Neopentyl alcohol

With the exception of neopentyl alcohol (mp 53°C), the amyl alcohols are clear, colorless Hquids under atmospheric conditions, with characteristic, slightly pungent and penetrating odors. They have relatively higher boiling poiats than ketonic or hydrocarbon counterparts and are considered iatermediate boiling solvents for coating systems (Table 1) (1—16). 

CAS Registry Number common name [71-41-0] -amyl alcohol [6032-29-7] j -amyl alcohol [584-02-1] [137-32-6] [123-51-3] iso amyl alcohol [75-85-4] / fZ-amyl alcohol [598-75-4] [75-84-3] neopentyl alcohol... 

Amination. Amyl alcohols can react with ammonia or alkylamines to form primary, secondary, or tertiary-substituted amines. Eor example, 3-methyl-butylamine [107-85-7] is produced by reductive ammonolysis of 3-methyl-1-butanol over a Ni catalyst at 150°C (59). Some diisoamyl- and triisoamyl amines are also formed in this reaction. Good selectivities (88%) of neopentyl amine [5813-64-9] are similarly produced by reductive ammonolysis of neopentyl alcohol (60). 

Condensation. The neopentyl trimethylolpropane carbonate [65332-76-5] formed from condensation of the trischloroformate of trimethylolpropane and neopentyl alcohol, is a clear yellow oil, useful as lubricant (77). 

Neopentyl alcohol is useful for preparation of masked polyol siUcate esters, capable of releasing the polyol under moisture conditions, in moisture-curable one-component Hquid polyurethane compositions (90). 

Reduction of Acids. Patents claim catalysts for the hydrogenation of neoacids in the vapor-phase to the neoalcohols in good yields. For example, neopentyl alcohol has been prepared by passing pivaUc acid (obtained by the Koch reaction of isobutylene) over a Cu0/Zn0/Al202 catalyst at... 

AH eight amyl alcohol isomers are available from fine chemical supply firms in the United States. Five of them, 1-pentanol, 2-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, and 2-methyl-2-butanol (/ fZ-amyl alcohols) are available in bulk in the United States in Europe all but neopentyl alcohol are produced (148,149). 

Esters derived from the primary alcohols are the most stable and those derived from the tertiary alcohols are the least stable. The decomposition temperature is lower in polar solvents, eg, dimethyl sulfoxide (DMSO), with decomposition occurring at 20°C for esters derived from the tertiary alcohols (38). Esters of benzyl xanthic acid yield stilbenes on heating, and those from neopentyl alcohols thermally rearrange to the corresponding dithiol esters (39,40). The dialkyl xanthate esters catalytically rearrange to the dithiol esters with conventional Lewis acids or trifluoroacetic acid (41,42). The esters are also catalytically rearranged to the dithiolesters by pyridine Ai-oxide catalysts (43) ... 

These reactions are also quite sensitive to steric factors, as shown by the fact that if 1-butene reacts with di(j iAisoamyl)borane the initially formed product is 99% substituted in the 1-position (15) compared to 93% for unsubstituted borane. Similarly, the product obtained from hydroformylation of isobutylene is about 97% isoamyl alcohol and 3% neopentyl alcohol (17). Reaction of isobutylene with aluminum hydride yields only triisobutjlaluininum. 

Pure neopentyl alcohol melts at about 55°. From time to time it will be necessary to circulate hot water through the takeoff condenser in order to facilitate removal of the alcohol. 

Neopentyl alcohol has been made by lithium aluminum hydride reduction of trimethylacetic acid and by treating ferf-butyl-magnesium chloride with methyl formate. ... 

The preparation of neopentyl alcohol from diisobutylene herein described represents an example of acid-catalyzed addition of hydrogen peroxide to a branched olefin, followed by an acid-catalyzed rearrangement of the tertiary hydroperoxide formed. In addition to neopentyl alcohol, there are formed acetone and also small amounts of methanol and methyl neopentyl ketone by an alternative rearrangement of the hydroperoxide. 

Much information on proton transfers has been obtained by NMR chemical exchange studies. An example is the proton exchange between neopentyl alcohol and acetic acid in acetic acid as the solvent. The reaction is... 

The neopentyl alcohol, prepared from the sulfonyl chloride (Pyr, 95% yield), is cleaved nucleophilically under rather severe conditions (Mc4N CP, DMF, 160°, 16 h, 100% yield). ... 

Neopentyl alcohol, 40, 76 Nickel catalyst for hydrogenation of resorcinol, 41, 56, 57 Nitramines from amines and acetone cyanohydrin nitrate, 43, 84 Nitration, of amines to nitramines by acetone cyanohydrin nitrate, 43, 83... 

Primary, secondary, and tertiary alcohols can be converted to any of the four halides by treatment with the appropriate NaX, KX, or NH4X in polyhydrogen fluoride-pyridine solution." This method is even successful for neopentyl halides. Another reagent that converts neopentyl alcohol to neopentyl chloride, in 95% yield, is PPh3-CCl3CN." ... 

The use of ethanol as an achiral auxiliary gave the adduct 53 with 55% ee, while neopentyl alcohol and methanol gave 96 and 87% ee, respectively. These results suggested that the achiral alcohol might exert a steric effect on the stereoselectivity. However, the increase in enantioselectivity from 55% to about 96% when 2,2,2-trifluoroethanol (TFE) was used instead of ethanol indicates a possible significant inductive effect also. Good enantioselectivities were also obtained with carboxylic acids and phenols. 

Further optimization of this reaction was carried out with TFE as an achiral adduct, since reaction with TFE is much faster than that with neopentyl alcohol. We found that dimethyl- and diethylzinc were equally effective, and the chiral zinc reagent could be prepared by mixing the chiral modifier, the achiral alcohol and dialkylzinc reagent in any order without affecting the conversion and selectivity of the reaction. However, the ratio of chiral to achiral modifier does affect the efficiency of the reaction. Less than 1 equiv of the chiral modifier lowered the ee %. For example with 0.8 equiv of 46 the enantiomeric excess of 53 was only 58.8% but with 1 equiv of 46 it was increased to 95.6%. Reaction temperature has a little effect on the enantiomeric excess. Reactions with zinc alkoxide derived for 46 and TFE gave 53 with 99.2% ee at 0°C and 94.0% ee at 40°C. 

Iridium-catalyzed transfer hydrogenation of aldehyde 73 in the presence of 1,1-dimethylallene promotes tert-prenylation [64] to form the secondary neopentyl alcohol 74. In this process, isopropanol serves as the hydrogen donor, and the isolated iridium complex prepared from [Ir(cod)Cl]2, allyl acetate, m-nitrobenzoic acid, and (S)-SEGPHOS is used as catalyst. Complete levels of catalyst-directed diastereoselectivity are observed. Exposure of neopentyl alcohol 74 to acetic anhydride followed by ozonolysis provides p-acetoxy aldehyde 75. Reductive coupling of aldehyde 75 with allyl acetate under transfer hydrogenation conditions results in the formation of homoallylic alcohol 76. As the stereochemistry of this addition is irrelevant, an achiral iridium complex derived from [Ir(cod)Cl]2, allyl acetate, m-nitrobenzoic acid, and BIPHEP was employed as catalyst (Scheme 5.9). 

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