Ethers, neopentyl

Alkyl(C8-W) glyddylether, Alkyl(C12-14) glyddyl ether Neopentyl glycol diglycldyl ether... 

Cyclohexanedimethanol diglycidyl ether Neopentyl glycol diglycidyl ether... 

A solution of (CH3)3C-CH=C=CLi, obtained by addition at -60°C of 0.20 mol of tert.-butylallene (see Chapter VI, Exp. 2) to a solution of 0.25 mol of ethyllithium in about 200 ml of diethyl ether (see Chapter II, Exp. 1) was warmed to 25°C and held at this temperature for 15 min. Subsequently the solution was cooled to below 0°C and 50 ml of saturated NH,C1 solution were added dropwise with vigorous stirring, keeping the temperature below 2o C. The upper layer v as separated off and the aqueous layer was extracted twice with 25-ml portions of diethyl ether. The combined solutions were dried over a small amount of magnesium sulfate. Slow distillation through a 40-cm Widmer column gave neopentyl acetylene (b.p. 76°C/750 mmHg, 20... 

Neopentyl glycol, or 2,2-dimethyl-1,3-propanediol [126-30-7] (1) is a white crystalline soHd at room temperature, soluble ia water, alcohols, ethers, ketones, and toluene but relatively iasoluble ia alkanes (1). Two primary hydroxyl groups are provided by the 1,3-diol stmcture, making this glycol highly reactive as a chemical intermediate. The gem-A methy configuration is responsible for the exceptional hydrolytic, thermal, and uv stabiUty of neopentyl glycol derivatives. 

Aliphatic Glycidyl Ethers. Aliphatic epoxy resins have been synthesized by glycidylation of difunctional or polyfunctional polyols such as a 1,4-butanediol, 2,2-dimethyl-l,3-propanediol (neopentyl glycol), polypropylene glycols, glycerol, trimethylolpropane, and pentaerythritol. 

Methyl isobutyl ketone was reduced with (- )-menthol-LAH in ether to give the (+ )-(S)-carbinol (53) in low optical yield. Methyl neopentyl ketone was similarly reduced to the (-I- )-carbinol, although pinacolone was reduced to only racemic alcohol. Maximum stereoselectivity in the reduction of both ketones and alkenynols was obtained with a 2 1 (-)-menthol-LAH reagent. The observed low stereoselectivity was attributed mainly to insufficient interaction of the remote isopropyl substituent on the menthyl group with the substituents on... 

N-NeoDentyl)-4-DihexylaminoDvrldinium Bromide (3h) The neopentyl salt was prepared in a similar manner from neopentyl mesylate, but reaction was carried out neat at 130 for 72 hr. Higher temperatures cannot be used, due to decomposition of neopentyl mesylate. The crude product was dissolved in water, basifled to neutralize any pyridinium salt, and was washed with petroleum ether to remove amine and unreacted neopentyl mesylate. The aqueous phase was acidified with HBr, and extracted with methylene chloride, to afford crude salt. Recrystallization from 20 1 ethyl acetate/acetonitrile affords the product (mp = 169-170 ). 

METHYL sec-BUTYL ETHER METHYL tert-BUTYL ETHER METHYL ISOBUTYL ETHER ETHYL PROPYL ETHER ETHYLENE GLYCOL MONOPROPYL NEOPENTYL GLYCOL... 

The reduction of free acids to alcohols became practical only after the advent of complex hydrides. Lithium aluminum hydride reduces carboxylic acids to alcohols in ether solution very rapidly in an exothermic reaction. Because of the presence of acidic hydrogen in the carboxylic acid an additional equivalent of lithium aluminum hydride is needed beyond the amount required for the reduction. The stoichiometric ratio is 4 mol of the acid to 3 mol of lithium aluminum hydride (Equation 12, p. 18). Trimethylacetic add was reduced to neopentyl alcohol in 92% yield, and stearic acid to 1-octadecanol in 91% yield. Dicarboxylic sebacic acid was reduced to 1,10-decanedioI even if less than the needed amount of lithiiun aluminum hydride was used [968]. 

High yields (76-81%) of alcohols are also obtained by adding solutions of acyl chlorides in anhydrous dioxane or diethyl carbitol to a suspension of sodium borohydride in dioxane and brief heating of the mixtures on the steam bath [751], by stirring solutions of acyl chlorides in ether for 2-4 hours at room temperature with aluminum oxide (activity I) impregnated with a 50% aqueous solution of sodium borohydride (Alox) (yields 80-90%) [1014], by refluxing acyl chlorides with ether solutions of sodium trimethoxyborohydride [99], or by treatment of acyl chlorides in dichloromethane solutions with tetrabutylammonium borohydride at —78° [771]. A 94% yield of neopentyl alcohol was achieved by the reaction of trimethylacetyl chloride with tert-butylmagnesium chloride [324]. 

Reduction of esters by trichlorosilane in tetrahydrofuran in the presence of tert-butyl peroxide and under ultraviolet irradiation gave predominantly ethers from esters of primary alcohols, while esters of tertiary alcohols were cleaved to acids and hydrocarbons. Esters of secondary alcohols gave mixtures of ethers and acids/hydrocarbons in varying ratios. 1-Adamantyl trimethylacetate, for example, afforded 50-100% yields of mixtures containing 2-42% of 1-adamantyl neopentyl ether and 58-98% of adamantane and trimethylacetic acid [1033]. 

Since the (—)-sparteine reagent does not support the deprotonation of the neopentyl carbamate 29a (1.5 equivalents of s-BuLi, diethyl ether, 5 h at —78 °C) it becomes evident that fraw5-l,2-bis(dimethylamino)cyclohexane, which is available in both enantiomers , is the chiral additive of choice for bulky alkyl carbamates. (—)-a-Isosparteine (14), which holds two fraw5-fused piperidine rings, does not support the deprotonation of alkyl carbamates at alP . 

Birch reduction of the norgetrel intermediate 5 oil owed by hydrolysis of the enol ether gives the enone oxidation of the alcohol at 17 leads to dione 7. Fermentation of that intermediate in the presence of the mold PeniciIlium raistricky serves to introduce a hydroxyl group at the 15 position W. Acetal formation with neopentyl glycol affords the protected ketone which consists of a mixture of the A and A isomers (2 ) hindrance at position 17 ensures selective reaction of the 3 ketone. The... 

Phosphorus oxytrichloride. Benzene, Neopentyl glycol, Pyridine, Petroleum ether, Ammonium fluoride... 

Nitric acid. Sulfuric acid, N-Methylhydroxy acetamide Phosphorus oxytrichloride. Benzene, Neopentyl glycol. Pyridine, Petroleum ether. Ammonium fluoride Thiophosphorus trichloride. Benzene, Neopentyl glycol. Pyridine, Petroleum ether. Ammonium fluoride Nitric acid. Sulfuric acid. Glycerol, Magnesium sulfate Anhydrous hydrazine. Cyanogen bromide. Isopropyl alcohol. Sodium nitrite. Sodium bicarbonate. Copper nitrate trihydrate. Nitric acid. Diethyl ether... 

Is)max as shown in the diagrams of Figures 17-19 for the three prepolymer types discussed before (polyester, polyether, and polybutadiene). In the examples shown (Is)m ax is about equal for a poly ether (all polypropylene oxide) and a polyester (ca. 49 parts poly (neopentyl glycol) azelate, 35 parts poly (tripropylene glycol) azelate, 10 parts bis (2-ethyl-hexyl) azelate, 6 parts glycerolmonoricinoleate), and about 2 points higher for a polybutadiene binder (ca. 75 parts polybutadiene and 25 parts of a saturated hydrocarbon as plasticizer). 

Neopentyl sulfides have been prepared by alkylation of sodium sulfide with neopentyl tosylate in high-boiling polar solvents,4,5 or in low yields by reduction of alkyl 2,2-dimethylpropanethioate with the combination of lithium aluminum hydride and a large excess of boron trifluoride-etherate. ... 

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