Di-n-butyl acetal

Finally, reaction of primary, secondary, or tertiary alcohols 11 with Me3SiCl 14 in the presence of equivalent amounts of DMSO leads via 789 and 790 to the chloro compounds 791 [13]. n-Pentanol, benzyl alcohol, yS-phenylefhanol or tert-butanol are readily converted, after 10 min reaction time, into their chloro compounds, in 89-95% yield, yet cyclohexanol affords after reflux for 4 h cyclohexyl chloride 784 in only 6% yield [13] (Scheme 6.5). 1,4-Butanediol is cyclized to tetrahydrofuran (THF) [13a], whereas other primary alcohols are converted in 90-95% yield into formaldehyde acetals on heating with TCS 14 and DMSO in benzene [13b] (cf also the preparation of formaldehyde di(n-butyl)acetal 1280 in Section 8.2.1). 

DMSO or other sulfoxides react with trimethylchlorosilanes (TCS) 14 or trimefhylsilyl bromide 16, via 789, to give the Sila-Pummerer product 1275. Rearrangement of 789 and further reaction with TCS 14 affords, with elimination of HMDSO 7 and via 1276 and 1277, methanesulfenyl chloride 1278, which is also accessible by chlorination of dimethyldisulfide, by treatment of DMSO with Me2SiCl2 48, with formation of silicon oil 56, or by reaction of DMSO with oxalyl chloride, whereupon CO and CO2 is evolved (cf also Section 8.2.2). On heating equimolar amounts of primary or secondary alcohols with DMSO and TCS 14 in benzene, formaldehyde acetals are formed in 76-96% yield [67]. Thus reaction of -butanol with DMSO and TCS 14 gives, via intermediate 1275 and the mixed acetal 1279, formaldehyde di-n-butyl acetal 1280 in 81% yield and methyl mercaptan (Scheme 8.26). Most importantly, use of DMSO-Dg furnishes acetals in which the 0,0 -methylene group is deuter-ated. Benzyl alcohol, however, affords, under these reaction conditions, 93% diben-zyl ether 1817 and no acetal [67]. 

Di-n-butyl acetal (Acetaldehyde di-n-butyl acekd). Place 44 g,... 

GH3GH(OG4H9-n)2 -> GH2=GHOG4H9-n Vinyl ethers. Acetaldehyde di-n-butyl acetal passed at 280-300 /15 mm through a catalyst prepared by heating 14%-GuS04-on-carbon at 350 in a N2-stream for 0.5 hr. n-butyl vinyl ether. Y 85%. F. e. s. O. Wichterle, J. Stepek, and V.Brajko, Goll. 26, 1099 (1961). 

Successful results have been obtained (Renfrew and Chaney, 1946) with ethyl formate methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl and iso-amyl acetat ethyleneglycol diacetate ethyl monochloro- and trichloro-acetates methyl, n-propyl, n-octyl and n-dodecyl propionates ethyl butyrate n-butyl and n-amyl valerates ethyl laurate ethyl lactate ethyl acetoacetate diethyl carbonate dimethyl and diethyl oxalates diethyl malonate diethyl adipate di-n-butyl tartrate ethyl phenylacetate methyl and ethyl benzoates methyl and ethyl salicylates diethyl and di-n-butyl phthalates. The method fails for vinyl acetate, ieri.-butyl acetate, n-octadecyl propionate, ethyl and >i-butyl stearate, phenyl, benzyl- and guaicol-acetate, methyl and ethyl cinnamate, diethyl sulphate and ethyl p-aminobenzoate. 

Place a mixture of 125 ml. of A.R. benzene and 32-6 g. of di-n-butyl d-tartrate (1) in a 500 ml. tluee-uccked flask, equipped with a Hershberg stirrer (Section 11,7) and a thermometer. Stir the mixture rapidly and add 58 g. of lead tetra-acetate (Section II30,U) in small portions over a period of 20 minutes whilst maintaining the temperature below 30 by occasional cooling with cold water. Continue the stirring for a further 60 minutes. Separate the salts by suction filtration and wash with two... 

Uses Preparation of butyl esters (e.g., butyl acetate, di-n-butyl phthalate), glycol ethers solvent for waxes, resins, gums, and varnishes hydraulic fluid ingredient in perfumes and flavors additive in deicing fluids polishes, floor cleaners, stain removers, and in some gasolines (antiicing) diluent for brake fluids humectant for cellulose nitrate. 

Phenolsolvan A process for extracting phenols from coke-oven liquor and tar acids from tar by selective solvent extraction with di-isopropyl ether (formerly with n-butyl acetate). Developed by Luigi in 1937. 

Schugerl 115] has recently furnished a detail analysis of the reactive extraction of penicdlin-G and V and precursors like phenyl and phenoxy acetic acids. Thirty different amines have been studied for reactive extraction of penicillins 116] in various solvents such as butyl acetate, chloroform, di-isopropyl ether, kerosene, dioctyl ether, etc. Tertiary amines in n-butyl acetate were found to be advantageous because of their low reactivity with solvent but the distribution coefficients of their complexes are significantly lower than those of secondary amines. While using quaternary ammonium salts for ion-exchange extraction, re-extraction is difficult and very large amounts of anion (e.g.. Cl ) are needed to recover penicillins. The basic relationship for distribution coefficient and extraction kinetics have now been fairly developed for amine-penicillin systems. 

Hill and Carothers (4) investigated the acetal interchange reaction with di-n-butyl formal and glycols (Equation 4). When n was 3 or 4, cyclic formals were the principal products. Fentamethylene glycol (n = 5) gave a sirupy liquid polymer. The reaction with decamethylene gly-... 

Alkylation of levorphanol with A/,N-dimethylformamide di-f-butyl acetal gave the r-butyl ether,<50a) which was of reduced analgesic (MW, RTF) activity and receptor binding affinity and lacked antitussive actions. 

N,N-dimethylformamide-di-t-butyl acetal has also been used to prepare by the author (1) to prepare other Step 4 derivatives illustrated in Eq. 1 ... 

---