Thiocarboxylic acid chlorides

Aryl thiocarboxylic acid chlorides. These compounds can be obtained from reaction of aryl carbodithioic acids with phosgene at 0-35° followed by thermolysis of the S-chlorocarbonyl derivatives below 1 torr. The products are stable for several months in the dark at 0". ... 

Sodium hydrogen sulfide Thiocarboxylic acid chlorides from dithiocarboxylic acid esters via dithiocarboxylic acids... 

The preparation of acid azides from thiocarboxylic acids/HNa or from acyl chlorides with dibenzyldi-methylammonium azidosulfonate has not yet found broad application (Scheme 42). 

An acyl transfer agent which can be used for the synthesis of acid anhydrides is obtained from the reaction of an acid chloride with 4-benzylpyridine (equation 24). In this way benzoic acid anhydride and cinnamic acid anhydride were obtained in 72% and 57% yields, respectively. As the intermediate, 1-acyl-4-benzylidene-l,4-dihydropyridines, can be isolated, Ais procedure should be well suited for the preparation of mixed anhydrides. Mixed aromatic and aliphatic anhydrides can be prepared with 2-ben-zoylthio-l-methylpyridinium chloride and salts of carboxylic acids. These reactions are carried out in aqueous solution. Iliey make use of the high reactivity of esters of thiocarboxylic esters towards nucleophiles. The mixed anhydrides of benzoic acid with 3-phenylpropanoic acid, phenoxyacetic acid, isobu-tyric acid, p-toluic acid and cinnamic acid were formed in 82, 79,61,91 and 66% yields, respectively. 

Crystalline adducts from thioamides and aromatic acid chlorides ate well known. A very convenient synthesis of diacyl sulfides and thiocarboxylic acids - proceeds via adducts of thio-DMF with acid chlorides. 

Thiocarboxylic acids are obtained by acylation of hydrogen sulfide (cf. page 642). For example, thiobenzoic acid is formed (61-76% yield) from benzoyl chloride and potassium hydrogen sulfide,426 and thioacetic acid (74% yield) when hydrogen sulfide is passed into acetic anhydride.427,428 This method can also be applied to other anhydrides.429... 

The acid chlorides specified in reaction (1) may be replaced by 5-esters of thiocarboxylic acids [i.e., RC(0)SC6H5 or RC(0)SC2H5 in place of RCOC1] 458 their reaction leads to separation of a thiophenol or an alkane-thiol, and these products do not consume a second molecule of the alkylidenephosphorane. The last statement is true also for the reaction with 1-acylimid-azoles described by Bestmann, Sommer, and Staab.459... 

Diethylaluminium cyanide is a valuable reagent for the conjugate addition of HCN to o , 3-unsaturated carboxylic acid derivatives [120]. Steroidal conjugate esters are somewhat resistant to HCN addition even with this powerful reagent and optimum yields of only 36-50% were obtained. With aj3-unsaturated acid chlorides and acid cyanides, however, the reaction proceeds smoothly in toluene at room temperature and, after hydrolysis the 0-cyanoacid was obtained in 71—73% yield. Conjugated steroidal thiocarboxylic S-esters react under similar conditions to give the product in yields of 85-87%. 

Thiocarboxylic acid esters from a-chlorimmonium chlorides -e- s. 19, 628 ... 

Prepn. from N,N-disubst. carboxylic acid amides—Thiocarboxylic acid esters Dithiocarboxylic, thiolic, and thionocarboxylic acid esters—Ring closures to heterocyclics s. 19, 628 a-chlorimmonium chlorides cf. M. Grdini6 and V. Hahn, J. Org. Chem. 30, 2381 (1965)... 

Thallium(l) thiolates have been introduced by Masamune et Their use is especially advantageous if 5-t-butyl thiocarboxylic esters are to be prepared which can serve as educts for macrolide synthesis. Zearalenone dimethyl ether ethylene acetal (22 cf. also Scheme 1) was obtained from the corresponding acid chloride and thallium(I) a-methylpropanethiolate via the S-f-butyl benzenecarbo-thioate (21 equation 14)... 

Maleic anhydride grafting (cont.) poly(styrene-co-divinylbenzene), 694 poly(styrene-co-isobutylene), 675, 689 poly(styrene-co-nfialeic anhydride), 676, 679 poly(vinyl acetate), 676, 694 poly(vinyl acetate-co-vinyl fluoride), 678 poly(vinyl alkyl ethers), 675, 679, 692, 701 poly(vinyl chloride), 683, 692, 693, 695, 702 poly(vinylidene chloride), 691 poly(vinyl toluene-co-butadiene), 689 radical—initiated, 459-462, 464-466, 471, 475, 476 radiation—initiated, 459, 461, 466, 471, 474 redox-initiated, 476 rubber, 678, 686, 687, 691, 694 to saturated polymers, 459-466, 475, 476 solvents used 460-463, 465, 466, 469, 474-476 styrene block copolymers, 679 tall oil pitch, 678, 697 terpene polymers, 679, 700 thermally-initiated, 462, 464-467, 469, 476 to unsaturated polymers, 459, 466-474 vapor-phase techniques, 464, 474, 475 to wool fibers, 476 Maleic anhydride monomer acceptor for complex formation, 207-210 acetal copolymerization, 316 acetone CTC thermodynamic constants, 211 acetone photo-adduct pyrolysis, 195, 196 acetylacetone reaction, 235 acetylenic photochemical reactions, 193-196 acrylamide eutectic mixtures, 285 acylation of aromatic acids, 97 acylation of aromatics, 91, 92 acylation of fused aromatics, 92, 95, 97, 98 acylation of olefins, 99 acylation of phenols, 94-96 acylic diene Diels-Alder reactions, 104-111, 139 addition polymer condensations, 503-505 adduct with 2-cyclohexylimino-cyclopentanedi-thiocarboxylic acid, 51 adducts for epoxy resins curing, 507-510 adduct with 2-iminocyclopentanedithiocarboxylic acid, 51... 

Thin-layer chromatography, MA detection, 10 Thioacetic acid, MA reaction, 51, 55 Thiocarboxylic acid salts, MA adducts, 51 Thiocyanates, isomerization catalyst, 13 Thioglycolic acid, disodium maleate reaction, 49 Thionyl chloride... 

Thiocarboxylic acid esters from a-chlorimmonium chlorides... 

The cyclization of 0,0-diethyl 2-quinolinylaminomethylenethion-malonate (1056) by heating in a mixture of polyphosphoric acid and phos-phoryl chloride afforded 55-60% of l-oxopyrimido[l,2-a]quinoline-2-car-boxylate (1055, R = Et, R2-R4 = H), while heating in Dowtherm A at 250°C led to 1 -oxopyrimido[ 1,2-a]quinoline-2-thiocarboxylate (1057) in 15-17% yields (74MIP1 84S152). 

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