From chloro ethers with

Aj Preparation of 3-Chloromethyl-6-Chloro-7-Sulfamyl-3,4-Dihydro-Benzothiadizine-1,1-Dioxide—Jo 8 ml of 40-50% chloroacetaldehyde aqueous solution and 7 ml of dimethyl-formamide are added 10 grams of 2,4-disulfamvl-5-chloroaniline. The mixture is heated on a steam bath for 2 hours after which it Is concentrated at reduced pressure. The residue Is triturated with water. The solid material is recrystallized from methanol-ether after-treatment with activated carbon to give 7.2 grams of product, MP 229°-230°C. 

The N-[/3-(o-chlorophenyl)-/3-hydroxyethyl] -isopropylamine obtained by the foregoing procedure was dissolved in about 3 liters of ether and dry hydrogen chloride gas was bubbled into the solution until it was saturated, whereupon the hydrochloride salt of N-[/3-(o-chloro-phenyl)-/3-(hydroxy)-ethyl] isopropylamine precipitated. The salt was separated from the ether by filtration, and was dissolved in two liters of anhydrous ethanol. The alcoholic solution was decolorized with charcoal and filtered. 

The residue was dissolved in 75 ml of tetrahydrofuran, treated with charcoal, and sodium sulfate and filtered. This solution was added to a solution in 250 ml of tetrahydrofuran of phenyl magnesium bromide prepared from 17.7 ml (0.17 mol) of bromobenzene. This mixture was stirred and heated under reflux for 1 hour. It was then cooled and diluted with 400 ml of ether and sufficient 3N hydrochloric acid to make it acidic. The aqueous phase was separated, adjusted to pH 8 with 3N sodium hydroxide and extracted 3 times with 200 ml of ether. The ether extracts were combined, washed with water and dried over sodium sulfate. The residue left on removal of the ether in vacuo was crystallized from petroleum ether to give 3.3 g of 7-chloro-2,3-dihvdro-1-methyl-5-phenvl-1 H-1,4-benzodiazepine, according to U.S. Patent 3,624,703. 

A solution of 200 g of 1 -p-chlorophenvl-2-phenyl-4-(N-pvrrolidino)-butanol-2 in 750 ml of concentrated hydrochloric acid is refluxed for 9 hours thereby causing a dehydration of the butanol compound, and the formation of the hydrochloric acid addition salt of a 1 -p-chloro-phenyl-2-phenyl-4-(N-pyrrolidino)-butene. The hydrochloride salt formed crystallizes in the oily lower layer of the two phase reaction mixture and is removed therefrom by filtration. The filtrate is again refluxed for 9 hours, cooled to0°C,and a second crop of the hydrochloric acid addition salt of the dehydration product is obtained and filtered off. The filtrate containing residual amounts of 1 -p-chlorophenyl-2-phenyl-4-(N-pyrrolidino)-butanol-2 is again refluxed for 9 hours to yield an additional crop of the salt of the dehydration product. The several fractions of the butene compound are combined and triturated with several small portions of hot acetone and recrystallized from alcohol-ether mixture. The hydrochl or ic acid addition salt of the dehydration product, 1 -p-chlorophenyl-2-phenyl-4-(N-pyrrolidino)-butene hydrochloride, melts at about 227°C to 228°C. 

A gas liquid chromatographic (GLC) method was described for determining residues of Bayer 73 (2-aminoethanol salt of niclosamide) in fish muscle, aquatic invertebrates, mud, and water by analyzing for 2-chloro-4-nitroaniline, a hydrolysis product of Bayer 73 [83]. Residues were extracted with acetone-formic acid (98 + 2), and partitioned from water samples with chloroform. After sample cleanup by solvent and acid base partitioning, the concentrated extract was hydrolyzed with 2N NaOH and H202 for 10 min at 95°C. The 2-chloro-4-nitroaniline was then partitioned hexane ethyl ether (7 + 3) and determined by electron capture GLC. Average recoveries were 88% for fish, 82% for invertebrates, 82% for mud, and 98% for water at 3 or more fortification levels. 

Typical procedure A mixture of the benzyl ether (0.246 g, 1 mmol) and p-phe-noxyphenyltellurium trichloride (0.403 g, 1 mmol) in anhydrous chloroform (15 ml) was stirred for 30 min at room temperature, then the solvent was evaporated and the residue was filtered through a column of silica gel eluting with chloroform. Evaporation of the solvent in a rotatory evaporator followed by recrystallization of the residue from chloro-form/petroleum ether and washing several times with petroleum ether gave 0.50 g (97%) of the product, m.p. 108-110°C. 

Zinc enolate 4, prepared from acetylene ether pyridine i-oxide, mercuric chloride, and zinc, adds to aldehydes to form a-chloro-3-hydroxy esters 5 in good yields ( ). Subsequent treatment with base gives trans-epoxyesters, one of which 6 is converted to 2-amino-2-deoxy-D-ribose stereoselectively in good yields (O. 

Preparation1 This reagent can be prepared in 66% yield by reaction of triflic acid with isopropenyltrimethylsilane, CH2=C(CH3)Si(CH3)3, which is available from Petrarch or which can be prepared by a Wurtz-Fittig reaction of 2-chloro-propene with sodium and chlorotrimethylsilane in ether/HMPT. 

N 14.12% yel scales(from ale), crysts (from MeOH) readily sol in ale, acet, benz or MeOH insol in w or petr eth was prepd by treating either l-chloro-2,4-dinitroresorcinol dimethyl-ether or l-chloro-4, 6-dinitroresorcinol dimethyl ether with cold HNOa or with mixed HN03-H2S04 acid(Refs 1,2 3). Its expl props were not detd Refs l)Beil 6 [826] 2)H.H.Schlubach ... 

Herrmann M, Bohlendorf B, Irschik H, Reichenbach H, Hofle G (1998) Maracin and Maracen New Types of Ethynyl Vinyl Ether and a-Chloro Divinyl Ether Antibiotics from Sorangium cellulosum with Specific Activity Against Mycobacteria. Angew Chem Int Ed 37 1253... 

A simple example involves the reaction of the silyl ether 213, made from the corresponding 4-hydroxy-alkene by treatment with (bromomethyl)chloro-dimethylsilane, with tributyltin hydride and a radical initiator. Bromine abstraction and intramolecular cyclization with the double bond leads to the bicyclic 214, which upon oxidation with hydrogen peroxide gives the branched-chain 215 in an overall yield of 73% from the alcohol precursor of 213 (Scheme 21). When the sequence is conducted with the C-4 epimeric starting alcohol, the final product again has the hydroxymethyl group cis-related to the hydroxy group.217... 

---