Ethers mercaptans

The hydroxyl groups on glycols undergo the usual alcohol chemistry giving a wide variety of possible derivatives. Hydroxyls can be converted to aldehydes, alkyl hahdes, amides, amines, a2ides, carboxyUc acids, ethers, mercaptans, nitrate esters, nitriles, nitrite esters, organic esters, peroxides, phosphate esters, and sulfate esters (6,7). 

Just as in the case of aromatic compounds isoparaffins can be alkylated with sources of alkyl groups other than olefins. Alkyl halides, alcohols, ethers, mercaptans, sulfides, etc., can be used. When olefins are used some alkyl fluorides from a combination of olefin and hydrogen fluoride are always formed. The quantity of this in the product can be greatly reduced by providing conditions under which the alkyl fluoride is used in alkylation. The apparent paradox is provided, in that the fluoride content of the product is lessened by further treatment with hydrogen fluoride. A more thorough treatment of the details of the alkylation of isoparaffins with olefins is found elsewhere in this volume. 

Tricresyl phosphate Hydrocarbons, esters, ethers, mercaptans 125... 

Saturated Aliphatic Compounds Containing Heteroatoms. A great variety of organic matter falls in this classification—for example, alcohols, ethers, mercaptans, amines, and halides. Two types of simple cleavage reactions may occur that are initiated or directed by the presence of the heteroatom (O, S, N, X, etc.), as exemplified by Equations 16.18 and 16.19 for ethyl ether. Heteroatoms that can stabilize the positive... 

A clear correlation between the preferential path of molecular ion decomposition and the nature of functional groups is observed for hydrocarbon derivatives [378]. For instance, the presence of amine, alcohol, ether, mercaptane, and other nucleophilic groups favours C—C bond cleavage in p-position to the functional group. Any electrophilic substituent introduced into an aromatic nucleus increases the probability of the latter decomposition. 

Sometimes analyses are required for particular compounds such as sulfur, chlorine and lead, or for specific components such as mercaptans, hydrogen sulfide, ethers and alcohols. 

In acetic acid solvent, ethylene gives 1,3-propanediol acetates (46) and propylene gives 1,3-butanediol acetates (47). A similar reaction readily occurs with olefinic alcohols and ethers, diolefins, and mercaptans (48). 

Vinyl ethers are prepared in a solution process at 150—200°C with alkaH metal hydroxide catalysts (32—34), although a vapor-phase process has been reported (35). A wide variety of vinyl ethers are produced commercially. Vinyl acetate has been manufactured from acetic acid and acetylene in a vapor-phase process using zinc acetate catalyst (36,37), but ethylene is the currently preferred raw material. Vinyl derivatives of amines, amides, and mercaptans can be made similarly. A/-Vinyl-2-pyrroHdinone is a commercially important monomer prepared by vinylation of 2-pyrroHdinone using a base catalyst. 

Apparently the alkoxy radical, R O , abstracts a hydrogen from the substrate, H, and the resulting radical, R" , is oxidized by Cu " (one-electron transfer) to form a carbonium ion that reacts with the carboxylate ion, RCO - The overall process is a chain reaction in which copper ion cycles between + 1 and +2 oxidation states. Suitable substrates include olefins, alcohols, mercaptans, ethers, dienes, sulfides, amines, amides, and various active methylene compounds (44). This reaction can also be used with tert-huty peroxycarbamates to introduce carbamoyloxy groups to these substrates (243). 

Both antimony tribromide and antimony ttiiodide are prepared by reaction of the elements. Their chemistry is similar to that of SbCl in that they readily hydroly2e, form complex haUde ions, and form a wide variety of adducts with ethers, aldehydes, mercaptans, etc. They are soluble in carbon disulfide, acetone, and chloroform. There has been considerable interest in the compounds antimony bromide sulfide [14794-85-5] antimony iodide sulfide [13868-38-1] ISSb, and antimony iodide selenide [15513-79-8] with respect to their soHd-state properties, ferroelectricity, pyroelectricity, photoconduction, and dielectric polarization. 

Telomerization Reactions. Butadiene can react readily with a number of chain-transfer agents to undergo telomerization reactions. The more often studied reagents are carbon dioxide (167—178), water (179—181), ammonia (182), alcohols (183—185), amines (186), acetic acid (187), water and CO2 (188), ammonia and CO2 (189), epoxide and CO2 (190), mercaptans (191), and other systems (171). These reactions have been widely studied and used in making unsaturated lactones, alcohols, amines, ethers, esters, and many other compounds. 

For example, carbon dioxide from air or ethene nitrogen oxides from nitrogen methanol from diethyl ether. In general, carbon dioxide, carbon monoxide, ammonia, hydrogen sulfide, mercaptans, ethane, ethene, acetylene (ethyne), propane and propylene are readily removed at 25°. In mixtures of gases, the more polar ones are preferentially adsorbed). 

Butyl ether Butyl carbitol /i-Butyl glycidyl ether Butyl mercaptan p-tert-Butyltoluene Carbon disulphide Carbon dioxide Carbon monoxide Carbon tetrachloride Carbonyl sulphide Carbary ... 

Ethyl chloride Ethyl ether Ethyl formate 2-Ethyl hexanol Ethyl mercaptan Ethyl silicate Ethylene... 

Methyl-3-heptanone Methylhydrazine Metolachlor Methyl mercaptan Methyl parathion Methyl phenol N-Methyl-2-pyrrolidinone Methyl tert-butyl ether Mevinphos ... 

The striking effect of the catalyst is exemplified by the reaction of pregna-4, 16-diene-3,20-dione (10) with benzyl mercaptan. In the presence of piperidine only conjugate addition occurs to give (11) whereas with pyridine hydrochloride only the 3-benzyl thioenol ether (12) is formed. In the presence of p-toluenesulphonic acid both reactions take place to yield (13). 

The A" -3-keto group can be selectively protected as a thioenol ether in the presence of a 17- or 20-ketone. High yields are obtained with benzyl mercaptan and pyridine hydrochloride as a catalyst. 

Treatment of aziridine-2-carboxylic ester 251 (Scheme 3.93) with benzyl mercaptan in the presence of boron trifluoride etherate afforded 252 in 71% yield [142]. Compound 252 has been transformed into peptide 253, an analogue of a penicillin precursor. 

Butyl cellosolve (2-butoxy ethanol) n-Butyl glycidyl ether n-Butyl mercaptan n-Butylamine p-tert-Butyltoluene... 

Butyl cellosolve, see 2-Butoxyethanol tert-Butyl chromate (as CrOj) n-Butyl glycidyl ether n-Butyl lactate Butyl mercaptan p-tert-Butyltoluene Cadmium, dust and salts (as Cd) Cadmium, fume (as Cd)... 

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]. 

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