Presence Of Copper Powder Research Articles

Reaction of 2-Aminobenzophenones with Aliphatic Acids in the Presence of Polyphosphoric Acid

Abstract The reaction of 2-aminobenzophenones with aliphatic acids, such as acetic acid, propionic acid, n-butyric acid, and bromoacetic acid, in the presence of polyphosphoric acid afforded 6-substituted 2-anilino-4-phenylquinoline derivatives in fairly good yields. Some of these quinolines were acetylated in the usual way, and the products, 2-(N-acetylanilino) quinolines, were treated with sodium ethoxide to give 1-quinolyl-2(1H)-quinolone derivatives. 2-Amino-5-chlorobenzophenone (Ic) reacted with an equimolar amount of 2-acetamido-5-methylbenzophenone to give 2-(2-benzoyl-4-methylanilino)-6-chloro-4-phenylquinoline, which was also obtained from the reaction of 2,6-dichloro-4-phenylquinoline with Ib in the presence of copper powder. It was found that the reaction mechanism in the formation of 2-anilinoquinolines is similar in type to that in Friedländer’s reaction. Furthermore, the structures of the 2-anilinoquinolines are discussed on the basis of our NMR spectral study.

Reactions of the free toluene-p-sulphonyl radical. Part II. Reactions with polycyclic aromatic hydrocarbons

Toluene-p-sulphonyl iodide, in the presence of copper powder, adds p·Me·C6H4·SO2· radicals to the meso-positions of both anthracene and 2,3-benzanthracene: there is no reaction with phenanthrene or 1,2-benzanthracene. In the absence of copper some meso-substitution of anthracene also occurs. With both 9-methyl and 9,10-dimethyl-anthracene side-chain substitution of hydrogen by p·Me·C6H4·SO2· occurs at a meso-methyl group. These reactions are interpreted in relation to the partial polar character of toluene-p-sulphonyl free radicals.

2-Chloro-4-amino-5-(p-halogenophenoxy)phenylthiocyanate類の合成およびその抗菌性について(第1報)

1) Application of 2, 4-dichloronitrobenzene to the potassium salts 2, 5-dichloro-, 2, 4, 5-trichloro-, p-fluoro-, and p-iodophenols, and p-chlorothiophenol, in the presence of copper powder, afforded (2-phenoxy-5-chloro)nitrobenzenes (III to VI) and [2-(4-chloro-phenylthio)-5-chloro] nitrobenzene (VII). These nitre compounds were reduced to the amino compounds (XI to XVIII) with stannous chloride and hydrochloric acid. Thiocyanation of these compounds, 2-amino-4-chlorophenol, and XIX, by treatment with ammonium thiocyanate and bromine in acetic acid afforded the thiocyano compounds (XXI to XXX). 2) Reaction of the potassium salts of p-chloro- and p-bromophenols with 2-chloro-, 4-bromo-, 2-chloro-4-fluoro-, and 2-chloro-4-iodo-nitrobenzenes, in the presence of copper powder, afforded the nitro compounds (XXXI to XXXVI), which were reduced with stannous chloride and hydrochloric acid to the amino compounds (XXXVII to XLII), and further derived to the thiocyano compounds (XLIII to XLVII) by treatment with ammonium thiocyanate and bromine. 3) All these thiocyanate compounds were submitted to antifungal tests against Candida and Trichophyton. None of the compounds showed much activity against Candida but some of the compounds had activity against Trichophyton comparable to or better than that of I.

Reactions of the Benzil-Triethyl Phosphite Adduct

Abstract The decomposition of benzil-triethyl phosphite adduct in the presence of copper powder or cupric sulfate has been studied. When benzil, triethyl phosphite and cupric sulfate were treated in boiling toluene. cis-dibenzoylstilbene and triethyl phosphate were obtained. When the reaction was carried out in the presence of active hydrogen compounds, such as alcohol, carboxylic acid and amine, the corresponding benzoin derivatives were obtained. Further, when the adduct was decomposed in the presence of phenyl isocyanate or dicyclohexylcarbodiimide, 3, 4, 5-triphenyl-4-oxazoline-2-one or 2-cyclohexylimino-3-cyclohexyl-4, 5-diphenyl-4-oxazoline was obtained, along with triethyl phosphate.

The decomposition of aryl diazonium borofluorides in nitrobenzene and ethyl benzoate in the presence of the free metal, copper powder

In the presence of copper powder the decomposition of aryl diazonium borofluorides in nitrobenzene and ethyl benzoate gives products of homolytic splitting of the diazonium salts. The synthesis of metalloorganic compounds from diazonium salts in the presence of metals occurs by a homolytic mechanism.

有機化合物とヒドラジンの反応 (第2報)

Reduction of 4-nitropyridine 1-oxide and 4-nitro-2-picoline 1-oxide with hydrazine hydrate in the presence of copper powder was examined. When 4-nitropyridine 1-oxide is heated with hydrazine hydrate in ethanol, in the presence of copper powder, it is reduced to 4, 4′-azoxypyridine 1, 1′-dioxide and to 4-aminopyridine 1-oxide by longer heating. If heated in diethylene glycol at a higher temperature of 180-200°, it forms 4-aminopyridine. It was assumed that this deoxygenation chiefly concerns the pyrolysis of 4-aminopyridine 1-oxide by copper catalyst.Under similar conditions, 4-nitro-2-picoline 1-oxide was reduced to 4, 4′-azo (2-picoline) 1-oxide, 4-amino-2-picoline 1-oxide and to 4-amino-2-picoline.

Synthesis of 2‐amino‐5‐ethoxypyridine

Abstract2‐Amino‐5‐ethoxypyridine has been synthesised starting from 2‐amino‐pyridine and 3‐ethoxypyridine. The synthesis from 2‐aminopyridine via 2‐amino‐5‐bromopyridine is not a feasible method of preparation because of the occurrence of various side‐reactions in the action of sodium ethylate on the latter substance in the presence of copper powder as a catalyst. The bromine atom is then replaced mainly by hydrogen instead of by ethoxyl, while simultaneously, one of the hydrogen atoms in the amino group is replaced by an ethyl group. An alternative route via 5‐bromo‐2‐nitro‐pyridine leads to no better result, since in this compound sodium ethylate replaces not the bromine atom but the nitro group by ethoxyl.2‐Amino‐5‐ethoxypyridine can be prepared in a satisfactory manner, however, from 3‐ethoxypyridine via 2‐bromo‐3‐ethoxy‐6‐nitropyridine.

Some reactions of 2‐bromo‐ and 3‐bromoquinolines

Abstract2‐ and 3‐Aminoquinolines were obtained by heating 2‐ and 3‐bromoquinoline respectively with liquid ammonia in the presence of copper powder as a catalyst. 2‐ and 3‐Cyanoquinolines were prepared from the corresponding bromoquinolines by heating with copper cyanide by the method described by Craig (4) for the preparation of 2‐cyanopyridine.The bromoquinolines do not react wih magnesium or with sodium malonate. 2‐Bromoquinoline reacts with potassium pyrrole to form 2‐ (2′ ‐pyrryl) ‐quinoline.