Secondary alcohols chloride

It will also reduce acid chlorides, acid anhydrides and aldehydes to primary alcohols, ketones to secondary alcohols, and amides to the corresponding amines R-CONHi -> R CHiNH. Nitro-hydrocarbons if aromatic are... 

Acetyl chloride reacts vigorously with primary and secondary alcohols to yield esters it also reacts readily with any water present to form acetic acid ... 

Esters of nitro alcohols with primary alcohol groups can be prepared from the nitro alcohol and an organic acid, but nitro alcohols with secondary alcohol groups can be esterified only through the use of an acid chloride or anhydride. The nitrate esters of the nitro alcohols are obtained easily by treatment with nitric acid (qv). The resulting products have explosive properties but are not used commercially. 

Vinyllithium [917-57-7] can be formed direcdy from vinyl chloride by means of a lithium [7439-93-2] dispersion containing 2 wt % sodium [7440-23-5] at 0—10°C. This compound is a reactive intermediate for the formation of vinyl alcohols from aldehydes, vinyl ketones from organic acids, vinyl sulfides from disulfides, and monosubstituted alkenes from organic halides. It can also be converted to vinylcopper [37616-22-1] or divinylcopper lithium [22903-99-7], which can then be used to introduce a vinyl group stereoselectively into a variety of a, P-unsaturated systems (26), or simply add a vinyl group to other a, P-unsaturated compounds to give y, 5-unsaturated compounds. Vinyllithium reagents can also be converted to secondary alcohols with trialkylb o r ane s. 

The reaction of alcohols and acid chlorides in the presence of magnesium has been described (68). With primary and secondary alcohols the reaction is very smooth, and affords high and sometimes quantitative yields. Difficulty esteritiable hydroxy compounds such as tertiary alcohols and phenols can be esteritied by this method. The reaction carried out in ether or benzene is usually very vigorous with evolution of hydrogen. 

Picolyl ethers are prepared from their chlorides by a Williamson ether synthesis (68-83% yield). Some selectivity for primary versus secondary alcohols can be achieved (ratios = 4.3-4.6 1). They are cleaved electrolytically ( — 1.4 V, 0.5 M HBF4, MeOH, 70% yield). Since picolyl chlorides are unstable as the free base, they must be generated from the hydrochloride prior to use. These derivatives are relatively stable to acid (CF3CO2H, HF/anisole). Cleavage can also be effected by hydrogenolysis in acetic acid. ... 

Because tertiary alcohols are so readily converted to chlorides with hydrogen chloride, thionyl chloride is used mainly to prepare primary and secondary alkyl chlorides. Reactions with thionyl chloride are nonrrally carried out in the presence of potassium carbonate or the weak organic base pyridine. 

Isobutylene, Amberlyst H-15, hexane. Methylene chloride can also be used as solvent, and in this case a primary alcohol was selectively converted to the /-amyl ether in the presence of a secondary alcohol. ... 

Picolyl ethers are prepared from their chlorides by a Williamson ether synthesis (68-83% yield). Some selectivity for primary vs. secondary alcohols can be achieved (ratios = 4.3-4.6 1). Picolyl ethers are cleaved electrolytically ( —1.4 V,... 

Triphenylphosphine in refluxing carbon tetrachloride converts primary and secondary alcohols into the corresponding chlorides under very mild conditions (/) with inversion of configuration (2, J). A suggested route for the transformation is shown. 

Primary and secondary alcohols are best converted into alkyl halides by treatment with either thionyl chloride (SOCl2) or phosphorus tribromicle (PB ). These reactions, which normally take place readily under mild conditions, are less acidic and less likely to cause acid-catalyzed rearrangements than the HX method. 

Aldehydes and ketones are among the most important of ail compounds, both in biochemistry and in the chemical industry. AUdehydes are normally prepared in the laboratory by oxidation of primary alcohols or by partial reduction of esters. Ketones are similarly prepared by oxidation of secondary alcohols or by addition of diorganocopper reagents to acid chlorides. 

Impurities consist of unreacted material, including alkanes and internal or branched alkenes, and other material which can be detected in the neutral oil fraction of AOS. Examination of this fraction also indicates the amount of unhydrolyzed material (sulfonate esters and sultones) and byproducts (secondary alcohols, unsaturated and 2-chloro-y-sultones) in the sample. Salt calculations are made to determine inorganic sulfates and sodium chloride. Determinations for alkalinity, color, and water are required to meet product... 

In 2003, Sigman et al. reported the use of a chiral carbene ligand in conjunction with the chiral base (-)-sparteine in the palladium(II) catalyzed oxidative kinetic resolution of secondary alcohols [26]. The dimeric palladium complexes 51a-b used in this reaction were obtained in two steps from N,N -diaryl chiral imidazolinium salts derived from (S, S) or (R,R) diphenylethane diamine (Scheme 28). The carbenes were generated by deprotonation of the salts with t-BuOK in THF and reacted in situ with dimeric palladium al-lyl chloride. The intermediate NHC - Pd(allyl)Cl complexes 52 are air-stable and were isolated in 92-95% yield after silica gel chromatography. Two diaster corners in a ratio of approximately 2 1 are present in solution (CDCI3). 

Secondary alcohols such as cyclohexanol or 2-butanol also react on heating for 20-120 min at 80 °C with TCS 14 in the presence of BiCl3 to give the chloro compounds cyclohexyl chloride 784 and 2-chlorobutane in 93 and 90% yield, respectively, HCl, and HMDSO 7 [11, 12]. Benzyl alcohol is transformed likewise by Me3SiCl 14 after 120 min. at 80 °C into benzyl chloride in quantitative yield. Analogously, esters such as 2-acetoxypropane 785 are also converted by TCS 14 in 100% yield into chloro compounds such as 786 and trimethylsilyl acetate 142. The yS-lactone 787 gives rise to 788... 

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]. 

Whereas the original Moffat-Pfitzner oxidation employs dicyclohexylcarbodiimide to convert DMSO into the reactive intermediate DMSO species 1297, which oxidizes primary or secondary alcohols via 1298 and 1299 to the carbonyl compounds and dicyclohexylurea [78-80], subsequent versions of the Moffat-Pfitzner oxidation used other reagents such as S03/pyridine [80a, 83] or oxalyl chloride [81-83] to avoid the formation of dicyclohexylurea, which is often difficult to remove. The so-called Swern oxidation, a version of the Moffat-Pfitzner oxidation employing DMSO/oxalyl chloride at -60°C in CH2CI2 and generating Me2SCl2 1277 with formation of CO/CO2, has become a standard reaction in preparative organic chemistry (Scheme 8.31). 

Primary and secondary alcohols are rapidly converted to chlorides by a 1 1 mixture of SOCl2 and benzotriazole in an inert solvent such as CH2C12.8... 

Distillation to small volume of a small sample of a 4-year-old mixture of the alcohol with 0.5% of the ketone led to a violent explosion, and the presence of peroxides was subsequently confirmed [1]. Pure alcohols which can form stable radicals (secondary branched structures) may slowly peroxidise to a limited extent under normal storage conditions (isopropanol to 0.0015 M in brown bottle, subdued light during 6 months to 0.0009 M in dark during 5 years) [2], The presence of ketones markedly increases the possibility of peroxidation by sensitising photochemical oxidation of the alcohol. Acetone (produced during autoxidation of isopropanol) is not a good sensitiser, but the presence of even traces of 2-butanone in isopropanol would be expected to accelerate markedly peroxidation of the latter. Treatment of any mixture or old sample of a secondary alcohol with tin(II) chloride and then lime before distillation is recommended [3], The product of photosensitised oxidation is 2-hydroperoxy-2-propanol [4]. 

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