Alcohols, general conversion

This procedure illustrates a general method for the preparation of 2-hydroxybicyclo[3.2.0]heptanes by copper(I)-catalyzed photobicyclization of 3-hydroxy-1,6-heptadienes, and a general route to the requisite dienes from allyl alcohols by conversion to 4-pentenals and treatment of the latter with vinyl Grignard reagents. 

Kinetic resolution of chiral aUylic alcohols.7 Partial (at least 60% conversion) asymmetric epoxidation can be used for kinetic resolution of chiral allylic alcohols, particularly of secondary allylic alcohols in which chirality resides at the carbinol carbon such as 1, drawn in accordance with the usual enantioface selection rule (Scheme I). (S)-l undergoes asymmetric epoxidation with L-diisopropyl tartrate (DIPT) 104 times faster than (R)-l. The optical purity of the recovered allylic alcohol after kinetic resolution carried to 60% conversion is often > 90%. In theory, any degree of enantiomeric purity is attainable by use of higher conversions. Secondary allylic alcohols generally conform to the reactivity pattern of 1 the (Z)-allylic alcohols are less satisfactory substrates, particularly those substituted at the /1-vinyl position by a bulky substituent. 

While PEGS can themselves serve as phase-transfer catalysts [86], onium salts are generally more effective as catalysts. Using the chemistry shown in Eq. 18, a methoxy-PEG5ooo derivative 47 was first treated with the Cs salt of 4-hydroxybenzyl alcohol to form the alcohol 48. Conversion of the alcohol to the bromide followed by reaction with tributylamine produced a quaternary ammonium salt 49. This salt was as active as low molecular weight salts in typical phase-transfer catalyzed reactions like those of alkyl halides with KI, KCN, phenol, and pyrrole [88]. Yields were often in the >90% range. Reactions were typically carried out at <40 °C and could be performed either with water or without solvent. Control experiments showed that the ammonium group of 49 was necessary as the simple alcoholic PEG derivative 48 was much less effec-... 

We ve already seen one general reaction of alcohols—their conversion to alkyl halides (Section 12.3). Tertiary alcohols react with HGl and HBr by an SnI mechanism through a carhocation intermediate. Primary and secondary alcohols react with SOCI2 and PBra by an Sn2 mechanism through backside attack on a chlorosulfite or dibromophosphite intermediate. 

The conversion of primary alcohols and aldehydes into carboxylic acids is generally possible with all strong oxidants. Silver(II) oxide in THF/water is particularly useful as a neutral oxidant (E.J. Corey, 1968 A). The direct conversion of primary alcohols into carboxylic esters is achieved with MnOj in the presence of hydrogen cyanide and alcohols (E.J. Corey, 1968 A,D). The remarkably smooth oxidation of ethers to esters by ruthenium tetroxide has been employed quite often (D.G. Lee, 1973). Dibutyl ether affords butyl butanoate, and tetra-hydrofuran yields butyrolactone almost quantitatively. More complex educts also give acceptable yields (M.E. Wolff, 1963). 

Secondary alcohols (C q—for surfactant iatermediates are produced by hydrolysis of secondary alkyl borate or boroxiae esters formed when paraffin hydrocarbons are air-oxidized ia the presence of boric acid [10043-35-3] (19,20). Union Carbide Corporation operated a plant ia the United States from 1964 until 1977. A plant built by Nippon Shokubai (Japan Catalytic Chemical) ia 1972 ia Kawasaki, Japan was expanded to 30,000 t/yr capacity ia 1980 (20). The process has been operated iadustriaHy ia the USSR siace 1959 (21). Also, predominantiy primary alcohols are produced ia large volumes ia the USSR by reduction of fatty acids, or their methyl esters, from permanganate-catalyzed air oxidation of paraffin hydrocarbons (22). The paraffin oxidation is carried out ia the temperature range 150—180°C at a paraffin conversion generally below 20% to a mixture of trialkyl borate, (RO)2B, and trialkyl boroxiae, (ROBO). Unconverted paraffin is separated from the product mixture by flash distillation. After hydrolysis of residual borate esters, the boric acid is recovered for recycle and the alcohols are purified by washing and distillation (19,20). 

Resorcinol or hydroquinone production from m- or -diisopropylben2ene [100-18-5] is realized in two steps, air oxidation and cleavage, as shown above. Air oxidation to obtain the dihydroperoxide (DHP) coproduces the corresponding hydroxyhydroperoxide (HHP) and dicarbinol (DC). This formation of alcohols is inherent to the autooxidation process itself and the amounts increase as DIPB conversion increases. Generally, this oxidation is carried out at 90—100°C in aqueous sodium hydroxide with eventually, in addition, organic bases (pyridine, imidazole, citrate, or oxalate) (8) as well as cobalt or copper salts (9). 

Sol—Gel Technology. The sol—gel process involves conversion of a metal alkoxide or mixture of metal alkoxides, dissolved in an organic solvent (generally the patent alcohol) into a hydroxooxyalkoxide sol, followed by gelation and sintering to give the desired ceramic material. 

Oxidation of Straight-Chain Alcohols. Two methods have been developed. One uses an air oxidation catalyzed by a metal, eg, copper, platinum, etc, whereas the other is a caustic oxidation. Generally, however, fatty alcohols are priced higher on the world market than their corresponding fatty acids and, consequently, these conversions are uneconomical. 

Completion of Esterification. Because the esterification of an alcohol and an organic acid involves a reversible equiUbrium, these reactions usually do not go to completion. Conversions approaching 100% can often be achieved by removing one of the products formed, either the ester or the water, provided the esterification reaction is equiUbrium limited and not rate limited. A variety of distillation methods can be appHed to afford ester and water product removal from the esterification reaction (see Distillation). Other methods such as reactive extraction and reverse osmosis can be used to remove the esterification products to maximize the reaction conversion (38). In general, esterifications are divided into three broad classes, depending on the volatility of the esters ... 

Catalytic esterification of alcohols and acids in the vapor phase has received attention because the conversions obtained are generally higher than in the corresponding liquid-phase reactions (7). 

Aluminum oxide has been the most widely used catalyst (151). At 320°C and 1.01—1.42 MPa, 50—66% conversion to alcohol based on the ether was obtained. Ethanol produced by the direct hydration of ether generally has a foul odor owing to the presence of polymeric hydrocarbon material, which can be removed by washing the aqueous alcohol with ether (152). 

The oxidation of alkenes and allylic alcohols with the urea-EL202 adduct (UELP) as oxidant and methyltrioxorhenium (MTO) dissolved in [EMIM][BF4] as catalyst was described by Abu-Omar et al. [61]. Both MTO and UHP dissolved completely in the ionic liquid. Conversions were found to depend on the reactivity of the olefin and the solubility of the olefinic substrate in the reactive layer. In general, the reaction rates of the epoxidation reaction were found to be comparable to those obtained in classical solvents. 

Conversion of Acid Chlorides into Alcohols Reduction Acid chlorides are reduced by LiAJH4 to yield primary alcohols. The reaction is of little practical value, however, because the parent carboxylic acids are generally more readily available and can themselves be reduced by L1AIH4 to yield alcohols. Reduction occurs via a typical nucleophilic acyl substitution mechanism in which a hydride ion (H -) adds to the carbonyl group, yielding a tetrahedral intermediate that expels Cl-. The net effect is a substitution of -Cl by -H to yield an aldehyde, which is then immediately reduced by UAIH4 in a second step to yield the primary alcohol. 

Notable examples of general synthetic procedures in Volume 47 include the synthesis of aromatic aldehydes (from dichloro-methyl methyl ether), aliphatic aldehydes (from alkyl halides and trimethylamine oxide and by oxidation of alcohols using dimethyl sulfoxide, dicyclohexylcarbodiimide, and pyridinum trifluoro-acetate the latter method is particularly useful since the conditions are so mild), carbethoxycycloalkanones (from sodium hydride, diethyl carbonate, and the cycloalkanone), m-dialkylbenzenes (from the />-isomer by isomerization with hydrogen fluoride and boron trifluoride), and the deamination of amines (by conversion to the nitrosoamide and thermolysis to the ester). Other general methods are represented by the synthesis of 1 J-difluoroolefins (from sodium chlorodifluoroacetate, triphenyl phosphine, and an aldehyde or ketone), the nitration of aromatic rings (with ni-tronium tetrafluoroborate), the reductive methylation of aromatic nitro compounds (with formaldehyde and hydrogen), the synthesis of dialkyl ketones (from carboxylic acids and iron powder), and the preparation of 1-substituted cyclopropanols (from the condensation of a 1,3-dichloro-2-propanol derivative and ethyl-... 

In a more general sense, this reduction method provides a convenient pathway for converting an aromatic carboxyl group to a methyl group (see Table I).7 Previously, this transformation has been achieved by reduction of the acid to the alcohol with lithium aluminum hydride, conversion of the alcohol to the tosylate, and a second reduction either with lithium aluminum hydride [Aluminate(l —), tetrahydro, lithium,... 

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