• Bulletin of the Korean Chemical Society
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• 제34권3호
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• pp.863-867
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• 2013

A series of azo disperse dyes having dicyanovinyl groups was synthesized by the Knoevenagel condensation with malononitrile from carbonyl substituted phenylazo disperse dyes which were prepared by conventional diazo coupling reaction of aniline derivatives as diazo components. A variety of coupling components such as anilines, an indole and a pyridone were used. The azo disperse dyes were evaluated for their spectral properties and dyeing assessment on the polyester fabrics. The azo disperse dyes containing dicyanovinyl groups showed bathochromic shifts and darker colors due to increased electron withdrawing strength in their azo components and extended conjugation by dicyanovinyl groups than their parent carbonyl substituted azo dyes. The dyes containing 2-acetylamino-5-methoxy substituent in the coupling component exhibited higher wavelength of maximum absorbance (${\lambda}_{max}$) and significant negative solvatochromism than those of other dyes due to intramolecular hydrogen bonding.

• Journal of Life Science
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• 제9권2호
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• pp.49-51
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• 1999

Reactions of 2,6-Lutidine with active methyl group anilines in the presence of sulfur gave the desired thioamides 1. Reactions of synthesized thioamides 1 with sulfur and SiO2 or SeO2 gave the corresponding amide 2. We now report conversion of thioamide to amide by using oxidzing inorganic reagant

• Macromolecular Research
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• 제13권1호
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• pp.2-7
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• 2005

A series of ethylene polymerization catalysts based on tridentate bis-imine ligands coordinated to iron and cobalt was reported. The ligands were prepared through the condensation of sterically bulky anilines with allyloxy-and benzyloxy-substituted 2,6-acetylpyridines. The pre-catalyst complexes were penta-coordinate species of the general formula $\{[(ArN=C(Me))_2(4-RO-C_5H_3N)]MCl_2\}$ (Ar=ortho dialkyl-substituted aryl ring; R=allyl, benzyl; M=Fe, Co). In the presence of ethylene and methyl alumoxane cocatalysts, these complexes were active for the polymerization of ethylene, with activities lower than those of metal complexes of the general formula $\{[(2-ArN=C(Me)_2C_5H_3N]MCl_2\}$ (Ar=ortho dialkyl-substituted aryl ring; M=Co, Fe), containing no substituents in 2,6-acetylpyridine ring. The effects of the catalyst structure and temperature on the polymerization activity, thermal properties, and molecular weight were discussed.

• Bulletin of the Korean Chemical Society
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• 제33권11호
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• pp.3571-3575
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• 2012

A number of novel small molecules, safrole oxide derivatives 4a-c, 6a-c, 9a-h, were synthesized by the reaction of safrole oxide with anilines 3 and 5, or its alkyl allyl ether derivative 7 with alkyl bromide 8 in moderate yields. The antiproliferative effects of all the target molecules on A549 cell growth were investigated and it was found that the 14 novel compounds could suppress A549 lung cancer cell growth. Among them, compound 6b was the most effective compound in inhibiting the proliferation of A549 cells.

• Bulletin of the Korean Chemical Society
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• 제24권7호
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• pp.993-998
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• 2003

In the aminolysis of phenacyl bromides ($YC_6H_4COCH_2Br$) with benzylamines ($XC_6H_4CH_2NH_2$) in acetonitrile, the Bronsted βx (βnuc) values observed are rather low ( βX = 0.69-0.73). These values are similar to those (βx $^~_=$ 0.7) for other aminolysis reactions of phenacyl compounds with anilines and pyridines, but are much smaller than those ( βx = 1.1-2.5) for the aminolysis of esters with benzylamines which are believed to proceed stepwise with rate-limiting expulsion of the leaving group. The relative constancy of the βx values (βx $^~_=$ 0.7) irrespective of the amine, leaving group and solvent can be accounted for by a bridged type transition state in the rate-limiting expulsion of the leaving group. Thus the aminolysis of phenacyl derivatives are proposed to proceed stepwise through a zwitterionic tetrahedral intermediate ($T^{\pm}$), with rate-limiting expulsion of the leaving group from $T^{\pm}$. In the transition state, the amine is bridged between the carbonyl and α-carbons, which leads to negligible effect of amine on the leaving group expulsion rate.

• Bulletin of the Korean Chemical Society
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• 제28권11호
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• pp.2003-2008
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• 2007

The aminolysis of diphenyl thiophosphinic chloride (2) with substituted anilines in acetonitrile at 55.0 oC is investigated kinetically. Kinetic results yield large Hammett ρX (ρnuc = ?3.97) and Bronsted βX (βnuc = 1.40) values. A concerted mechanism involving a partial frontside nucleophilic attack through a hydrogen-bonded, four-center type transition state is proposed on the basis of the primary normal kinetic isotope effects (kH/kD = 1.0-1.1) with deuterated aniline (XC6H4ND2) nucleophiles. The natural bond order charges on P and the degrees of distortion of 42 compounds: chlorophosphates [(R1O)(R2O)P(=O)Cl], chlorothiophosphates [(R1O)(R2O)P(=S)Cl], phosphonochloridates [(R1O)R2P(=O)Cl], phosphonochlorothioates [(R1O)R2P(=S)Cl], chlorophosphinates [R1R2P(=O)Cl], and chlorothiophosphinates [R1R2P(=S)Cl] are calculated at the B3LYP/ 6-311+G(d,p) level in the gas phase.

• Bulletin of the Korean Chemical Society
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• 제28권11호
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• pp.2009-2014
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• 2007

The aminolysis of diphenyl thiophosphinic chloride (2) with substituted anilines in acetonitrile at 55.0 oC is investigated kinetically. Kinetic results yield large Hammett ρX (ρnuc = ?3.97) and Bronsted βX (βnuc = 1.40) values. A concerted mechanism involving a partial frontside nucleophilic attack through a hydrogen-bonded, four-center type transition state is proposed on the basis of the primary normal kinetic isotope effects (kH/kD = 1.0-1.1) with deuterated aniline (XC6H4ND2) nucleophiles. The natural bond order charges on P and the degrees of distortion of 42 compounds: chlorophosphates [(R1O)(R2O)P(=O)Cl], chlorothiophosphates [(R1O)(R2O)P(=S)Cl], phosphonochloridates [(R1O)R2P(=O)Cl], phosphonochlorothioates [(R1O)R2P(=S)Cl], chlorophosphinates [R1R2P(=O)Cl], and chlorothiophosphinates [R1R2P(=S)Cl] are calculated at the B3LYP/ 6-311+G(d,p) level in the gas phase.

• Bulletin of the Korean Chemical Society
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• 제14권5호
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• pp.621-625
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• 1993

Kinetic studies are conducted for the reactions of Y-benzoyl, Y-benzenesulfonyl and Y-benzyl halides with X-anilines in acetonitrile, and the transition state (TS) structures and their variations with substituents X and Y are discussed. The magnitude of the cross-interaction constants, $\rho$xy, is the largest and the inverse secondary kinetic isotope effect (SKIE), $k_H/k_D$ < 1.0, with deuterated aniline nucleophiles is the smallest for benzoyl fluoride reflecting the tightest TS for this compound. The SKIEs for sulfonyl halides are relatively large due to a relatively large, diffuse nature of the reaction center, S, causing weaker steric hindrance to the vibrations of the two N-H(D) bonds. For benzoyl and sulfonyl halides, the trends in $k_H/k_D$ and $Ir_XI$ variations with $\sigma$Y contradict each other, which is rationalized by the negative charge accumulation on the reaction center, CO and SO$_2$, causing inefficient transfer for the substrate with an electron donating substituent.

• 대한화학회지
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• 제29권4호
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• pp.441-447
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• 1985

몇가지 벤즈아닐리드 유도체를 합성하여 광반응될 때 생성물의 구조를 밝혔으며, 메카니즘을 연구하였다. 치환된 아닐린에 benzoyl chloride 유도체를 넣어 아실화하여 benzanilide 유도체를 합성하였다. N, N-dibenzoylaniline 유도체는 뜨거운 benzoyl chloride 유도체에 아닐린을 소량씩 가하여 얻었다. 2-chlorobenzanilide와는 달리 2-methylbenzanilide나 2'-methylbenzanilide는 photo-Fries형 생성물을 주었다. 2-위치에 니트로기가 도입된 benzanilide는 광반응을 하지 않았다. 들뜬 상태가 광반응을 할만큰 충분한 에너지를 갖고 있지 않기 때문이라고 생각한다. N, N-dibenzoylaniline이나 N, N-di-(2-chlorobenzoyl) aniline의 광반응으로 부터 쉽게 photo-Fries형 반응을 할때 단일선 상태가 상관하는것 같다. 왜냐하면 산소가 반응에 아무런 영향이 없기 때문이다. 극성이 작은, 또 점성이 낮은 용매에서 양자수득률이 좋았다. 단일 들뜬상태에서 카르보닐탄소와 질소사이 결합이 끊어져 용매 바구니라디칼 쌍이 되었다가 반전되어 재결합하면 생성물이 된다고 생각된다.

• Applied Biological Chemistry
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• 제41권6호
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• pp.471-476
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• 1998

신 농약을 개발할 목적으로 선도화합물인 티아졸린의 곁가지를 변화시킨 새로운 2-이미노티아졸린 유도체를 합성하여 항균활성을 검색하였다. 디키틴과 아닐린으로부터 제조된 아세토아세트아닐리드 유도체를 브롬화하여 상응하는 감마-브로모아세토아세트아닐리드 유도체를 얻고 이를 티오우레아 유도체와 반응시켜 2-이미노티아졸린 유도체를 합성하였다. 2-이미노티아졸린의 항균활성을 검색하고자 6 종류의 대표적인 식물 병원균에 대한 시험(in vivo)을 하였다. 2-페노치환체들은 벼도열병균에 대하여 250 ppm에서 탁월한 항균성을 나타냈다. 1차 활성시험에서 방제가 90이상으로 평가된 것만 선발하여 2차 활성시험(농도저하 시험)을 수행하였다. 2-아릴기에 전자주게보다 전자 끌게, 전자끌게 중에서도 할로겐치환체가 도입된 경우에 고 활성을 나타냈으며 불소원자가 치환된 경우에 활성이 비교적 양호하였다.