New Quinoline Derivatives on the Basis of (4-Hydroxy-2-methylquinolin-3-yl)acetic Acid

A procedure was developed for the synthesis of (4-hydroxy-2-methylquinolin-3-yl)acetic acid and the corresponding acyl chloride. Reactions of the latter with o-aminobenzenethiol, o-phenylenediamine, o-aminophenol, anthranilic acid, and thiosemicarbazide gave, respectively, 2-(4-hydroxy-2-methylquinolin-3-ylmethyl)-1,3-benzothiazole, -benzoxazole, -benzimidazole, 2-(4-hydroxy-2-methylquinolin-3-ylmethyl)-4H-3,1-benzoxazin-4-one, and 4-hydroxy-2-methyl-3-(5-sulfanyl-1H-1,2,4-triazol-3-ylmethyl)quinoline.     

Reactivity of 3-formyl- and 3-cyanothiochromones toward some N- and C-nucleophiles. Novel synthesis of 3-substituted 2-aminothiochromones

The reactions of 3-formylthiochromone with o-phenylenediamines, o-aminobenzenethiol, and indoles proceeded at the aldehyde group to give 3-(benzimidazol-2-yl)thiochromone, 3-(benzothiazol-2-yl)thiochromone, and 3-di(indol-3-yl)methylthiochromones, respectively. 3-Formyl- and 3-cyanothiochromones react with primary aromatic amines and phenylhydrazine to give the corresponding anils and phenylhydrazones of 3-formyl- and 2-amino-3-formylthiochromones. The reaction of 3-cyanochromones with o-phenylenediamines gave 2-amino-3-[(2-aminophenyl)iminomethyl]-4H-chromen-4-ones.     

Novel polycyclic heterocycles. VIII. 6,11-dihydro-12H-dibenzo[b,f] [1,4]thiazocines and their derivatives

6,11-Dihydro-12H-dibenzo[b,f][1,4]thiazocine, 4 , and its 2-chloro, 7 , and 2-(trifluoromethyl)-, 1 , derivatives, were prepared by the reaction of an o-aminobenzenethiol and α,α-dibromo-o-xylene. Acylation and alkylation at position-12 gave a series of ω-haloacyl-, ω-amino-acyl, and ω-aminoalkyl derivatives of these heterocycles. The conformations, proton magnetic resonance spectra, and x-ray crystallographic studies of these compounds are discussed.     

Studies on phenothiazines. Part 7. Synthesis of 3-substituted 2-aminobenzenethiols and their conversion into phenothiazines

Synthesis of substituted 1-nitrophenothiazines is reported by the Smiles rearrangement in situ, which involves condensation of 3-chloro or methyl-2-aminobenzenethiol with o-halonitrobenzenes (2,4,6-trinitochloro-benzene, 1,4-dichloro-2,6-dinitrobenzene, 2,4,6-tribromo-1,3-dinitrobenzene) in the presence of ethanolic sodium hydroxide. Ir and mass spectral studies are included.     

Efficient propylphosphonic anhydride (®T3P) mediated synthesis of benzothiazoles,benzoxazoles and benzimidazoles

Propylphosphonic anhydride (®T3P) promotes cyclization of o-aminobenzenethiol, o-aminophenol, and o-phenylenediamine with carboxylic acids under microwave irradiation. The one-pot procedure is efficient and allows short reaction times, easy workup, and good yields. Thus, we describe here a method for quick preparation of benzothiazoles, benzoxazoles and benzimidazoles.     

Recyclization of ethyl 1-alkyl-5-benzoyl-6-methylsulfanyl-2-oxo-1,2-dihydropyridine-3-carboxylates into Bicyclic <Emphasis Type="Italic">N</Emphasis>-alkyl-5-benzoyl-2-oxo-1,2-dihydropyridine-3-carboxamide derivatives by the action of nitrogen-containing 1,4- and 1,5-binucleophiles

Reactions of ethyl 1-alkyl-5-benzoyl-6-methylsulfanyl-2-oxo-1,2-dihydropyridine-3-carboxylates with nitrogen-containing 1,4- and 1,5-binucleophiles (o-phenylenediamine, o-aminobenzenethiol, ethane-1,2-diamine, and propane-1,3-diamine) involved recyclization, leading to the formation of fused N-alkyl-5-benzoyl- 2-oxo-1,2-dihydropyridine-3-carboxamides, diethyl 6,6′-oxybis(1-alkyl-5-benzoyl-2-oxo-1,2-dihydropyridine-3-carboxylates), and diethyl 6,6′-[ethane-1,2-diyl(or propane-1,3-diyl)diimino]bis(1-alkyl-5-benzoyl-2-oxo-1,2-dihydropyridine-3-carboxylates), depending on the reactant ratio. The sequence of formation of intermediate recyclization products was determined.     

Relative reactivity in the condensation of 2H-isoindole- and 2H-indazole-4,7-dione derivatives with o-aminobenzenethiol and its derivatives

The effects of substituents on the condensation of o-aminobenzenethiol derivatives with 2H-isoindole- and 2H-indazole-4,7-dione derivatives were studied by competitive reactions.     

Synthesis of indeno[2,1-b][1,4]benzothiazine derivatives from 2-bromoinden-1-ones

2-Bromoinden-1-ones 2 were condensed with 6-substituted 3-aminopyridine-2(1H)-thiones to produce a new type of 4-azaindeno[2,1-b][1,4]benzothiazine derivatives 3 . Substituted 6-phenylindeno[2,1-b][1,4]benzothiazines 4 were also prepared by reacting 2-bromo-5-methoxy- and 2,6-dibromo-5-methoxyinden-1-ones with o-aminobenzenethiol.     

Carbamates,thiolcarbamates, dithiocarbamates and thioncarbamates derived from 2-benzothiazolinone and benzoxazolinone

The reaction of 3-(2-hydroxyethyl)-2-benzothiazoline with methyl, phenyl isocyanate, or dimethylcarbamoyl chloride afforded the carbamates 1–4 . The carbanilate 5 was prepared by the reaction of 2-benzothiazolinone with 3-chloropropyl-N-methylcarbanilate under basic conditions. The reaction of the appropriate 2-benzothiazolinone with the appropriate 2-chloro or 3-chloropropyl disubstituted thiolcarbamate under basic conditions furnished the thiolcarbamates 6–14 . The thiolcarbamate 15 was prepared by the reaction of sodium di-isopropylthiolcarbamate with 3-(chloromethyl)-2-benzothiazolinone. The reaction of 3-(chloromethyl)-2-ben-zothiazolinone and related compound with the appropriate sodium or triethylamine salt of disubstituted dithiocarbamate afforded the dithiocarbamate 16–22 . The reaction of the appropriate xanthate with the potassium salt of bromoacetic acid and the appropriate secondary amine afforded the thionocarbamates 23–29 . The thionocarbamate 30 was synthesized by the reaction of 5-chloro-2-benzothiazolinone with 3-chloropropyl diethylthionocarbamate.     

Perhaloketones XIX . Derivatives of benzo-N-heterocycles

A study was made of the behavior of imidazole and six benzo-N-heterocyclic compounds upon direct treatment with anhydrous and hydrated hexafluoro- and sym-tetrafluorodichloroacetones. Two of the compounds did not react, and four gave addition compounds. Indole reacted with both ketones in the 3-position. Heterocyclic precursors were made by reacting o-phenylenediamine, o-aminophenol, and o-aminobenzenethiol with hexafluoroacetone hydrate, thus introducing the 2-hydroxyhexafluoro-2-propyl moiety into the ring para to the amino group. A similar product was made from o-phenylenediamine and tetrafluorodichloroacetone. These compounds were then converted to twenty-eight heterocyclic derivatives. Four of the latter underwent haloform cleavage of the hydroxyhexahalopropyl group, a novel, but not widely applicable, preparative approach to the corresponding heterocyclic carboxylic acids.     

Reaction of 2,3-epoxyoctafluorobutane with 2-aminobenzenethiol

The reaction of 2,3-epoxyoctafluorobutane with 2-aminobenzenethiol in N,N-dimethylacetamide gave 3-(2-aminophenylsulfanyl)-1,1,1,3,4,4,4-heptafluorobutane-2,2-diol. In the reaction of the same compounds in dioxane, 2,3-bis(trifluoromethyl)-3,4-dihydro-2H-1,4-benzothiazin-2-ol was formed as a result of primary attack by the amino group in 2-aminobenzenethiol on the epoxy ring. The same product was obtained by treatment with 2-aminobenzenethiol of 2,3-bis(trifluoromethyl)-2H-1,4-benzoxazin-2-ol which was synthesized from 2,3-epoxyoctafluorobutane and 2-aminophenol.     

2-Alkoxy-3,4-dihydropyrans as modular substrates to construct polyheterocycles by reacting with NH2-containing bisnucleophiles

2-Alkoxy-3,4-dihydropyrans were proved to be a class of powerful modular substrates to construct polyheterocycles by reacting with NH₂-containing dinucleophiles, such as anthranilamide, 2-aminobenzenethiol, 1-(2-aminophenyl)pyrrole, and 2-(o-aminophenyl)indole in the presence of LiBr·H₂O. A three-component reaction of isatoic anhydride, 2-alkoxy-3,4-dihydropyran and amine was also developed as well.     

Synthesis of 2-oxo and 2-thioxo-3(2H)-benzothiazoleethanimic acid anhydride with acetic acid and related products

The reaction of the appropriate 2-benzothiazolinone with 2-chloroacetamide under basic conditions afforded the 2-oxo-3(2H)-benzothiazolineacetamides 6–9. The 2-thioxo-3(2H)-benzothiazolineacetamide ( 10 ) was prepared by the reaction of 3-(carbethoxymethyl)benzothiazoline-2-thione with ammonium hydroxide. The reaction of acetamides 6–10 with the appropriate anhydride containing a catalytic amount of the sodium salt of the acid corresponding to the anhydride afforded the titled compounds 11–18 in excellent yields. The omission of the catalyst in the same reaction furnished a mixture containing 57% of the titled compound, 37% of the nitrile and 6% of an unknown. Possible mechanism and supporting nmr, ir and mass spectral data are discussed.     

Heterocyclic compounds from 3,3-dimercapto-1 -aryl-2-propen-1-ones. Note 2. Condensation with o-aminothophenol and o-aminophenol

The condensation of 3,3-dimercapto-1-phenyl-2-propen-1-one with o-aminothiophenol and o-aminophenol in hot xylene gave 2-phenacylbenzothiazole ( 3 ) and 2-phenacylbenzoxazole ( 5 ). When the reaction with o-aminophenol was carried out in hot benzene, 2-beuzoylthioacctamidophenol ( 4 ) was obtained, which, heated in hot xylene gave 5. Ethyl benzoylacetale by reaction with o-aminothiophenol gave 3 , whereas by reaction with o-aminophenol gave no heterocyclic compound. However, we were able to isolate 2-benzoylacetamidophenol ( 6 ), ethyl β-phenyl-β-(o-hydroxy)phenyliminopropionate ( 7 ), and 2-[β-(o-hydroxy)anilino] cinnamoylamidophenol ( 8 ). Ir and nmr spectra of synthesized compounds point out the existence of tautomers.     

Heterocyclic derivalives of naphthalene-1,8-dicar boxylie anhydride. Part III. Benzo[k,l] thioxanthene-3,4-dicarboximides

Condensation of 4-bromo- ( 4 ) and 4-nilro-l,8-naphthalimides ( 5 ) with 2-aminobenzenethiol gave 4-(2-aminoulicnylthio)-1,8-naphthalimides ( 7 ). Cyclisalion of 7 by the: Pschorr reaction afforded benzo[k,l] thioxanthene-3,4-dicarboximides ( 8 ), also obtained by reaction ol amities with benzo[k,l] thioxanthene-3,4-dicarboxylie anhydride ( 11 ).     

Synthesis,Structure and Reactivity of Organoindium 1,2-Benzenedithiolates and 2-Amidobenzenethiolates

Organoindium compounds of redox active 1,2-benzenedithiolate and 2-amidobenzenethiolate ligands were synthesized and tested for reactivity against mild oxidants. The reaction of Me₃In and (NCN)InMe₂ [NCN=2,6-bis(dimethylaminomethy)phenyl] with 3,4-toluenedithiol (H₂tdt) at room temperature afforded [MeIn(tdt)(py)]₂ ( 1 ) and (NCN)In(tdt) ( 2 ), respectively. A similar reaction of Me₃In with 2-aminobenzenethiol (H₂abt) in toluene under reflux afforded [MeIn(abt)(py)]₂ ( 3 ). The reaction of (NCN)InCl₂ with one equivalent of Li₂(abt) or two equivalents of Li(Habt) afforded the compounds [(NCN)In(abt)]⋅LiCl(thf)₂ ( 4 ⋅LiCl(thf)₂) and (NCN)In(Habt)₂ ( 5 ), respectively. The X-ray crystal structures of 1 and 3 are similar and show dimeric structures via μ-S-(tdt) and μ-N-(abt) ligands, respectively. Compounds 2 and 4 possess similar monomeric structures and tridentate NCN pincer ligands. DFT computational studies have been used to rationalize the observed solid-state structures and discern the potential reactivity of compounds 1 – 4 against oxidants. The reaction of 1 and 2 with excess iodine resulted in loss of the 3,4-toluenedithiolate ligand and the formation of the oligomeric disulfide [tdt]_n, while 3 and 4 showed no reactivity under similar conditions. This contrasts the reactivity of previously reported organoindium o-amidophenolate complexes which undergo oxidative addition of iodine to afford ligand-centered radical species.     

Synthesis and characterization of novel chalcogen and pnictogen coordinated Bi(III) complexes—the first Se,Se′ coordinated Bi metallacycle

Inorganic and organometallic Bi(III) complexes with five-membered heterocycles were studied. The preparation, properties, and spectroscopic characterization (¹H NMR, IR, MS-fragmentation behaviour) of the new compounds are reported. The first member of Se coordinated Bi metallacycles is presented. Bi organyles with the o-aminobenzenethiol ligand system, at present widely investigated, are described as o-aminobenzenethiolate and o-aminobenzenethioldiate derivatives.     

Synthesis of 3-substituted-2-benzothiazolinone, 2-benzoxazolinone and benzothiazoline-2-thione

The reaction of 2-benzothiazolinone, 2-benzoxazolinone or benzothiazoline-2-thione under basic conditions with various electrophiles afforded the titled compounds 1-13, 29-31 and 40-48. The 3-(substituted-aminomethyl)-2-benzothiazolinone and related compounds 14-25 were prepared by the reaction of 3-(hydroxymethyl)-2-benzothiazolinone or the appropriate 2-benzothiazolinone and formaldehyde with the appropriate amine or substituted aniline. The reaction of 9, 13 or 25 with methyl iodide afforded the quaternary ammonium iodides 26-28. The reaction of the appropriate potassium salts of various phenol with 3-(chloromethyl)-2-benzothiazolinone afforded the 3-(substituted-phenoxymethyl)-2-benzothiazolinone and related compounds 32-39. The ethyl or isopropylxanthates 49-54 were synthesized by the reaction of 3-(chloromethyl)-2-benzo-thiazolinone and appropriate compounds with potassium ethyl or isopropyl xanthate. The reaction of 3-(chloromethyl)-2-benzothiazolinone with sodium sulfide afforded the sulfide 55.     

Reaction of 2,5-(Dibenzothiazolin-2-yl)thiophene with Some Metal Ions

2,5-(Dibenzothiazolin-2-yl)thiophene has been synthesized by the reaction of 2,5-thiophenedicarboxaldehyde and $\text{o}$-aminobenzenethiol. It reacts as a neutral ligand with Pd(II). However, it reacts as a dianion with Cu(II), Ag(I), Cd(II), Pb(II) and Zn(II), suggesting that the ligand is bonded as the conjugate base of the Schiff base 2,5-thiophenediylbis{N-(pheylen-2-thiol)aldimine}. Its behavior with Hg(II), Ru(III), Pt(II), Rh(III) and Ni(II) involves the opening of one of the thiazoline rings of the ligand.     

Darstellung,Eigenschaften und Molekülstrukturen von Dimethylmetallalkoxiden und ‐amiden des Aluminiums und Galliums

Preparation, Properties, and Molecular Structures of Dimethylmetal Alkoxides and Amides of Aluminium and Gallium Dimethylaluminium‐ ( 1 ) and Dimethylgallium‐o‐methoxyphenyl‐1‐ethoxide ( 2 ) were obtained by reaction of Me₃Al and Me₃Ga respectively with o‐Methoxyphenyl‐1‐ethanol in n‐pentane. Dimethylaluminium‐ ( 3 ) and dimethylgallium‐o‐methoxyphenyl‐2‐ethylamide ( 4 ) were prepared by treatment of Me₂AlCl and Me₂GaCl respectively with Lithium‐o‐methoxyphenyl‐2‐ethylamide. Trimethylgallium‐o‐methoxyphenylmethylamine‐Adduct ( 5 ) was isolated using reaction of Me₃Ga with the corresponding amine. The compounds were characterised by ¹H‐, ¹³C‐, and ²⁷Al n.m.r. spectroscopy. The molecular structures of 2 and 5 were determined by X‐ray diffraction. Compounds 1 – 4 form brigded dimeric molecules. The bond distances of the central Ga₂O₂ ring in 2 correspond to those of compounds of similar structure.