Sulfur oxychlorides Thionyl chloride

Solvents that meet all or most of the criteria are propylene carbonate, dimethyl sulfoxide, 4-butyrolactone, acetonitrile, sulfur dioxide, thionyl chloride, and phosphorus oxychloride. Certain other solvents, with fairly low s values, such as tetrahydrofuran, dimethoxyethane, and 1,3-oxolane are used in conjunction with a high s solvent, in order to reduce the viscosity without impairing excessively the other desirable properties of the co-solvent. All these solvents are on the List, with properties shown in the tables mentioned. Commercial implementation of such batteries has been highly successful, with energy densities of primary dischargeable batteries of 0.3 W h g 1 or 0.5 W h cm 3 and a self discharge rate of < 2% per year of the open-circuit battery being achieved. 

Further relation between the hydroxyl groups was discovered by Orekhov and his co-workers (39, 40). When platynecine was treated with a variety of reagents (sulfuric acid, thionyl chloride, phosphorus trichloride, phosphorus pentachloride, or phosphorus oxychloride), it underwent the loss of a molecule of water to form anhydroplatynecine, CgHisNO, b.p. 

Synonyms Sulfinyl chloride Sulfur chloride oxide Sulfurous dichloride Sulfurous oxychloride Sulfur oxychloride Thionyl dichloride... 

Thionyl chloride behaves in some circumstances as though it dehydrates by tran -diaxial elimination, as described for phosphorous oxychloride. For example, the 5a-alcohol (102) undergoes anti-Saytzelf elimination to give the A" -olefin. In this particular example, phosphorous oxychloride-pyridine does not work, and acetic anhydride-sulfuric acid gives the A -isomer (ref. 185, p. 199). 

The known dibromide 464 was converted in good yield to the dinitrile 465 by reaction with buffered potassium or sodium cyanide. Reaction of 2,5-dimethoxycarbonyl-3,4-dicyanomethylthiophene 465 with thionyl chloride and selenium oxychloride gave thieno[3,4-f]thiophene 466 and selenolo[3,4-f]thiophene 467, respectively (Scheme 57) <2002JOC2453>. In the case of thionyl chloride as the sulfur transfer reagent, an intermediate sulfoxide 468 must be involved, which then suffers a spontaneous base-catalyzed Pummerer reaction to give 466 in high yield. 

Hydroxymethylpyridazines are easily oxidized with selenium dioxide to the corresponding aldehydes. Oxidation of the corresponding secondary alcohols with chromic acid in aqueous sulfuric acid gives ketones, while oxidation of a hydroxymethyl group with permanganate leads to the pyridazinecarboxylic acids. Hydroxymethyl groups are converted into chloromethyl groups with thionyl chloride or phosphorus oxychloride. 

Molecular halogens react with the thiones to give initially 1 1 adducts, formulated probably as 3-halothio-l,2-dithiolylium halides (42). For chlorine, these types convert to 3-chloro-1,2-dithiolylium salts (35a X = C1) (81AHC(23)i5l, 76PS(i)i85). Other more easily controlled halogen sources may be used, including thionyl chloride, oxalyl chloride, sulfur chloride and phosphorus oxychloride (70LA(742)103). A possible pathway for reaction with oxalyl chloride is shown in Scheme 19. 

Conditions for the ring closure of readily available 3-(2-hydroxy-2-phenylethyl)-2-iminotetrahydro-l,3-thiazole (263) (82S511) to (262), the racemate of the anthelmintic tetramisole, involve (a) dehydration with concentrated sulfuric acid or (b) reaction with thionyl chloride, phosphorus oxychloride or phosphorus pentachloride in the presence of base followed by dehydrochlorination (66JMC545,68JOC1350). 

A wide variety of dehydrating agents have been employed. In addition to those already mentioned are sulfuric acid, potassium bisulfate, formic acid, thionyl chloride, iodine, acetic anhydride, phosphorus oxychloride, and phosphorus pent-oxide. It should be noted that the free olefinic acids are sometimes decatboxylated under conditions similar to those described for certain of these dehydrations (cf. method 27). 

The electron-deficient atom with which the alcohol reacts may not be a carbon atom. It may be sulfur as in thionyl chloride (SOCI2) or toluene-4-sulfonyl chloride (MeC H4S02Cl), nitrogen as in nitrosyl chloride (NOCl), phosphorus as in phosphorus oxychloride (POCI3) or phosphorus pentachloride (PCI5) or chromium(Vr) as in chromium trioxide (CrOj). In each case, esters of the corresponding inorganic acids are formed. Many of these esters are very reactive and form intermediates in reaction sequences. 

Phosphorus pentachloride, a key industrial compound with annual world production of about 2X lO kg, is used to make other compounds. It reacts with sulfur dioxide to produce phosphorus oxychloride (POCI3) and thionyl chloride (SOCI2). Draw a Lewis structure and name the molecular shape of each product. 

The mechanism of dehydration of alcohols by hexamethylphosphortri-amide , phosphorus oxychloride and thionyl chloride in the presence of bases , and sulfur tetrafluoride have been studied. Kirk and Shaw have shown that it is unwise to assume a r/-stereospecificity in dehydration with phosphorus oxychloride or thionyl chloride with basic catalysts. The stereoselectivity is greatly dependent upon the basicity and steric environment of the base. Various steroidal alcohols undergo stereoselective iy -elimination upon treatment with methyl (carboxysulfamoyl) triethylammonium hydroxide inner salt . 

Other halides which have been added to carbodiimides include phosphorus trichloride, phosphorus oxychloride, sulfur dichloride, sulfuryl chloride, and thionyl chloride ( ), and product formation was judged on the basis of disappearance of the cumulative double bond absorption of the carbodiimides. 

Sulfurous anhydride. See Sulfur dioxide Sulfurous dichloride. See Thionyl chloride Sulfurous oxide. See Sulfur dioxide Sulfurous oxychloride. See Thionyi chioride Suifur oxide. See Sulfur dioxide Sulfur oxychloride. See Thionyl chloride... 

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