Oxide chlorides from thionyl chloride

Apart from the work toward practical lithium batteries, two new areas of theoretical electrochemistry research were initiated in this context. The first is the mechanism of passivation of highly active metals (such as lithium) in solutions involving organic solvents and strong inorganic oxidizers (such as thionyl chloride). The creation of lithium power sources has only been possible because of the specific character of lithium passivation. The second area is the thermodynamics, mechanism, and kinetics of electrochemical incorporation (intercalation and deintercalation) of various ions into matrix structures of various solid compounds. In most lithium power sources, such processes occur at the positive electrode, but in some of them they occur at the negative electrode as well. 

Compounds (11) were also prepared in low yield by oxidation of the bishydrazine (20) by sodium hypochlorite (72JA8497), potassium ferricyanide or potassium permanganate (Scheme 3) (73CB3097). The l,4-dibenzyl-5,6-diphenyl compound (22) was prepared from 1,1,4,4-tetrabenzyltetrazene (21) by oxidative cyclization using thionyl chloride (73CL51). 

The crystal and molecular structures of disulfane 1-oxides (R = 4-tolyl) and of trisulfane 2-oxides have been determined by X-ray diffraction. The latter compounds are usually obtained from thionyl chloride and thiols (RSH) in ether or in the presence of pyridine (equations 154 and... 

Treatment of 2,2,4,4-tetramethyl-3-thietanone with diiron nonacarbonyl gives the binuclear iron complex 381. 2,2-Dimethyl-3-thietanone undergoes oxidative dimerization to 382 on treatment with potassium ferricyanide. Methylene-3-thietanones such as 359 add chlorine from thionyl chloride to the carbon-carbon double bond. 2,2,4,4-tetramethyl-3-thietanone is converted to the 3-thione in 14% yield by treatment with hydrogen sulfide-hydrogen chloride. Electrochemical reduction of the thione produces radical anions. 

Salts of the [UC16] ion have been prepared by precipitation from thionyl chloride solutions of U(V) which were in turn prepared by the prolonged (2 weeks) refluxing of U03 with thionyl chloride3 or by the addition of solid UC15 TCAC, where TCAC = trichloro-acryloyl chloride.4 This latter extremely moisture-sensitive compound was in turn prepared by the reaction of U3 O 8 with hexachloro-propene.1,4 The method of preparation described here,2 which is applicable to the preparation of certain salts of the [UC16] ion, is based on chlorine oxidation in nitromethane solutions of the easily prepared and stored [UC16]2- salts. Some of the known salts of... 

Freeman and Smith (32) have prepared the anhydrous chlorides of a number of lanthanides and of thorium by dehydrating the hydrated chlorides with thionyl chloride. Although efforts to obtain anhydrous plutonium trichloride in this way were unsuccessful, it is believed that this may be a useful procedure for actinide elements such as actinium, americium, and curium that have a particularly stable (III) oxidation stage. In general, aqueous methods for preparing tetrachlorides are of little value but anhydrous trichlorides, particularly of the transuranium elements, can be obtained readily from the hydrated trichlorides by dehydration in an atmosphere of hydrogen chloride. 

Other important cycloelimination procedures correspond to an elimination of H2O from cyclic ketones. Thus, the a-hydrogen atoms of semicarbazones of cyclic ketones are removed by oxidative cyclization with thionyl chloride or selenium dioxide (Scheme 8-7). The 1,2,3-thiadiazoles (71) or 1,2,3-selenadiazoles (72) which result from these reactions can be cleaved in a second step to yield cyclic alkynes (Scheme 8-8) [28]. Several fragmentation conditions are known, among them thermal decomposition and base-induced cleavage. The mechanism of these reactions has been studied in detaU [29]. It has been noted that the crucial step is the cleavage of the carbon-sulfur or carbon-selenium bond, as in this step the geometrical strain is introduced into the system. Clearly, due to the weakness of the C —Se... 

Dicyano-l,2,3-trithiole 2-oxide (143) has been prepared from the silver salt of 2,3-dimercaptomaleonitrile (142) and thionyl chloride (66HC(2l-i)67). Similarly, the reaction of ethylene glycol (144) with thionyl chloride gave 1,3,2-dioxathiolane 2-oxide (145), the parent compound of saturated five-membered cyclic sulfites (see Chapter 4.33). 

A number of 1,2,3-oxathiazole 5-oxides are prepared from the reaction of thionyl chloride with various ethane derivatives having vicinal oxygen- and nitrogen-containing groups. Reaction of the 2-aminoethanol derivative (146) with SOCI2 gave (147) (see Chapter 4.34). 

Benzisothiazoles are best prepared by oxidative cyclization of o-aminothiobenz-amides (see Section 4.17.9.1.1), reaction of o-toluidines with thionyl chloride (see Section 4.17.9.2.1) or by sulfuration of 2,1-benzisoxazoles (see Section 4.17.10.2). 1,2-Benzisothiazoles can also be prepared from o-disubstituted benzene compounds, cyclodehydration of o-mercaptobenzaldoximes or oxidative cyclization of p-mercaptobenzylamines (see Section 4.17.9.1.1) being the most convenient. Both series of benzo compounds are readily substituted at the 5- and 7-positions by electrophilic reagents. 

The a -halosulfone, required for the Ramberg-Backlund reaction, can for example be prepared from a sulfide by reaction with thionyl chloride (or with N-chlorosuccinimide) to give an a-chlorosulfide, followed by oxidation to the sulfone—e.g. using m-chloroperbenzoic acid. As base for the Ramberg-Backlund reaction have been used alkoxides—e.g. potassium t-butoxide in an etheral solvent, as well as aqueous alkali hydroxide. In the latter case the use of a phase-transfer catalyst may be of advantage. ... 

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... 

Treatment of pyridyl carbinol 51 with thionyl chloride leads to the corresponding chloride (52), Treatment of that intermediate with 5-methoxy-2-mercaptobenzimidazole (53), obtained from reaction of 4-methoxy-q-phenylenediamine with potassium ethylxanthate leads to displacement of halogen and formation of the sulfide (54). Finally, oxidation with 3-chloroperbenzoic acid produces the sulfoxide omeprazole (55) fl7]. 

It was quite recently reported that La can be electrodeposited from chloroaluminate ionic liquids [25]. Whereas only AlLa alloys can be obtained from the pure liquid, the addition of excess LiCl and small quantities of thionyl chloride (SOCI2) to a LaCl3-sat-urated melt allows the deposition of elemental La, but the electrodissolution seems to be somewhat Idnetically hindered. This result could perhaps be interesting for coating purposes, as elemental La can normally only be deposited in high-temperature molten salts, which require much more difficult experimental or technical conditions. Furthermore, La and Ce electrodeposition would be important, as their oxides have interesting catalytic activity as, for instance, oxidation catalysts. A controlled deposition of thin metal layers followed by selective oxidation could perhaps produce cat-alytically active thin layers interesting for fuel cells or waste gas treatment. 

Aziridine-2-carboxylates 12 (Scheme 3.4) have also been prepared from 3-hy-droxy-a-amino esters 9 by treatment with sulfuryl chloride in place of tosyl or mesyl chloride. Treatment of 9 with thionyl chloride in the presence of triethylamine, followed by oxidation of 10 with sodium periodate and a catalytic amount of... 

This intermediate would be further oxidized by thionyl chloride and solvolyzed by ethanol to the pyridinium chloride hydrochloride. According to this reaction route, the stoichiometric ratio of pyridine to thionyl chloride for the overall process would be about 1 1. Varying ratios of thionyl chloride have been used6-8 and varying yields of the product have been reported, ranging from 60% of crude product7 to 48% of recrystallized product.8 In one run in which the checkers used one-half the specified amount of thionyl chloride, the yield was unaffected. The submitters report yields in the range 58-62% by the procedure described here. 

Materials and Purification. Chemicals were purchased from Aldrich chemical company and used as received unless otherwise noted 1,1,1,3,3,3-hexamethyl disilazane, ethylene glycol, triphosgene, poly(ethylene oxide) (MW = 600), poly(tetramethylene oxide) (MW = 1000), poly(caprolactonediol) (MW = 530), toluene diisocyanate (TDI), anhydrous ethanol (Barker Analyzed), L-lysine monohydride (Sigma) and methylene bis-4-phenyl isocyanate (MDI) (Kodak). Ethyl ether (Barker Analyzer), triethylamine and dimethyl acetamide were respectively dried with sodium, calcium hydride and barium oxide overnight, and then distilled. Thionyl chloride and diethylphosphite were distilled before use. 

Luminol amidine 132, synthesized from luminol and the Vilsmeier reagent from DMF and thionyl chloride, has been proposed as a suitable luminol derivative for analytical purposes because, unlike luminol, it can be easily purified by recrystallization from water. 132 exhibits a chemiluminescence quantum yield of about 20% of luminol in ferricyanide-catalyzed oxidation by aqueous alkaline hydrogen peroxide Amax of the emission is 452 nm 196>. 

Treatment of enantiomerically pure (R,R)- and (A,A)-l,2-bis(pentafluorophenyl)ethane-l,2-diamines with thionyl chloride gave the corresponding thiadiazolidine 1-oxides in high yield <2004BCJ1001>. A series of Aralkyl-substituted thiadiazolidine 1,1-dioxides 171 were also prepared from the starting 1,2-diamine 170 by treatment with sulfamide followed by a regioselective monoalkylation (Scheme 26) <2005BML4212>. 

The conventional synthesis of trans-2,5-dialkyl phospholanes starting from a chiral 1,4-diol is shown in Scheme 24.1. Originally, these 1,4-diols were obtained via electrochemical Kolbe coupling of single enantiomer a-hydroxy adds [25], but this method proved to be commercially impracticable and has since been replaced by more viable biocatalytic routes [26]. Reaction of the chiral 1,4-diol with thionyl chloride followed by ruthenium-catalyzed oxidation with so-... 

Anthrapyrimidine and its substituted derivatives are obtained by condensation of 1-aminoanthraquinone (or its derivatives) with formamide or aqueous form-aldehyde/ammonia in the presence of an oxidant, such as ammonium vanadate or m-nitrobenzosulfonic acid. A newly developed, more simple route proceeds via formamidinium chloride, which is prepared from 1-aminoanthraquinone with di-methylformamide and thionyl chloride or phosphorus oxychloride. Cyclization in a solvent in the presence of ammonium acetate affords the desired product ... 

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