Ethers 1-chloroalkyl

Cross-linked macromolecular gels have been prepared by Eriedel-Crafts cross-linking of polystyrene with a dihaloaromatic compound, or Eriedel-Crafts cross-linking of styrene—chloroalkyl styrene copolymers. These polymers in their sulfonated form have found use as thermal stabilizers, especially for use in drilling fluids (193). Cross-linking polymers with good heat resistance were also prepared by Eriedel-Crafts reaction of diacid haUdes with haloaryl ethers (194). 

Isoprene reacts with a-chloroalkyl ethers in the presence of ZnCl in diethyl ether from 0—10°C. For example,a-chloromethyl methyl ether at 10°C gives a 6 1 ratio of the 1,4-adduct, (F)4-chloro-l-methoxy-2-methyl-2-butene, to the 1,2-adduct, 2-chloro-l-methoxy-2-methyl-3-butene. Other a-chloroalkyl ethers react in a similar manner to give predominately the 1,4-addition product. A wide variety of aHyUc chlorides and bromides and a-chloroethers and esters add primarily 1,4- to isoprene in the presence of acid catalysts (8). 

Chloroalkyl ethersf (chloromethyl, chloroethyl, and mixed ethers)... 

In analogy to alkylation with chloroalkyl ethers, methyl ot-methoxyperfluoro-propionate reacts with 2,6-dimethylphenol to give the bispheiiol [7] (equation 7)... 

Chloroalkyl-2-naphthyltellurium dichloride (general procedure). 2-Naphthyltellurium trichloride (2.98 g, 0.83 mmol) is heated under reflux with the olefin (1.2 mmol) in dry, ethanol-free CHCI3 (15 mL) until the trichloride has dissolved (0.5-1 h). Filtration from a small amount of elemental Te and evaporation gives an oil or a semi-solid that is recrystallized from a large amount of petroleum ether at 40-60°C. The reactions with propene and 2-butenes are performed in a sealed tube at 80°C. The yields are in the range 70-95%. 

Environmental Protection Agency Ambient Water Quality Criteria for Chloroalkyl Ethers,... 

Ambient Water Quality Criteria for Chloroalkyl Ethers, pp C-25, C-27. Springfield, VA, National Technical Information Service, US Environmental Protection Agency, 1980... 

World Health Organization Environmental Health Criteria 201 Selected Chloroalkyl Ethers, pp 1-75, International Programme on Chemical Safety, 1998... 

WHO (1998) Selected Chloroalkyl Ethers (Environmental Health Criteria 201), Geneva, Interna-... 

Very good yields, mild conditions, regioselectivity, versatility in the choice of the two reacting species (easy access to thermodynamic versus kinetic silyl enol ethers as well as to the required a-chloroalkyl phenyl sulfides) give to these sequences a particularly wide scope. Neopentylation is one illustration of their utility [325]. 

Isoprene reacts with cr-chloroalkyl ethers in the presence of ZnCh in diethyl ether from 0-10 C ... 

QUELET REACTION. Passage of dry hydrogen chloride through a solution in inligroin of a phenolic ether and an aliphatic aldehyde in the presence or absence of a dehydration catalyst to yield (y-chloroalkyl derivatives by substitution in the para position to the ether group or in the ortho position in pom-substituted phenolic ethers. 

EPA OSW Hazardous Haste Constituent (Appendix VIII, chloroalkyl ethers, N.O.S.) NA 40 CFR 261 EPA 1980b... 

When the olefin carries a hydroxyl group in a y- or -position to the double bond, a cyclic ether is isolated instead of the 2-chloroalkyl aryl tellurium dichloride2. 

As described in Section II.A, the tandem sequence reaction of organolithium compounds with carbon monoxide followed by reaction with suitable electrophiles provides an useful tool for the preparation of diphenyldialkyl carbinols, and the reaction could be easily extended to produce substituted cyclic ethers in a one-pot synthesis. Thus, by carrying out the carbonylation of phenyllithium in the presence of conveniently substituted chloroalkyl bromides, Br(CH2)3+ Cl, at -78 °C, the oxo-lithiated intermediates 243 are obtained and cyclized to 244 by warming up the reaction mixture (Scheme 74)21. 

Phenylthioalkylation of silyl enol ethers. Silyl enol ethers of ketones, aldehydes, esters, and lactones can be alkylated regiospecifically by a -chloroalkyl phenyl sulfides in fhe presence of a Lewis acid. Zinc bromide and titanium(IV) chloride are the most effective catalysts. The former is more satisfactory for enol ethers derived from esters and lactongs. ZnBr2 and TiCL are about equally satisfactory for enol ethers of ketones. The combination of TiCL and Ti(0-f-Pr)4 is more satisfactory for enol ethers of aldehydes. Since the products can be desulfurized by Raney nickel, this reaction also provides a method for alkylation of carbonyl compounds. Of more interest, sulfoxide elimination provides a useful route to a,B-unsaturated carbonyl compounds. 

Alkyl and aryl A -substituted 1,2,5-thiadiazolidine-1,1-dioxides 316 are synthesized in good yield from the reaction of sulfuryl chloride with 2-chloroethylamine. 2-Chloroethylamine hydrochloride is heated at 80°C with sulfuryl chloride in acetonitrile, and corresponding mono(chloroalkyl)sulfamyl chloride 314 is then extracted with diethyl ether to separate from unreacted amine hydrochloride. This ether solution is added to a solution of primary amine, and the resultant A -aryl (chloroalkyl)sulfamide 315 is treated with potassium carbonate in DMSO to afford A -substituted 1,2,5-thiadiazolidine-l,1-dioxides 316 <03TL5483>. 

Episulfonium ions were also proposed as intermediates in the geminal alkylation of /3-arylthio-a-chloroalkyl ethers <2006EJ01317>. 

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