Carbon thionyl chloride

Sodium hydrogen carbonate Thionyl chloride Copper iodide Diazomethane Imidazole Trifluoroacetic acid Sodium methoxide 7-Bromo-3a,8b-cis-3a,8b-dihydro-3H-5-cyclopenta[b] benzofurancarboxylic acid... 

Solvent Methyl formate Dimethyl sulfoxide Propylene carbonate Thionyl chloride... 

Triiodobenzoyl chloride. Reflux 5 g. of 3 4 5-triiodo-benzoic acid, m.p. 289-290°, gently with 10 ml. of redistilled thionyl chloride for 2 hours. Distil off the excess of thionyl chloride on a water bath, and recrystallise the residue from carbon tetrachloride - light petroleum with the use of a little decolourising charcoal. The yield of the acid chloride (bright yellow needles, m.p. 138°) is 3-8 g. it keeps well in a stoppered bottle. 

A simpler nonphosgene process for the manufacture of isocyanates consists of the reaction of amines with carbon dioxide in the presence of an aprotic organic solvent and a nitrogeneous base. The corresponding ammonium carbamate is treated with a dehydrating agent. This concept has been apphed to the synthesis of aromatic and aUphatic isocyanates. The process rehes on the facile formation of amine—carbon dioxide salts using acid haUdes such as phosphoryl chloride [10025-87-3] and thionyl chloride [7719-09-7] (30). 

Monsanto has disclosed the use of carbon dioxide—amine complexes which are dehydrated, at low temperatures, with phosphoryl chloride [10025-87-3] or thionyl chloride [7719-09-7] as a viable route to a variety of aUphatic isocyanates. The process rehes on the facile formation of the intermediate salt (30).REPLACEVariations of this process, in which phosgene is used as a dehydrating agent, have been reported earlier (84). Table 2 Hsts commercially available aUphatic isocyanates. 

Acid Chloride Formation. Monoacid chlorides of maleic and fumaric acid are not known. Treatment of maleic anhydride or maleic acid with various reagents such as phosgene [75-44-5] (qv), phthaloyl chloride [88-95-9] phosphoms pentachloride [10026-13-8] or thionyl chloride [7719-09-7] gives 5,5-dichloro-2(5JT)furanone [133565-92-1] (4) (26). Similar conditions convert fumaric acid to fumaryl chloride [627-63-4] (5) (26,27). NoncycHc maleyl chloride [22542-53-6] (6) forms in 11% yield at 220°C in the reaction of one mole of maleic anhydride with six moles of carbon tetrachloride [56-23-5] over an activated carbon [7440-44-4] catalyst (28). 

Direct halogenation of sucrose has also been achieved using a combination of DMF—methanesulfonyl chloride (88), sulfuryl chloride—pyridine (89), carbon tetrachloride—triphenylphosphine—pyridine (90), and thionyl chloride—pyridine—1,1,2-trichloroethane (91). Treatment of sucrose with carbon tetrachloride—triphenylphosphine—pyridine at 70°C for 2 h gave 6,6 -dichloro-6,6 -dideoxysucrose in 92% yield. The greater reactivity of the 6 and 6 primary hydroxyl groups has been associated with a bulky halogenating complex formed from triphenylphosphine dihaUde ((CgH )2P=CX2) and pyridine (90). 

At present, thionyl chloride is produced commercially by the continuous reaction of sulfur dioxide (or sulfur trioxide) with sulfur monochloride (or sulfur dichloride) mixed with excess chlorine. The reaction is conducted in the gaseous phase at elevated temperature over activated carbon (178). Unreacted sulfur dioxide is mixed with the stoichiometric amount of chlorine and allowed to react at low temperature over activated carbon to form sulfuryl chloride, which is fed back to the main thionyl chloride reactor. 

Qindamycin, 7(5)-7-chloro-7-deoxyliQcomycin [18323-44-9] (1, R = H, R = Q), also known as Cleocin, first resulted from the reaction of lincomycin and thionyl chloride (54) improved synthetic methods involve the reaction of lincomycin and triphenylphosphine dichloride or triphenylphosphine in carbon tetrachloride (55). Clindamycin is significantly more active than lincomycin against gram-positive bacteria in vitro, and is absorbed rapidly following oral adnainistration. Clindamycin 2-palmitate [36688-78-5], (6, R = R = OC(CH2) 4CH2), 2-palmitate ester of clindamycin, is... 

Halogens add to the double bond of the alcohol to afford the corresponding dihalo derivatives, eg, CgH CHXCHXCH20H, where X = Cl or Br. The allyHc chloride C H Cl [2687-12-9] can be obtained by treatment of the alcohol with hydrochloric acid, thionyl chloride, or carbon tetrachloride—triphenylphosphine as the halogen donor. 

Treatment of coal with chlorine or bromine results in addition and substitution reactions. At temperatures up to 600°C chlorinolysis produces carbon tetrachloride, phosgene, and thionyl chloride (73). Treatment with fluorine or chlorine trifluoride at atmospheric pressure and 300°C can produce large yields of Hquid products. 

Carbon disulfide Ethyl nitrite Thionyl chloride-fluoride... 

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. 

Alcohol attack generates an unstable intermediate that undergoes nucleophilic attack by CL at carbon. Compare electrostatic potential maps of methanol, thionyl chloride intermediate, and phosphorus trichloride intermediate. What features of these maps are consistent with an electrophilic reactive intermediate ... 

The reaction of ethylene carbonate with acid imides which yields V-hydroxyethyl derivatives w as applied to 6-azauracil. In agreement with the foregoing findings, 6-azauracil produced a 3-(2-hydroxyethyl) derivative (65) which w as treated with thionyl chloride to convert... 

Synthesis of the remaining half of the molecule starts with the formation of the monomethyl ether (9) from orcinol (8). The carbon atom that is to serve as the bridge is introduced as an aldehyde by formylation with zinc cyanide and hydrochloric acid (10). The phenol is then protected as the acetate. Successive oxidation and treatment with thionyl chloride affords the protected acid chloride (11). Acylation of the free phenol group in 7 by means of 11 affords the ester, 12. The ester is then rearranged by an ortho-Fries reaction (catalyzed by either titanium... 

A solution of 54.1 grams of 1-formyl-4-(3 -chloropropyl)-piperazine, [prepared by formylat-ing 1-(3 -hydroxypropyl)-piperazine by refluxing in an excess of methyl formate, purifying the 1-formyl-4-(3 -hydroxypropyl)-piperazine by vacuum distillation, reacting this compound with an excess of thionyl chloride at reflux and isolating the desired 1-formyl-4-(3 -chloropropyl)-piperazine by neutralization with sodium carbonate solution followed by distillation] in 200 ml of toluene is added. The reflux period Is continued for 4 hours. 

Leclanche or dry cell Alkaline Cell Silver-Zinc Reuben Cell Zinc-Air Fuel Cell Lithium Iodine Lithium-Sulfur Dioxide Lithium-Thionyl Chloride Lithium-Manganese Dioxide Lithium-Carbon Monofluoride... 

Hydrazine 835 underwent ring closure with one carbon cyclizing reagents to afford 837 and/or /V-acyl derivatives 836. The N-acyl derivatives underwent cyclization on treatment with phosphorus oxychloride. They were also prepared by the reaction of hydrazones 838 with thionyl chloride (84JHC1565). Compound 835 underwent ring closure with carbon disulfide and ethyl chloroformate to give 839 (Scheme 169). 

Polychlorination processes have included exhaustive chlorination in the presence of antimony pentachloride, which destroyed the molecule (1882JCS412). Chlorine in carbon tetrachloride gave 3,4,6,8-tetrachlo-roquinoline chlorine dissolved in thionyl chloride gave the 4,5,7,8-isomer, whereas thionyl chloride alone produced a mixture of 3,4,5,6,7,8-hexachloro- (57%) and 3,4,6,8-tetrachloro- (37%) quinolines (73YZ73 74S356, 74URP432143). 

The Li-SOCl2 battery consists of a lithium-metal foil anode, a porous carbon cathode, a porous non-woven glass or polymeric separator between them, and an electrolyte containing thionyl chloride and a soluble salt, usually lithium tetrachloro-aluminate. Thionyl chloride serves as both the cathode active material and the elec-... 

Although the detailed mechanism for the reduction of thionyl chloride at the carbon surface is rather complicated and has been the subject of much controversy, the battery reactions are described as follows ... 

A 200-ml., round-bottomed flask equipped with a magnetic stirring bar is charged with 11.6 g. (0.1 mole) of hexanoic acid (Note 1) and 10 ml. of carbon tetrachloride. After 28.8 ml. (0.4 mole) of thionyl chloride (Note 2) is added to the solution, an efficient reflux condenser with an attached drying tube is fitted to the flask. The solution is then stirred and heated with an oil bath at 65° for 30 minutes (Note 3). 

The flask is removed from the oil bath and cooled to room temperature. To the reaction mixture are added successively 21.4 g. (0.12 mole) of finely powdered Nduomosuccininiide (l-bromo-2,5-pyrrolidinedione) (Note 4), 50 ml. of carbon tetrachloride, and 7 drops of aqueous 48% hydrogen bromide (Note 5). The flask is heated at 70 for 10 minutes (Note 6), and the temperature of the bath is then increased to 85° until the color of the reaction becomes light yellow (ca. 1.5 hours Note 7). The reaction mixture is cooled to room temperature, and the carbon tetrachloride and excess thionyl chloride are removed under reduced pressure (Note 8). The residue is suction filtered, and the solid (Note 9) is washed several times with carbon tetrachloride (total 20 ml.) and the combined filtrate collected in a 50-rnl. flask. The solvent is removed from the solution as before, and the residue is distilled into a dry ice-cooled receiver (short-path column) to give, after a small forerun, 16.1-17.1 g. (76-80%) of 2-bromohexanoyl chloride, b.p. 44-47 (1.5 mm.) as a clear, slightly yellow oil, n12 d 1.4707. This material is of sufficient purity for most synthetic purposes (Note 10). 

Fisher Scientific Company (reagent-grade) or Matheson Coleman and Bell. The first two were slightly yellow, and the latter was colorless however, the yields of final product were identical with each brand. The excess thionyl chloride serves as a drying agent for the hexanoic acid and as a solvent for the IV-bromosuecinimide, which is not very soluble in carbon tetrachloride. 

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