Alicyclic alcohols

The applicability to alicyclic alcohols may be limited, since the mechanistic course via a cyclic transition state requires a suitably positioned hydrogen in order to afford the desired product. 

Unavailable because experimental methods for estimation of this parameter for alicyclic alcohols are lacking in the documented literature... 

Unavailable because experimental methods for estimation of this parameter for unsaturated alicyclic alcohols are lacking in the documented literature. However, its high solubility in water suggests its adsorption to soil will be nominal (Lyman et al., 1982). 

Some alicyclic alcohols are important as synthetic sandalwood fragrances. A few alicyclic aldehydes are valuable perfume materials and are obtained by Diels Alder reactions using terpenes and acrolein. Esters derived from hydrogenated aromatic compounds, such as /cr/-butylcyclohexyl and decahydro-/3-naphthyl acetates, are also used in large amounts as fragrance materials. 

The hydroxyl group of a primary, secondary, or tertiary acyclic or alicyclic alcohol may be protected by conversion into (a) an ether, (b) a silyl ether, or (c) an ester. The most important method for the protection of a 1,2- or 1,3-diol is conversion into (d) a cyclic acetal. 

Esterification with alicyclic alcohols proceeds best when the alcohol is saturated with hydrogen chloride and treated with an excess of the carboxylic acid (the Fischer-Speier method) a very impure ester results if sulphuric acid is used as the catalyst. 

This procedure has been used successfully for conversion of various aliphatic and alicyclic alcohols to the corresponding iodides. Yields of iodides from 1-propanol, 2-methyl-1-propanol, 2-methyl-2-propanol, and cyclohexanol were 95, 88, 90, and 79.5%, respectively. 

Ipatieff et al. studied the hydrogenolysis of various aliphatic and alicyclic alcohols in the presence of a Ni-Al203 catalyst at 210-225°C and 10 MPa H2.304 3,3-Dimethyl-1-butanol yielded a mixture of 2,2-dimethylbutane and neopentane as the main products, while in the presence of either Ni-kieselguhr or Raney Ni, neopentane was formed in > 95% yields (eq. 13.161). 

Methyl ethers of aliphatic and alicyclic alcohols are also cleaved with Lewis acids and in Scheme 1,4 we showed a methyl ether deprotection in a synthesis... 

In the case of an intramolecular ene reaction, a ring is formed or broken. For example, alicyclic alcohols 8.40 and 8.42 were obtained from linalool (8.39) and dehydrolinalool (8.41), respectively. 

Substitution of H in an alkane by an OH group causes down field shifts of 35-52 ppm for C-1,5-12 ppm forC-2, and upfield shift of about 0-6 ppm for C-3. Shifts for several acyclic and alicyclic alcohols are given in Table 4.11. 

Symmetrical secondary or tertiary alicyclic alcohols are readily dehydrated to only one olefin in each case. Examples include cyclopentene from cyclopentanol and phosphoric acid, cyclohexene from cyclohex-anol over alumina," cycloheptene from cycloheptanol and /6-naphthalene-... 

Esters react with certain di-Grignard reagents to give tertiary alicyclic alcohols in 20-67% yields/ ... 

Under these conditions saturated primary and secondary aliphatic and alicyclic alcohols are recovered essentially unchanged. This selectivity was illustrated impressively by conversion of Z-3-methyl-2-pentene-l,5-diol (4) by treatment with the complex (I) in methylene chloride briefly at - 20° and then at 0° for 1 hr. into the allylic monochloride (5), isolated in 87% yield. 

Stereoselective, fused-ring alicyclic alcohols are prepared in 10-77% yields from haloalkylalicyclic ketones. The cyclic ketones range from C5 to C7, with iodo-, bromopropyl-, or bromobutyl-substitution in the 2-position. Bicyclo[3.3.0]octan-l-ols, [4.3.0]nona-l-ols, [4.4.0]deca-l-ols, and [5.3.0]decan-l-ols are also prepared. When the side chain is extended to iodopentyl, no bicyclic products are obtained. Usually the ring fusion is cisoid [53],... 

A broad variety of substrates were efficiently glycosylated by glycosidases such as aliphatic and alicyclic alcohols [14], phenols, oximes, steroids and terpenes [15], amino acids [16], alkaloids [17] and many other substances. 

There are a number of classifications analogous to those of hydrocarbons (1) paraffinic or simple alcohols, whose formula may be represented as CnHa+1 (2) olefinic or fatty alcohols that contain one or more double bonds (3) alicyclic alcohols, closed-ring structures that may or may not contain a double bond, e.g., cyclohexanol (4) aromatic alcohols in which the hydroxyl group is attached to a benzene... 

Doddrell et al. (80, 66) have examined the angular dependence of V(C-C) in a number of aliphatic and alicyclic alcohols. In contrast to the carboxylic acids, 37(C-C) is observed to be a maximum, 5-4 Hz, for a dihedral angle near 0°. For the trans arrangement, — 180°, 3/(C-C) is 3-2 Hz. At dihedral angles of 90 and 270°, 3/(C-C) is less than 0-4 Hz. Observed 3/(C-C) values for the alcohols and carboxylic acids (66, 80, 52) have been compared with values calculated (INDO-FPT) for the model compounds butane, 2-butanol, and butanoic acid. The calculated coupling constants are given in Table V. (80) Also, experimental and calculated 3J(C-C) values for the carboxylic acids are shown in Fig. 2. The calculations, which assumed only the Fermi contact... 

Gracza, L. and Ruff, P. (1986) Uber die hoheren Alkohole von Piperis methystici rhizoma Aliphatic and alicyclic alcohols of Piperis methystici rhizoma. Archive der Pharmazie, 319, TTS-All. 

Substitution of H in an alkane by an OH group moves the signal to the left by 35-52 ppm for C-l, 5-12 ppm for C-2, and to the right by about 0-6 ppm for C-3. Shifts for several acyclic and alicyclic alcohols are given in Table 5.11. Acetylation provides a useful diagnostic test for an alcohol The C-l absorption moves to the left by about 2.5-4.5 ppm, and the C-2 absorption moves to the right by a similar amount a 1,3-diaxial interaction may cause a slight ( 1 ppm) shift to the left of C-3. 

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