Pyridines from thioureas

Furium. N[4-(5-Nitro-2-furanyl)-2-thia2olyl]acetamide, has demonstrated activity against baciUi and pathogenic enterobacteria (24). The product, prepared from thiourea and 2-bromo-l-(5-nitro-2-furanyl)ethanone followed by acetylation of the intermediate aminothia2ole with acetic anhydride in pyridine (25), is marketed in several countries for both human and veterinary use. 

The sole report in the literature of a pyridine nucleus prepared from thioureas is that of Cottis and Tieckelmann,216 who obtained 2-amino-3,5-dicyano-6-alkylthiopyridines (99) by treating 2-alkyl-2-thiopseudo-urea hydrogen sulfates with l,l-dicyano-2-ethoxyethene (98). Careful attention to the concentration of 98 and base led to good yields of 99 otherwise, the products of the reaction were pyrimidines.218... 

Amino-4,5,6,7-tetiahydrothiazolo 5,4c pyridine, from 3-bromo-4-piperidone hydrochloride and thiourea, 230 2-Aminothiazole, 566 deamination of, 272 diazo coupling, 103 labelled from C-thiourea, 214 mechanism of formation, 232 pKa, 92... 

Various types of six-membered rings are formed from thioureas. Elimination of isothiocyanate from the butadienylthiourea ArNHC(S)NH(CH=CH)2CHO yields pyridine, whereas the oxazine (48) arises from ketone (47). The... 

The synthesis of these disubstituied thioureas takes place in three steps. First the alkyl bromide is prepared by the action of hydrobromic acid on the corresponding alcohol (518). Then the dialkylcyanamide is obtained by treatment at 25°C with calcium cyanamide. The yields are of the order of 30 to 60%. Thioureas are obtained in a third step from the cyanamide by reaction at 40 C with HjS in the presence of pyridine. Yields ranged from 57 to 90% (518),... 

Nitrogen nucleophiles used to diplace the 3 -acetoxy group include substituted pyridines, quinolines, pyrimidines, triazoles, pyrazoles, azide, and even aniline and methylaniline if the pH is controlled at 7.5. Sulfur nucleophiles include aLkylthiols, thiosulfate, thio and dithio acids, carbamates and carbonates, thioureas, thioamides, and most importandy, from a biological viewpoint, heterocycHc thiols. The yields of the displacement reactions vary widely. Two general approaches for improving 3 -acetoxy displacement have been reported. One approach involves initial, or in situ conversion of the acetoxy moiety to a more facile leaving group. The other approach utilizes Lewis or Brmnsted acid activation (87). 

The DPA ester is formed from the acid chloride in pyridine (40-96% yield). It is cleaved oxidatively by treatment with NBS followed by thiourea (40-88% yield). ... 

Direct measurements on metals such as iron, nickel and stainless steel have shown that adsorption occurs from acid solutions of inhibitors such as iodide ions, carbon monoxide and organic compounds such as amines , thioureas , sulphoxides , sulphidesand mer-captans. These studies have shown that the efficiency of inhibition (expressed as the relative reduction in corrosion rate) can be qualitatively related to the amount of adsorbed inhibitor on the metal surface. However, no detailed quantitative correlation has yet been achieved between these parameters. There is some evidence that adsorption of inhibitor species at low surface coverage d (for complete surface coverage 0=1) may be more effective in producing inhibition than adsorption at high surface coverage. In particular, the adsorption of polyvinyl pyridine on iron in hydrochloric acid at 0 < 0 -1 monolayer has been found to produce an 80% reduction in corrosion rate . 

Salts of dithiocarbamic acid can be prepared by the addition of primary or secondary amines to carbon disulfide. This reaction is similar to 16-9. Hydrogen sulfide can be eliminated from the product, directly or indirectly, to give isothiocyanates (RNCS). Isothiocyanates can be obtained directly by the reaction of primary amines and CS2 in pyridine in the presence of DCC. ° In the presence of diphenyl phosphite and pyridine, primary amines add to CO2 and to CS2 to give, respectively, symmetrically substituted ureas and thioureas ... 

The earliest NLO studies involving metal pyridyl complexes were reported by Frazier et al. in 1986 who investigated the SHG properties of various group 6 metal pyridyl carbonyls.63 Although most of the complexes tested show little or no activity, (6) and (7) have respective SHG efficiencies of 0.2 and 1.0 times ADP using a 1,064 nm laser.63 Shortly after, Calabrese and Tam reported SHG from the Re1 complex (8).64 Subsequent studies by Eaton and Tam et al.65,66 describe the preparation of inclusion compounds of various metal complexes with thiourea or tris-ort/ o-thymotide. Unfortunately, none of the complexes [W(CO)5L] (L = pyridine, py, or a 4-substituted py) produce SHG-active materials.65,66... 

Some 2-(chloromethyl) derivatives of kojic acid form quaternary salts with tertiary aliphatic amines80-86 and with thiourea.83 Quaternary pyridin-ium salts (LXII) were obtained by Looker and Okamoto81 from LX and LXI in dry pyridine. Water-insoluble derivatives of kojic acid could be rendered water-soluble by these quaternizations. 

In a chemical model for oxidative phosphorylation77 the anaerobic oxidation of iV-benzyl 1,4-dihydronicotinamide by a pyridine solution of haemin was accompanied by the synthesis of ATP from ADP and inorganic phosphate. In support of an alternative chemical model involving sulphenyl phosphates as the reactive species,78 lipophilic thioureas have been shown to inhibit mitochondrial oxidative phos-... 

Chloro-l-methylpyridinium iodide (683) functions as an important mediator in a variety of different reactions. Esters are formed in high yield from acids and alcohols when reacted with one equivalent of (683) in the presence of two equivalents of triethylamine (Scheme 158) (75CL1045). cv-Hydroxy acids are lactonized under similar conditions (76CL49). The pyridinium salt (683) will also convert thioureas into carbodiimides (77CL575) and pyridine-2-thiones to pyridyl sulfides (75CL1159). 

Oxygen can be transferred from the arene oxides to nitrogen-, sulfur-, or phosphorus-containing substrates like pyridine, thiourea, N-methyl-benzothiazol-2-thione, thioacetamide, thiosemicarbazide, thiols, thio ethers, triphenylphosphine,21,160,161 etc. Parent hydrocarbons are formed as products.162 Thus the dimethoxycarbonyl oxide 269 on heating with pyridine produces 9,10-dimethoxycarbonylphenanthrene (270). The reaction of 1 or its... 

The chemical fixation of C02 in the presence of DBU or DBN led to l//-quinazoline-2,4-diones 115 <02T3155>, 5-acylated thiouracils 116a,b were obtained from pyridin-3- and 4-yl thioureas <02AJC287>, and dihydropyrimidines were obtained by an improved Biginelli reaction protocol... 

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