Cyclopentane, acidity

Scheme 7.11 Sequential reduction to chiral cyclopentane acid 26.

The standard nomenclature for this family of readily released fatty acids from tissues and organs and the synthetic prostaglandin-like compounds is derived from the C-20 cyclopentane acid skeleton of the hypothetical prostanoic acid 1. 

The majority of acids contained in the diesel cuts are cyclic and come from cyclopentane or cyclohexane. They are better known as naphthenic acids / ... 

It is important that the synthesis should be carried out as quickly as possible, particularly the washing with alkah at 0°, since the latter tends to convert the product into cyclopentane-a-hydroxycarboxyhc acid. 

Cyclopentene derivatives with carboxylic acid side-chains can be stereoselectively hydroxy-lated by the iodolactonization procedure (E.J. Corey, 1969, 1970). To the trisubstituted cyclopentene described on p. 210 a large iodine cation is added stereoselectively to the less hindered -side of the 9,10 double bond. Lactone formation occurs on the intermediate iod-onium ion specifically at C-9ot. Later the iodine is reductively removed with tri-n-butyltin hydride. The cyclopentane ring now bears all oxygen and carbon substituents in the right stereochemistry, and the carbon chains can be built starting from the C-8 and C-12 substit""" ... 

The following acid-catalyzed cyclizations leading to steroid hormone precursors exemplify some important facts an acetylenic bond is less nucleophilic than an olelinic bond acetylenic bonds tend to form cyclopentane rather than cyclohexane derivatives, if there is a choice in proton-catalyzed olefin cyclizations the thermodynamically most stable Irons connection of cyclohexane rings is obtained selectively electroneutral nucleophilic agents such as ethylene carbonate can be used to terminate the cationic cyclization process forming stable enol derivatives which can be hydrolyzed to carbonyl compounds without this nucleophile and with trifluoroacetic acid the corresponding enol ester may be obtained (M.B. Gravestock, 1978, A,B P.E. Peterson, 1969). 

Elemental sulfur reacts with alkanes such as cyclopentane in the presence of superacidic trifluoromethanesulfonic acid to give symmetrical dialkyl sulfides in moderate yields. 

The term naphthenic acid, as commonly used in the petroleum industry, refers collectively to all of the carboxyUc acids present in cmde oil. Naphthenic acids [1338-24-5] are classified as monobasic carboxyUc acids of the general formula RCOOH, where R represents the naphthene moiety consisting of cyclopentane and cyclohexane derivatives. Naphthenic acids are composed predorninandy of aLkyl-substituted cycloaUphatic carboxyUc acids, with smaller amounts of acycHc aUphatic (paraffinic or fatty) acids. Aromatic, olefinic, hydroxy, and dibasic acids are considered to be minor components. Commercial naphthenic acids also contain varying amounts of unsaponifiable hydrocarbons, phenoHc compounds, sulfur compounds, and water. The complex mixture of acids is derived from straight-mn distillates of petroleum, mosdy from kerosene and diesel fractions (see Petroleum). 

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). 

Several procedures for making glutaric acid have been described in Organic Syntheses starting with trimethylene cyanide (28), methylene bis (malonic acid) (29), y-butyrolactone (30), and dihydropyran (31). Oxidation of cyclopentane with air at 140° and 2.7 MPa (400 psi) gives cyclopentanone and cyclopentanol, which when oxidized further with nitric acid at 65—75° gives mixtures of glutaric acid and succinic acid (32). 

Camphoric acid (l,2,2-trimethyl-cyclopentan-lr,3c-dicarboxylic acid)... 

At low temperature a 1 1 adduct of thioacetic acid and an enamine could be prepared (709). The previously described reaction of aminomethylene ketones with hydrogen peroxide was extended to bisaminomethylene compounds. However, acylated cyclohexenamines led to cyclopentane-carboxamides (770), Trichloromethyl adducts of enamines and the rearranged amine derivatives were described in a further study (777). 

In addition to unsaturated fatty acids, several other modified fatty acids are found in nature. Microorganisms, for example, often contain branched-chain fatty acids, such as tuberculostearic acid (Figure 8.2). When these fatty acids are incorporated in membranes, the methyl group constitutes a local structural perturbation in a manner similar to the double bonds in unsaturated fatty acids (see Chapter 9). Some bacteria also synthesize fatty acids containing cyclic structures such as cyclopropane, cyclopropene, and even cyclopentane rings. 

In fact, esters of amino alcohols and 2,2-disubstituted plii iiylacetic acids show useful antitussive activity the mecha-lM iii of action may include bronchiodilation. Double alkylation III the anion of phenylacetonitrile with 1,4-dibromobutane gives llit i cyclopentane-substituted derivative (33). Saponification... 

A novel ring closure was discovered by Stork (6) in which the pyrrolidine enamine of a cycloalkanone reacts with acrolein. The scheme illustrates the sequence in the case of 1-pyrrolidino-l-cyclohexene, and the cyclopentane compound was found to undergo the reaction analogously. The procedure details the preparation of the bicyclo adduct and its cleavage to 4-cyclooctenecarboxylic acid. 

Fig. 7-6). Two unichiral amides which have been known capable of this reaction are 1-phenylethylamine [15] and l-(l-naphthyl)ethylamine [16]. Marfey s reagent [N-a-(2,4-dinitro-5-fluorophenyl)-L-alaninamide] was introduced as a reagent to deriva-tize amino acids with cyclopentane, tetrahydroisoquinoline or tetraline structures [17]. Simple chiral alcohols such as 2-octanol can also be used to derivatize acids such as 2-chloro-3-phenylmethoxypropionic acid [18]. 

Oxygen compounds in crude oils are more complex than the sulfur types. However, their presence in petroleum streams is not poisonous to processing catalysts. Many of the oxygen compounds found in crude oils are weakly acidic. They are carboxylic acids, cresylic acid, phenol, and naphthenic acid. Naphthenic acids are mainly cyclopentane and cyclohexane derivatives having a carboxyalkyl side chain. 

PGF2a- The cyclopentane ring of the Corey lactone (9) is the host of four contiguous stereogenic centers. Retrosynthetic simplification of 9 provides 10, a construct which is more complex than 9 Nevertheless, intermediate 10 possesses structural features that satisfy the requirement for the iodolactonization transform. The iodolactone in 10 constitutes the retron for the iodolactonization transform.11 Cleavage of the indicated bonds in 10 sacrifices two of the five stereocenters and provides unsaturated carboxylic acid... 

Stork s elegant use of a protected cyanohydrin function in the synthesis of PGF2a (2) is also noteworthy. The electron-withdrawing cyano substituent in intermediate 21 (Scheme 7) confers nucleophilic potential to C-9 and permits the construction of the saturated cyclopentane nucleus of PGF2a (2) through intramolecular alkylation. In addition, the C-9 cyanohydrin function contained within 40 is stable under the acidic conditions used to accomplish the conversion of 39 to 40 (see Scheme 7), and it thus provides suitable protection for an otherwise labile /J-hydroxy ketone. 

Furthermore, intramolecular cyclization of acyclic chiral imines, in which the imine and the enone groups are separated by alkyl chains, yield optically active cyclohexane and cyclopentane derivatives. /ra .v-l,2-Disubstitutcd carbocyclic compounds are exclusively or predominantly formed with diastereomeric ratios in the range 80 20 100 0, strongly dependent on the conditions used to induce cyclization, i.e. heat, pressure or Lewis acid (MgBr2) catalysis227. 

An allylsilane-generating CM using catalyst C between the sensitive /J-lactone 319 and allyltrimethylsilane served to introduce the allylsilane moiety in intermediate 320 as an inconsequential mixture (ca. 3 1) of (EIZ)-isomers in 80% yield. Cyclization of /J-lactone 320 with TiCl4 smoothly delivered cyclopentane 321 with inversion at the /J-carbon. Acid 321 was converted to key aldehyde 322 in three steps. The convergent fragment coupling was performed by a uniquely... 

Cyclopentane, methyl-, 55, 62 Cyclopentanol, p-toluenesulfonate [Ben-zenesulfonic acid, 4-methyl-, cyclo-... 

Sodium metaperiodate [Metapenodic acid, sodium salt], 55, 68 Sodium, toluene dispersion of, 55, 65 Spiro[cyclopentane-l,l -indene], 55, 94 CE) Stilbene [Benzene, 1,1 (1,2-ethenediyl)-bis-], 55,115... 

Which of the following mixtures would you expect to show a positive deviation, negative deviation, or no deviation (that is, form an ideal solution) from Raoult s law Explain your conclusion, (a) HBr and H,0 (b) formic acid, HCOOH, and benzene (c) cyclopentane, C5H10, and cyclohexane, QHi2. 

In the electrolysis of quinuchdine-2-carboxylic acid decarboxylation occurs without rearrangement (Table 12, No. 5). Stereospecifically substituted cyclopentanes, that... 

Epoxidation of substituted spiro[cyclopentane-l,9 -fluorene]-2-enes 68 with a peroxidic reagent was studied [98], The spiro olefins react with m-chloroperbenzoic acid (mCPBA) in chloroform at 3 °C to give a mixture of the epoxides. In all cases (2-nitro (68b), 4-nitro (68c), 2-fluoro (68d) and 2-methoxyl (68e) groups), the iyn-epoxides, i.e., the syn addition of the peroxidic reagent with respect to the substituent, is favored. For example, for 6 nsyn anti = 63 31 for 68c syn anti = 65 35. Thus, a similar bias is observed in both the reduction of the carbonyl derivatives of 30 and the epoxidation of the derivatives of 68. 

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