Phenyl-ethyl-carbinol

The same method may be used without modification for preparing phenyl ethyl carbinol using a corresponding quantity of ethyl iodide. See Appendix, p. 307. 

There exist three isomers of phenyl-propyl alcohol, all of which have been prepared and described, and, although not yet introduced into commerce, may eventually be so. These are as follows Benzyl-methyl-carbinol, CgHj. CHj. CH(OH)CHg, boiling at 215° phenyl-ethyl-carbinol, CgHg. CH(OH)CH2. CHg, boiling at 221° and benzyl-dimethyl-carbinol, C Hg. C(OH)(CHg)2, melting at 21° and boiling at 225°. 

The first example of a [l,2]-Wittig-type rearrangement was reported in 1924 by Schorigin, and was discovered during studies on the reactivity of benzyl ethers towards alkali metals. Schorigin found that heating a mixture of benzyl ethyl ether (4) with metallic sodium to 130-210 °C generated a small amount (13%) of phenyl ethyl carbinol (5). 

Percentage Reduced to Carbinol 35.7, as phenyl methyl carbinol 26, as phenyl ethyl carbinol 43, as benzyl isopropyl carbinol 41, as phenyl n-propyl carbinol... 

Phenyl-ethyl alcohol, or benzyl carbinol, has been known for many years, but its powerful rose odour has been entirely overlooked, its discovery having been made by an ordinary research chemist and not a perfumery expert. Its preparation was described in the Berichte (9, 373) in 1876, but the product there noted was evidently impure, as its boiling-point is recorded as 212°. Commercial specimens vary greatly in both their odour and their keeping properties, some samples deteriorating in odour very rapidly. It is, therefore, very important to -obtain it in a state of the highest purity. It has the following characters —... 

Trade Names. Phenoxanol (IFF), Phenylhexanol (Firmenich), Mefrosol (Quest). l-Phenyl-3-methyl-3-pentanol [10415-87-9], phenethyl methyl ethyl carbinol... 

Phenyl methyl carbinol Acetophenone or ethyl- R A. K salt, H20 — 124(W) 138... 

SYNS 3-PENTANOL,3-METHYL-l-PHENYL- PHENETHYLMETHYLETHYLCARBINOL PHENYLETHYL METHYX ETHYL CARBINOL... 

Methyl-l-phenyl-3-pentanol [10415-87-9], phenethyl methyl ethyl carbinol... 

D isomer. See Carbetamide Phenylethyl carbinol. See Hydrocinnamic alcohol 1-Phenyl-1-propanol Phenylethyl cinnamate 2-Phenylethyl cinnamate. See Phenethyl cinnamate Phenyl ethyl cyclohexyl ether. See Cyclohexyl phenethyl ether... 

Phenylethyl methyl ethyl carbinol. See 1-Phenyl-3-methyl-3-pentanol Phenylethyl methyl ethyl carbinol acetate. See Phenethyl methyl ethyl carbinyl acetate P-Phenylethyl methyl ketone. See Benzyl acetone... 

Camphorquinone, 77 Carbazole reaction, 9 Carbinol, o-aminophenyl methyl, 55 benzyl isopropyl, 54 phenyl ethyl, 54 phenyl methyl, 44, 54 phenyl ra-propyl, 54 Carone, 75 Carveol, dihydro-, 73 Carvone, 71, 72 Catechol, 39, 42 4-chloro-, 42... 

Analogously, aryl 2-chloro[l- C]ethyl carbinols 49 (Figure 11.19) are accessible by CBS- or IpCaBCl-mediated reduction of aryl (2-chloro)ethyl[carbonyl- C]ketones e.e.s are usually > 90%. Replacement of chlorine with iodine followed by treatment with a primary amine converted haloalcohol 49 (Ar = thien-2-yl) into the 3-aryl-3-hydroxy[3- C]propy-lamine derivative 52, which served as the penultimate intermediate in the preparation of the carbon- 14-labeled CNS-active drug duloxetine" . Furthermore, Mitsunobu reaction (DEAD or ADDP, PhsP or BU3P) on 49 (Ar = phenyl) in the presence of various phenols provided the respective (R)- j8-haloethers with inversion of the configuration at the stereogenic center. This route was followed for the synthesis of [ CJatomoxetine and one of its metabolites. ... 

Triphenyl-carbinol, (C6H5)3COHy from Ethyl Benzoate and Phenyl Magnesium Bromide. (Grignard Reaction 6 (a).)... 

Compared with asymmetric ethylation, reports on asymmetric phenylation are limited. We disclosed the enantioselective phenylation using diphenylzinc prepared in situ from phenyl Grignard reagent and zinc chloride. This method needs a stoichiometric amount of chiral amino alcohol DBNE 18 but good ee of 82% was achieved [32], A catalytic phenylation was examined using planar chiral compound 1 based on ferrocene, and chiral diaryl carbinols of moderate ee were provided from diphenylzinc and 4-chlorobenzaldehyde (Scheme 10) [33]. A catalytic and highly enantioselective phenylation was realized by binaphthyl-based chiral catalyst 23. In this reaction, the addition of 2 equivalents of diethyl-zinc against catalyst increases the yield and ee [34]. Recently, chiral amino alcohol DPMPM 9 was also reported to be an efficient catalyst for asymmetric phenylation [35]. 

When the carbinol substituents (R) were the bulky 5-ler -butyl-2-(n-octyloxy)phenyl group, optimum enantioselectivities were achieved with the catalytic use of the corresponding Cu(II) complex (2) in both enantiomeric forms. Specific applications of the Aratani catalysts have included the synthesis of chrysanthemic acid esters (Eq. 5.6) and a precursor to permethrinic acid, both potent units of pyrethroid insecticides, and for the commercial preparation of ethyl (S)-2,2-dimethylcyclopropanecarboxylate (Eq. 5.2), which is used for constructing cilastatin. Several other uses of these catalysts and their derivatives for cyclopropanation reactions have been reported albeit, in most cases, with only moderate enantioselectivities [26-29],... 

We have systematically examined the facility with which DTPP promotes the cyclodehydration of simple diols to cyclic ethers 1,3-propanediol (1) - oxetane (2) (2-5%) 1,4-butanediol (3) te-trahydrofuran (4) (85%) 1,5-pentanediol (5) - tetrahydropyran (6) (72%) 1,6-hexanediol (7) - oxepane (8) (55-68%). Increased alkyl substitution at the carbinol carbon s gnificantly diminishes the facility for cyclic ether formation. For example, a mixture of meso- and d, 1 —2, 6-heptanediol gave only 6-10% of the cis- and trans-2,6-dimethyltetrahydropyrans when treated with DTPP. While diol 1 resists cyclodehydration with DTPP to oxetane, some 2,2-di-substituted 1,3-propanediols are readily converted to the appropriate oxetanes [e.g., 2-ethyl-2-phenyl-l,3-propanediol -> 3-ethyl-3-phenyloxetane (78%)]. 

Chloromercuri methyl)-ethyl phenyl carbinol, 196. l-Chloromercuriinethyl-6-methyl-l 2-dihydrobenzofurane, 216. 

When ethyl iodide is reacted with benzaldehyde in ether, the expected ethyl phenyl carbinol is isolated in a lower yield (25%) than the by-products benzyl alcohol (35%) and ethyl phenyl ketone (35%). In THF, benzyl alcohol is the major product (50%) with the carbinol isolated in only a 10% yield. With ethyl bromide in ether, the major product is the ketone (55%). In THF, the carbinol is the predominant product, being isolated in a 70% yield [2],... 

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