diethyl sodiummalonate. 

Herman, D.C., Fedorak, P.M., Costerton, J.W. 1993. Biodegradation of cycloalkane carboxylic acids in oil sand tailings. Canadian Journal of Microbiology, Vol.39, No 6, pp.576-580. 

In 1894, Alexie Favorskii published an early account of the rearrangement of simple acyclic a-halo ketones. This was followed in subsequent years with additional reports/ In 1914, he published the cyclic version featuring the ring contraction of 2-chlorocyclohexanone. This modification makes this transformation a reliable way to sjmthesize 1-substituted cycloalkane carboxylic acid derivatives. Later in the century, the rearrangement found application in the modification of steroids. Only in the last half of the 20 century has a clearer picture of the mechanism appeared. ... 

The malonic ester synthesis can also he used to prepare cycloalkane-carboxylic acids. For example, when 1,4-dihromohutane is treated with diethyl malonate in the presence of 2 equivalents of sodium ethoxide base, the second alkylation step occurs intramolecularly to yield a cyclic product. Hydrolysis and decarboxylation then give cyclopentanecarhoxylic acid. Three-, four-, five-, and six-membered rings can all be prepared in this way. 

The name naphthenic acid is derived from the early discovery of monobasic carboxyUc acids in petroleum, with these acids being based on a saturated single-ring stmcture. The low molecular weight naphthenic acids contain alkylated cyclopentane carboxyUc acids, with smaller amounts of cyclohexane derivatives occurring. The carboxyl group is usually attached to a side chain rather than direcdy attached to the cycloalkane. The simplest naphthenic acid is cyclopentane acetic acid [1123-00-8] (1, n = 1). 

Oxidative reactions frequently represent a convenient preparative route to synthetic intermediates and end products This chapter includes oxidations of alkanes and cycloalkanes, alkenes and cycloalkenes, dienes, aromatic fluorocarbons, alcohols, phenols, ethers, aldehydes and ketones, carboxylic acids, nitrogen compounds, and organophosphorus, -sulfur, -selenium, -iodine, and -boron compounds... 

Similar to the intramolecular insertion into an unactivated C—H bond, the intermolecular version of this reaction meets with greatly improved yields when rhodium carbenes are involved. For the insertion of an alkoxycarbonylcarbene fragment into C—H bonds of acyclic alkanes and cycloalkanes, rhodium(II) perfluorocarb-oxylates 286), rhodium(II) pivalate or some other carboxylates 287,288 and rhodium-(III) porphyrins 287 > proved to be well suited (Tables 19 and 20). In the era of copper catalysts, this reaction type ranked as a quite uncommon process 14), mainly because the yields were low, even in the absence of other functional groups in the substrate which would be more susceptible to carbenoid attack. For example, CuS04(CuCl)-catalyzed decomposition of ethyl diazoacetate in a large excess of cyclohexane was reported to give 24% (15%) of C/H insertion, but 40% (61 %) of the two carbene dimers 289). 

Significant synthetic applications of the nickel-salen catalysts are the formation of cycloalkanes by reduction of <>, -a-dihaloalkanes255,256 and unsaturated halides,257,258 the conversion of benzal chloride (C6H5CHC12) into a variety of dimeric products 259 the synthesis of 1,4-butanediol from 2-bromo- and 2-iodoethanol260 or the reduction of acylhalides to aldehydes261 and carboxylic acids.262... 

Few examples of preparatively useful intermolecular C-H insertions of electrophilic carbene complexes have been reported. Because of the high reactivity of complexes capable of inserting into C-H bonds, the intermolecular reaction is limited to simple substrates (Table 4.9). From the results reported to date it seems that cycloalkanes and electron-rich heteroaromatics are suitable substrates for intermolecular alkylation by carbene complexes [1165]. The examples in Table 4.9 show that intermolecular C-H insertion enables highly convergent syntheses. Elaborate structures can be constructed in a single step from readily available starting materials. Enantioselective, intermolecular C-H insertions with simple cycloalkenes can be realized with up to 93% ee by use of enantiomerically pure rhodium(II) carboxylates [1093]. 

Cycloalkanes with carboxyl substituents are named as cycloalkanecar-boxylic acids. Unsaturated acids are named using the name of the alkene with -e replaced with -oic acid. The chain is numbered starting with the carboxyl group, a number designates the location of the double bond and Z or E is used. 

Oxidations of hydrocarbons (cycloalkanes, cycloalkenes, aromatics) photo-catalyzed by metallotetrapyrroles lead to the formation of epoxides, aldehydes, ketones, alcohols, and carboxylic acids both in solutions and polymer matrices. These processes frequently occur as selective (one-product formation) reactions. Irradiation with visible light has a pronounced accelerating effect on such important industrial processes as the oxidation of thiols to disulfides (Merox process [265]) in a treatment of petroleum distillates or waste water cleaning. 

Linear/cycloalkane o2 Alcohols, ketones, carboxylic acids [19]... 

The Bashkirov oxidation (liquid-phase oxidation of n-alkanes or cycloalkanes in the presence of boric acid and hydrolysis) yields the corresponding secondary alcohols [16, 17]. The reaction is used industrially for oxidation of C10 to C18 n-alkanes, providing raw materials for detergents and for oxidation of cyclododecane to cyclo-dodecanol as an intermediate for the production of Nylon 12 (Table 1, entry 8). The process is not of much commercial importance in the western world, however. Oxidation in the absence of boric acids usually leads to mixtures of alcohols, ketones, and carboxylic acids (Table 1, entry 9). 

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