Thionyl nitrate, reaction with

Thionyl chloride nitrate and thionyl nitrate are prepared in situ from the reaction of a solution of thionyl chloride in THF with one and two equivalents of silver nitrate respectively, during which time silver chloride precipitates from solution. ... 

Lomustine Lomustine, l-(2-chloroethyl)-3-cyclohexyl-l-nitrosourea (30.2.4.3), is made by reacting ethanolamine with cyclohexylisocyanate, which forms l-(2-hydroxyethyl)-3-cyclohexylurea (30.2.4.1). Upon reaction with thionyl chloride, the hydroxyl gronp in it is replaced with a chlorine atom, giving l-(2-chloroethyl)-3-cyclohexylurea (30.2.4.2). This is nitrated in non-aqueons conditions with formic acid and sodinm nitrite to give lomustine (30.2.4.3) [67,68]. 

Nitration of hydroxypropiophenone (7-1) followed by conversion of the phenol to its methyl ether by means of methyl iodide provides the intermediate (7-2) the nitro group is then reduced to the corresponding amine (7-3) by catalytic reduction. The newly introduced amine is then replaced by a nitrile group by successive conversion to the diazonium salt by means of nitrous acid followed by treatment with cuprous cyanide (7-4). Reaction with aluminum chloride removes the methyl ether to afford the ortho acylphenol (7-5). This is converted to the chromone (7-6) as above by reaction with benzoyl chloride and sodium benzoate. The nitrile is next hydrolyzed to the carboxylic acid (7-7) by means of sulfuric acid. The acid is then converted to its acid chloride by means of thionyl chloride and that treated with 2-(A -piperidyl)ethanol (7-8). There is thus obtained flavoxate (7-9) [8], a muscle relaxant whose name reflects its flavone nucleus. 

Propoxybenzoic acid is obtained by the interaction of / -hydroxy benzoic acid and -propyl chloride in an alkaline medium, whieh on nitration yields the corresponding 3-nitro analogue. Subsequent treatment with thionyl ehloride yields an aeid ehloride whieh is then eoupled with 2-(diethylamino) ethanol yields the proxymetacaine base. This on reaction with an equimolar quantity of HCl gives the official compoimd. 

Activated primary nitro compoimds, i.e., those bearing an electron withdrawing group (EWG) geminal to the nitro group (i.e., 13 R = EWG), usually undergo dehydration reaction with acids [90] or under acylation conditions [86] or on thermolysis [91]. Some activated nitro compoimds have also been reported to imdergo dehydration to nitrile oxides 5 on treatment with Ce(III) ammonium nitrate [92] and thionyl chloride [93]. 

Two diphenylaminophthalides have been synthesized The 3,3-diphenyl-6-aminophthalide [24] was synthesized in 20% yield by the following sequence of reactions which was patterned after early work °. This series involved nitration of phthalimide, hydrolysis and dehydration to 4-nitrophthalic anhydride, Friedel-Crafts reaction with benzene to 2-benzoyl-5-nitrobenzoic acid, cyclization with thionyl chloride to the pseudoacid chloride, Friedel-Crafts reactions with benzene, and, finally reduction of the nitro group to the amino function with Adams catalyst. 

An unsuccessful attempt to repeat this reaction was made by Bird however, he was able to show that dibenzothiophene 5-oxide did, in fact, react with either thionyl chloride or phosphorus oxychloride to yield 2-chlorodibenzothiophene in good yield. Since all methods of nitration of dibenzothiophene yield a mixture of 2-nitrodibenzothio-phene and dibenzothiophene 5-oxide, which have identical melting points, it was concluded that the earlier workers had in fact been working with the sulfoxide and not the nitro compound. The reaction was rationalized as being a deoxygenative halogenation of a heterocyclic 5-oxide akin to the Meisenheimer reaction of A-oxides, which already had precedents in the sulfoxide field. Unfortunately the 2-chlorodibenzothiophene prepared by this route is contaminated with 2,8-dichlorodibenzothiophene which cannot be removed by crystallization. The best method of preparation of this compound is therefore via a Sandmeyer reaction on 2-aminodibenzothiophene. ... 

The data on the synthesis of nitrated 2,1-benzisothiazoles are rather scarce in comparison with the corresponding benzisoxazoles. It has been reported that, like other 2-aminotoluenes, 2-amino-4-nitrotoluene reacts with thionyle chloride in xylene to form 6-nitro-2,l-benzisothiazole, whereas 2-amino-5-nitrotoluene does not enter into this reaction (Scheme 2.93) [543],... 

A bicyclic derivative (105) of a 1,3-diazepine was prepared by treating 94 [R = NH(CH2)2OH] with thionyl chloride and then potassium hydroxide.108 Nitration of 105 gave the nitrate salt of 106.105 The reaction of 94 (R = SR4) with isothiocyanates has been studied.105 ... 

The diols (97) from asymmetric dil droxylation are easily converted to cyclic sii e esters (98) and thence to cyclic sulfate esters (99).This two-step process, reaction of the diol (97) with thionyl chloride followed by ruthenium tetroxide catalyzed oxidation, can be done in one pot if desired and transforms the relatively unreactive diol into an epoxide mimic, ue. the 1,2-cyclic sulfate (99), which is an excellent electrophile. A survey of reactions shows that cyclic sulfates can be opened by hydride, azide, fluoride, thiocyanide, carboxylate and nitrate ions. Benzylmagnesium chloride and thie anion of dimethyl malonate can also be used to open the cyclic sulfates. Opening by a nucleophile leads to formation of an intermediate 3-sidfate aiuon (100) which is easily hydrolyzed to a -hydroxy compound (101). Conditions for cat ytic acid hydrolysis have been developed that allow for selective removal of the sulfate ester in the presence of other acid sensitive groups such as acetals, ketals and silyl ethers. 

Triazolo[4,5-derived from the reaction of 5,6-diaminouracils with sodium nitrate and thionyl chloride, respectively (54JA2798 65CB1060 74M11 78H1437 89MI16) Scheme 54). 

Dipropalin can be prepared starting from p-cresol. p-Cresol is nitrated, and the dinitro-p-cresol (I) obtained is converted with thionyl chloride into 4-chloro-3,5-dinitrotoluene (II). This is then reacted with di-n-propylamine to give dipropalin. The reaction scheme is as follows ... 

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