• Journal of the Korean Chemical Society
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• v.34 no.6
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• pp.652-657
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• 1990

Primary amines react with 1,6-hexanediol at 180$^{\circ}C$ for 5 h under argon atmosphere in the presence of both $RuCl_3{\cdot}3H_2$O and $PR_3$ to give N-substituted perhydroazepine derivatives in good yields. For aromatic amines such as anilines, $RuCl_3{\cdot}3H_2$O combined with $PPh_3$ showed the highest catalytic activity. On the other hand, in the reaction of aliphatic amines, $RuCl_3{\cdot}3H_2$O combined with $PBu_3$ showed the highest catalytic activity. These differences may be attributed to the difference in the basicity of these amines. Less basic aromatic amines may require less basic phosphines, while more basic aliphatic amines may require more basic phosphines as the ligands.

• Journal of the Korean Chemical Society
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• v.41 no.2
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• pp.69-76
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• 1997

Kinetic studies for the nucleophilic substitution reactions of the benzoic anhydrides with anilines in methanol-acetonitrile mixtures at$35.0{\circ}C$have been carried out in order to elucidate the reaction mechanism. Individual rate constants$k_{XY}$and$k_{XZ}$were decided from the ratios of the reaction products for the competitive substitution reaction at either one of the two carbonyl carbons in benzoic anhydride. Transition state structure and reaction mechanism were elucidated by the Hammett$p_x,\;p_y$and$p_z$values and cross interaction constant$p_x\;p_y$and$p_zvalues. The reaction of the benzoic anhydride has been proposed to proceed by a frontside attack$S_N2 $mechanism with four-membered ring transition state from unusually large magnitude of the$ρ_X,\;ρ_{XY},\;ρ_{XZ}$and positive$p_Y$values.

• Journal of the Korean Chemical Society
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• v.29 no.4
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• pp.426-436
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• 1985

Preparative and kinetic photochemical reactions of several benzanilides were studied. Several substituted benzanilides were synthesized by acylation of substituted anilines with substituted benzoyl chlorides. While benzanilide gave a photo-Fries type reaction product, 2-chlorobenzaniline, 2-bromobenzanilide, and 2-methoxybenzanilide gave a photocyclization reaction product, phenanthridone. Since 8-chlorophenanthridone was obtained from 2,2'-dichlorobenzanilide, the carbonyl phenyl is the excited site. Quantum yield of photocyclization of 2-chlorobenzanilide, 2'-chlorobenzanilide, and 2-methoxybenzanilide were obtained. 2-Chlorobenzanilide was photocyclized effectively and 2'-chlorobenzanilide ineffectively. Since the oxygen present in the reaction medium retarded the photocyclization reaction of 2-chlorobenzanilide, the triplet state of 2-chlorobenzanilide is involved. The mechanism of the photocyclization of 2-chlorobenzanilide is suggested: $\pi-complex$ between carbonyl phenyl and N-phenyl was formed from the triplet state of 2-chlorobenzanilide; neighbour phenyl (N-phenyl) assists for leaving of chlorine from carbonyl phenyl to make an intermediate, cyclized conjugated radical, because electron donating group on the N-phenyl ring accelerated the reaction; hydrogen detachment from the intermediate is obviously not a rate determined step because there was no isotope effect on the rate of photocyclization. The photocyclization reaction rate of 2-methoxybenzanilide was faster in the presence of oxygen than in the absence of oxygen. Thus, the singlet excited state of 2-methoxybenzanilide is involved in the reaction. Probably, the intermediate, methoxyhydro-phenanthridone is oxidized by oxygen in the medium to give phenanthridone.

• Applied Biological Chemistry
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• v.30 no.3
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• pp.227-233
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• 1987

Some derivatives of 3-(benzothiazol-2-yl)-1-methyl urea were synthesized by reaction of methyl isocyanate with 2-aminobenzothiazole derivatives prepared by thiocyanation of various substituted anilines. The compounds synthesized were identified by IR, NMR and mass spectra as 3-(5-methyl benzothiazol-2-yl)-1-methyl urea, 3-(5,6-dimethyl benzothiazol-2-yl)-1-methyl urea, 3-(6-ethyl benzothiazol-2-yl)-1-methyl urea, 3-(6-methoxy benzothiazol-2-yl)-1-methyl urea, 3-(6-chloro benzothiazol-2-yl)-1-methyl urea, and 3-(5, 6-dichloro benzothiazol-2-yl)-1-methyl urea. These compounds were subjected to the test for pre-emergence herbicidal activity in the pots with wettable powder formulation. All of these compounds showed pre-emergence herbicidal activity on the grasses (Digitaria adscendens HENR and Setaria viridis P. BEAUV) and broad-leaf weeds (Portulaca oleraces L. and Chenopodium album L.) at the dosage of 800g a.i. per 10a. Of the 6 compounds, 3-(6-ethyl benzothiazol-2-yl)-1-methyl urea showed the highest herbicidal effect on both the grasses and broad-leaf weeds. Even at the rate of 50g a.i. per 10a, this compound inhibited the growth of grasses, selectively.

• Applied Biological Chemistry
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• v.26 no.4
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• pp.231-238
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• 1983

N-Benzoylglycylanilide and N-benzoylalanylanilide derivatives were synthesized from N-benzoylglycine and N-benzoylalane with anilines. respectively. The products were identified by elemental analysis, IR, UV and NMR spectra with N-benzoylglycylanilide (I), N-benzoylglycyl-o-toluidide(II), N-benzoylglycyl-m-toluidide(III), N-benzoylglycyl-p-toluidide(IV), N-benzoyl-L-alanylanilide(V), N-bnzoyl-L-alanyl-o-toluidide(VI), N-benzoyl-L-alnnyl-m-toluidise(VII), N-benzoyl-L-alanyl-p-toluidide(VIII). These compounds were tested for their phytotoxicity to the germination and seedling growth of rice, radish, green pea plants and turf grass. Among them, N-benzoyl-Lalanyl-m-toluidide had strongly inhibitory effect on the seedling growth of radish seeds, and N-benzoyl-L-alanylanilide showed an inhibitory activity especially upon the seedling growth of turf seeds. In addition, the inhibitory rate of plant seed growth differed with the isomeric position(ortho, meta and para) of methyl group; N-benzoylglycyl-m-toluidide was more effective than both N-benzoylglycyl-o-toluidide and N-benzoylglycyl-p-toluidide derivatives, and also N-benzoyl-L-alanyl-m-toluidide was more effective than both N-benzoyl-L-alanyl-o-toluidide and N-benzoyl-L-alanyl-p-toluidide.

• Nuclear Engineering and Technology
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• v.5 no.1
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• pp.44-54
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• 1973

In order to clarify an effective procedure of labelling organic chloro compounds by $^{38}$ Cl, phenyl chloro derivatives(7 kinds), chloro nitrobenzenes(6 kinds), chloro anisoles(2 kinds), chloro anilines(3 kinds), chloro toluenes(3 kinds), benzyl cholorides(4 kinds), and other comparing samples(3 kinds) were irradiated in the TRIGA Mark-II research reactor and the inorganic $^{38}$ Cl yields were compared with the irradiation times after extracting the inorganic portion with an aqueous solution of alkali. It was found that the relative change between the inorganic $^{38}$ Cl yield and the irradiadiation time depends a great deal on the state of the sample, and a solid sample gave a lower and steady inorganic yield. The inorganic $^{38}$ Cl yield was decreased in the order of phenyl chloro derivatives < chloro tol uene$^{38}$ Cl yield of homo functional compounds and the number of chlorine atoms on the benzene ring. Generally, poly chloro substituted derivatives could give a higher yield than those of less chloro substituted. The results were discussed and the feasibility of these results for labelling purpose was criticized.