Thiobenzoates

Thioacids (191) react with ia -thiocyanatoacetophenone to produce 2-mercapto-4-phenylthiazole (192) (Scheme 99). With tbioacetic acid 192 is obtained directly while with thiobenzoic acid, an acyclic intermediate (193) has been isolated that is cyclized by heating with dilute acid (Scheme 100) (143). 

Pd(dba)DPPB, 2-thiobenzoic acid, THF, 70-100% yield.Tertiary allyl-amines are cleaved efficiently at 20°, but secondary allylamines require heating to 60° to achieve cleavage. Thus, it is possible to monodeallylate a diallylamine by running the cleavage at 20°. "... 

Some rather unexpected formations of 5,6-dihydro-l,3-4i/-oxazines have also been noted, e.g., reaction of y-bromopropyl iminobenzoate with hydrogen sulfide, which yielded in addition to the main product (thiobenzoate) small amounts of (35) ... 

Protected 3-methyl-D-cystein (257 Scheme 3.94), a structural unit of the peptide antibiotics nisin and subtilin, has been synthesized through the ring-opening of the aziridinecarbamide 254 with thiobenzoic acid (255) [143, 144]. The reaction took place overnight at room temperature and in methylene chloride to give 256 in greater than 95% yield. 

Table 12. Crystal and molecular data of mesogenic phenyl thiobenzoates...

Skinner, Molnar Suarez (1964) studied the cement-forming potential of 28 liquid aromatic carboxylic acids with zinc oxide. Twelve yielded cohesive products of some merit. Of particular interest were cements formed with hydrocinnamic, cyclohexane carboxylic, p-tertiary butyl-benzoic, thiobenzoic and cyclohexane butyric acids. One of these cements is on the market as a non-eugenol cement. It is very weak with a compressive strength of 4 0 MPa, a tensile strength of 11 MPa and a modulus of 177 MPa, and is only suitable as a temporary material (Powers, Farah Craig, 1976). 

Thiobenzoic acid, 32,101 Thiocarbonyl perchloride, 32, 69 Thiolacetic acid, 31,105... 

However, the switchover from an A2 to an A1 hydrolysis is a very common mechanistic pathway in strong acid media, probably more common than the pure A2 mechanism. Excess acidity analyses have shown that thioacetic acid, several thiobenzoic acids, and many thiolbenzoate and thionbenzoate esters show this sort of mechanism switch.179 Acylals and thioacylals also show this behavior,116 with thioacylals using two water molecules and acylals one. Many hydroxamic acids react this way,127,216 as do esters of various types,41,217,218 episulfoxides219 and aryloxatriazoles.220 Acylhydrazines can also show a mechanism switch of this sort, although with these substrates the situation is somewhat more complex.221... 

Potassium 4-chloro-3,5-dinitrobenzene-sulfonate, 31, 46 Potassium cyanate, 31, 9 Potassium cyanide, 30,84 32,31,63 37,47 Potassium ethyl malonate, 37, 34 Potassium ethyl xanthate, 30, 56 Potassium fluoride, 36, 40 Potassium iodide, 30, 34 31, 31, 66 Potassium metal, 37, 29, 30 Potassium methyl sulfate, 31, 73 Potassium nitrate, 31, 46 Potassium 1-nitropropylnitronate, 37, 24 Potassium oxalate, 34, 83 Potassium permanganate, 30, 87 31, 59 Potassium sulfide, 32, 103 Potassium thiobenzoate, 32, 101 Potassium thiocyanate, 32, 39, 40 Prins reaction, 33, 72 Propane, 1, 3-dibromo-2, 2-Ws-(bromo-methyl)-, 31, 82... 

Several Me2SO adducts of rhodium(II) of the general type [Rh2(OOCR)4(Me2SO)2] have been synthesized (284,388) and their thermal decomposition via a two-step loss of sulfoxide studied (52). In addition, Me2SO adducts of rhodium(II) thioacetate (46) and thiobenzoate (45, 47) complexes have been reported. Coordination of the sulfoxide moieties via sulfur is reported on the basis of spectroscopic data. 

PPh3)(C6H5GOS)2RuB10H8 321 formed from the reaction of closo-[B10H10]2- and (PPh3)2RuGl2 has two -polyhedral thiobenzoate sulfur atoms.186... 

A procedure, which has been used successfully for the synthesis of dialkyl thioethers from thioacetamide has been extended to the preparation of a range of 5-alkyl thiocarboxylic esters [35] (Table 4.20). The intermediate 5-acyl ethaniminium salt (Scheme 4.14) is not stable and is converted directly into the 5-alkyl thioester. The choice of catalyst affects the yield of the thioesters. Thus, 5-n-octyl thiobenzoate... 

Martens, J. Praefcke, K. Schwarz, H. Spectroscopic Investigations. IX. Analytical Importance of the Ortho Effect in Mass Spectrometry. Benzoic and Thiobenzoic... 

The kinetics of oxidation of several para-substituted anilines and aliphatic acetals by peroxomonosulfate in aqueous acetic acid have been investigated. In the oxidation of sulfides to sulfoxides by peroxymonosulfate (Oxone), the observed increase in second-order rate constants with increasing concentration of H2SO4 has been shown to be due to the increasing polarity of the medium, rather than to acid catalysis. Similar conclusions were arrived at for the oxidation of aryl thiobenzoates and thiol-phosphorus(V) esters. 

S-phenyl thiobenzoate typical procedure in the presence of diphenyl disulphide. Photolysis of the telluroester (Ar = 4-FCgH4) in the presence of 6 equiv of diphenyl disulphide according to the standard for the formation of selenoesters gave 71% of the thiobenzoate after chromatography on silica gel (eluent hexane/ ethyl acetate, 9 1). The product had a melting point and spectral characteristics in accordance with those described in the literature. 

The potentially terdentate ligand, thiodiethanol (88), forms 1 1 complexes and 1 2 complexes with C0CI2. The former are five-co-ordinate and the latter octahedral. 1 1 Complexes of Co and diethylenetrithioacetic acid, ethylene-dithiodiacetic acid, and ethylidenetetrathiotetra-acetic acid have all been reported." " Potassium monothiobenzoate reacts with an equimolar quantity of CoSO in aqueous solution to yield green crystals of the pseudo-tetrahedral dinuclear complex [Co2(SOCPh)4 ], which contains both bidentate and bridging thiobenzoate ligands. ... 

---