• 한국진공학회:학술대회논문집
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• 한국진공학회 2011년도 제41회 하계 정기 학술대회 초록집
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• pp.207-207
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• 2011

Aromatic nitriles possess versatile utilities and are indispensible not only in organic synthesis but also in chemical industry. In fact, the nitrile group is an important precursor for various functional groups such as aldehydes, amines, amidines, tetrazoles, amides, and their carboxyl derivatives. Representative methods for the preparation of organonitriles with cyanide-containing reagents are the Sandmeyer and Rosenmund-von Braun reactions. Recently, a catalytic route to aryl nitriles has been reported on the basis of the chelation-assisted C-H bond activation or metal-catalyzed cyanation of haloarenes. In those cyanation protocols, the "CN" unit is provided from metal-bound precursors of MCN (M=Cu, K, Na, Zn), TMSCN, or K3Fe(CN)6. Additionally, it can be generated in situ from nitromethane or acetone cyanohydrin. Herein, we report the first example of generating "CN" from two different, readily available precursors, ammonia and N,N-dimethylformamide (DMF). In addition, its synthetic utility is demonstrated through the Pd-catalyzed cyanation of arene C-H bonds.

• Bulletin of the Korean Chemical Society
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• 제25권10호
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• pp.1545-1550
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• 2004

meso-Functionalized dipyrromethanes 6-10 were synthesized by acid-catalyzed addition of pyrrole to ${\alpha}$-position of 2-alkenyl pyrroles. The regiochemistry of the reaction can be explained by either the formation of more stable carbocation intermediate or ${\beta}$-addition of ${\alpha},{\beta}$-unsaturated carbonyl compounds. The starting 2-alkenyl pyrroles were synthesized by Aldol condensation of 2-formylpyrrole with active methylene compounds such as nitromethane, diethylmalonate and malononitrile. Attempted ‘2+2' condensation of meso-diethylmalonyldipyrromethane, meso-(p-tolyl)dipyrromethane and p-tolualdehyde afforded three different porphyrins 12, 13 and 14 in reasonable yields. On the other hand, meso-(nitromethyl)dipyrromethane with p-(tbutyl) benzaldehyde resulted in the formation of three different porphyrins such as 5,15-dicyano-10,20-diarylporphyrin (16), 5-cyano-15-formyl-10,20-diarylporphyrin (17) and 5,15-diformyl-10,20-diarylporphyrin (18) in low yields. Conversion of nitromethyl groups to nitrile and (or) formyl group was observed under the porphyrin forming conditions.

• Bulletin of the Korean Chemical Society
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• 제34권7호
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• pp.2125-2130
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• 2013

A new nickel(II) complex $[NiL^1]^{2+}$ ($L^1$ = 1-(2-aminoethyl)-3-(N-{2-aminoethyl}aminomethyl-1,3-diazacyclohexane) containing one 1,3-diazacyclohexane ring has been prepared selectively by the metal-template condensation of formaldehyde with N-(2-aminoethyl)-1,3-propanediamine and ethylenediamine at room temperature. The complex reacts with nitroethane and formaldehyde to yield the pentaaza macrocyclic complex $[NiL^2]^{2+}$ ($L^2$ = 8-methyl-8-nitro-1,3,6,10,13-pentaazabicyclo[13.3.1]heptadecane) bearing one C-$NO_2$ pendant arm. The reduction of $[NiL^2]^{2+}$ by using Zn/HCl produces $[NiL^3(H_2O)]^{2+}$ ($L^3$ = 8-amino-8-methyl-1,3,6,10,13-pentaazabicyclo[13.3.1]heptadecane) bearing one coordinated C-$NH_2$ pendant arm that is readily protonated in acid solutions. The hexaaza macrocyclic complex $[NiL^4]^{2+}$ ($L^4$ = 8-phenylmethyl-8-nitro-1,3,6,8,10,13-hexaazabicyclo[13.3.1]heptadecane) bearing one N-$CH_2C_6H_5$ pendant arm has also been prepared by the reaction of $[NiL^1]^{2+}$ with benzylamine and formaldehyde. The nickel(II) complexes of $L^1$, $L^2$, and $L^4$ have square-planar coordination geometry in the solid states and in nitromethane. However, they exist as equilibrium mixtures of the square-planar $[NiL]^{2+}$ (L = $L^1$, $L^2$, or $L^4$) and octahedral $[NiL(S)_2]^{2+}$ species in various coordinating solvents (S); the proportion of the octahedral species $[NiL(S)_2]^{2+}$ is strongly influenced by the ligand structure and the nature of the solvent. Synthesis, spectra, and chemical properties of the nickel(II) complexes of $L^1-L^4$ are described.

• 한국식품과학회지
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• 제32권1호
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• pp.56-61
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• 2000

청갓으로 만든 갓김치의 휘발성 화합물의 종류를 GC/FID와 GC/MSD를 사용하여 분리 동정하고, 발효 숙성 중 isothiocyanates와 그 유도체함량의 변화를 측정하였다. 청갓 김치의 수증기 증류물로부터 14종의 휘발성화합물을 분리, 동정하였으며 그 중 hexadecanoic acid를 비롯한 acid와 nitromethane등의 hydrocarbons류가 전체의 63%이상을 차지하였다. 갓의 특징적인 자극성 성분으로 알려진 isothiocyanates와 유도체들의 함량은 전체화합물의 30%로, 2-phenylethyl isothiocyanate가 주요성분이었고, 그밖에 benzothiazole 2-methylbenzothiazole, 2-(3H)-benzothiazolone 등이 동정되었다. 청갓 김치의 발효숙성 중 isothiocyanates와 그 유도체들의 상대적 함량 변화는 저장4일 이후부터 뚜렷하게 감소되었으며, 그 중 2-phenylethyl isothiocyanate경우 저장 7일째에 50%이상, 저장 14일째에는 80%이상 소실되는 것으로 나타났다.