Cyanation of Anilines to Aryl Nitriles Using tert-Butyl Isocyanide: A Simple and Copper-free Procedure

Poh Wai Chia,Fu Siong Julius Yong,Habsah Mohamad,Su-Yin Kan 대한화학회 2019 Bulletin of the Korean Chemical Society Vol.40 No.10

In this manuscript, a simple and copper-free procedure for the synthesis of aryl nitrile derivatives from anilines is described. Under the improved protocol, the anilines were reacted with tert-butyl isocyanide under a mild reaction condition without the use of solvents and copper catalyst to synthesize benzonitriles. This copper-free Sandmeyer-type reaction could tolerate a range of anilines bearing different functional groups and also can be conducted even without the exclusion of air. In addition, this method has afforded the aryl nitriles in moderate to good yields (52?81%). The obtained results in this study reveal that the tert-butyl isocyanide as a potential cyanide source for the cyanation reaction.

Palladium-Catalyzed Domino Heck-Cyanation Cascade to 3-Cyanomethyl 2,3-Dihydrobenzofuran and 2,3-Dihydroindoles

이현승,김고훈,Jin Woo Lim,김재녕 대한화학회 2011 Bulletin of the Korean Chemical Society Vol.32 No.3

Palladium-Catalyzed Domino Heck-Cyanation Cascade to 3-Cyanomethyl 2,3-Dihydrobenzofuran and 2,3-Dihydroindoles

Lee, Hyun-Seung,Kim, Ko-Hoon,Lim, Jin-Woo,Kim, Jae-Nyoung Korean Chemical Society 2011 Bulletin of the Korean Chemical Society Vol.32 No.3

A New Combined Source of “CN” from N,N-Dimethylformamide and Ammonia in the Palladium-Catalyzed Cyanation of Aryl C-H Bonds

Jiho Choi,Jinho Kim,Sukbok Chang 한국진공학회 2011 한국진공학회 학술발표회초록집 Vol.41 No.-

Palladium nanoparticles anchored polydopamine-coated graphene oxide/Fe3O4 nanoparticles (GO/Fe3O4@PDA/Pd) as a novel recyclable heterogeneous catalyst in the facile cyanation of haloarenes using K4[Fe(CN)6] as cyanide source

Hojat Veisi,Taiebeh Tamoradi,Asra Rashtiani,Saba Hemmati,Bikash Karmakar 한국공업화학회 2020 Journal of Industrial and Engineering Chemistry Vol.90 No.-

Pd(0) nanoparticles stabilized over polydopamine (PDA) capped magnetic GO/Fe3O4 nanocomposites(GO/Fe3O4@PDA/Pd) have been synthesized in variable Pd load following a post grafting approach. Pd hasbeen reduced in situ by the functionalized PDA avoiding the use of external harsh reductant. Thestructural properties of the synthesized materials were studied by different analytical techniques likeField Emission Scanning electron microscopy (FESEM), Energy Dispersive X-ray Spectroscopy (EDX), HighResolution Transmission Electron Microscopy (HRTEM), Fourier Transformed Infrared (FT-IR) spectroscopy,Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES), Thermo Gravimetric Analysis(TGA), Powder X-Ray Diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS). The novel GO/Fe3O4@PDA/Pd(0) nanocomposite exhibited excellent performance as a reusable catalyst in the facilecyanation of aryl halides using K4[Fe(CN)6] as a low cost and safe cyanating agent. The aryl nitriles wereobtained in good to excellent yields and the catalyst was recycled up to 13 times with minimal change inits catalytic activity.

4-cyano-3, 5-difluorophenol의 새로운 합성법

송정섭(Song Jeong-Sup) 한국산학기술학회 2006 한국산학기술학회논문지 Vol.7 No.6

액정 재료의 중간제로 사용되는 4-cyano-3, 5-difluorophenol를 3,5-difluorophenol을 출발물질로 하여 요오드 치환반응 및 시안화반응으로 이루어지는 2 단계로 합성하였다. 생성된 4-cyano-3 ,5-di fluorophenoI은 분광학적 방법으로 분석하여 표준 시료와 비교 확인되었다. 4-Cyano-3,5-difluorophenol, useful as intermediate in the manufacturing of liquid crystals, was prepared by the regioselective iodination of 3,5-difluorophenol to give 4-iodo-3,5-difluorophenol, which was then converted to 4-cyano-3,5-difluorophenol under a mild reaction condition. The reaction products were characterized by spectroscopic methods and confumed by comparison of these analytical data with reported values in the literatures.

Cyanate를 섭취한 흰쥐에서 운동으로 인한 혈액성분의 변화

김태형,박덕일,박재식,주영은 慶北大學校 醫科大學 1989 慶北醫大誌 Vol.30 No.3

Cyanate는 헤모글로빈과 결합하여 carbamylation을 형성하여 산소결합력을 증가시킨다고 한다. 그러나 혈액의 carbamylation 상태에서 운동을 하였을 경우 혈중 성분의 변화에 대한 보고는 드문 것 같다. 따라서 조직 저산소증 상태에서 운동을 부하하였을 경우의 혈중 유산농도, 2,3-DPG, 헤마토크릿, 헤모글로빈, pH, 그리고 탄산가스 및 산소 분압의 변화를 측정하였다. Sprague-Dawley 숫컷 쥐를 실험대상으로 하여 2주간 cyanate를 섭취케한 cyanate 섭취군과 생리적식염수를 섭취케한 대조군으로 나누고 이를 다시 운동을 한 군과 하지 않은 군으로 나누었다. 운동은 17℃ 수온에서 5분간 유영시켰으며 실험결과는 다음과 같다. Cyanate 섭취군에서는 대조군에 비하여 헤모글로빈의 함량이 증가하였다. 2,3-DPG는 유의한 감소를 하였고 HCO_3^-는 증가하여 대사성염기증을 나타내었다. 따라서 carbamylation의 형성과 더불어 이들 인자 때문에 산소결합력은 증가할 것으로 생각된다. 이런 상태에서 운동을 시켰을 때 유산은 양군 모두 증가하였으며 특히 cyanate 섭취군은 대조군보다 더 많이 증가하여 양군에 유의성을 나타내었다. 따라서 pH도 운동 후 양군에서 안정시보다 산성화하였다. 그리고 2,3-DPG도 양군 모두 증가의 경향을 보였으며 cyanate 섭취군이 대조군보다 더 많이 증가하는 것 같았다. 따라서 산성화와 2,3-DPG 증가는 조직에 산소를 공급하는데 도움을 줄 것으로 생각한다. 헤마토크릿과 헤모글로빈은 cyanate 섭취군에서는 변화가 없었지만 대조군에서는 유의하게 증가하였다. 탄산가스와 산소의 분압은 운동으로 인한 과호흡으로 탄산가스의 분압은 감소하였고 산소의 분압은 증가하였다. Cyanate is known to bind with hemoglobin and, through carbamylation, to increase its oxygen binding capacity. However, the effect of carbamylated blood to exercise in the rat has not been studied satisfactorily. Thus, the following experiment was performed to examine the changes of blood lactate, 2, 3-diphosphogylcerate(2, 3-DPG), hematocrit, hemoglobin, pH and partial pressures of CO_2 and O_2 after exercise in cyanate-induced tissue hypoxia. Male Sprague-Dawley rats employed for this experiment were divided into two groups. Cyanate was given for 2 weeks to one group and, as a control, normal saline was given to the other group. Each group was further divided into exercise and non-exercise group. The exercise groups were forced to swim in 17℃ water for 5 minutes. The results obtained are summarized as follows. In cyanate group at rest, the hemoglobin content was increased, 2, 3-DPG was reduced, and bicarbonate ion was increased to reveal a metabolic alkalosis. These factors, 2, 3-DPG and pH, seem to magnify the increase of hemoglobin-oxygen binding capacity primarily caused by carbamylation. After exercise, blood lactate was increased and consequently pH was acidified in both groups and especially showed a significantly higher lactate level in the cyanate group than the control. And 2, 3-DPG also showed an increasing tendency in both groups, cyanate group showing more increase than the control. The hematocrit and hemoglobin were not changed in cyanate group, but they were significantly increased in control group. Hyperventilation due to exercise caused a decrease of blood PCO_2 and an increase of blood PO_2.

Cyanate가 배양한 피부 섬유아세포에서 제1형 교원질 유전자 발현에 미치는 영향

박재홍 ( Jae Hong Park ),김병천 ( Byung Chun Kim ),이규석 ( Kyu Suk Lee ) 대한피부과학회 2003 대한피부과학회지 Vol.41 No.4

N/A Background : Fibrosis is a common response to various insults or injuries and can be the outcome of any perturbation in the cellular function of any tissue. Peritoneum is always exposed to the waste products during peritoneal dialysis. In aqueous solution, there is partial and spontaneous decomposition of urea to ammonia, carbonate and cyanate. Cyanate reacts irreversibly with the N-terminal groups of amino acid, peptides and many proteins by a process known as carbamylation and may contribute to peritoneal injury with fibrosis. But only little is known about the molecular and cellular mechanism underlying the effect of cyanate on the expression of type I collagen in cultured skin fibroblasts. Objective : The purpose of this study was to examine the effect of cyanate on type I collagen gene expression in cultured skin fibroblasts. Methods : In this study, the effects of cyanate were examined by Northern blot hybridization, chloramphenicol acetyltransferase (CAT) assay, and immunohistochemical stain in cultured human fibroblasts. Results : In Northern blot hybridization, steady-state levels of al(I) procollagen mRNA were increased 2-fold at 100 μmol of cyanate compared to untreated control, Cyanate caused an alteration in the at(I) Procollagen mRNA expression in a dose-related fashion. In CAT assay, the relative CAT activity was 1.0 in the untreated control, 0.9 at a concentration of 0.1 μmol, 2.3 at 10 μmol, and 2.6 at a 100 μmol. Cyanate caused a marked increase on type I collagen gene promoter activity In imunohistochemical stain with anti-type I collagen antibody, type I collagen was markedly increased in cultured fibroblasts by cyanate. Conclusion : These results indicate that cyanate may be a powerful up-regulator of type I collagen production through the transcriptional activation of gene expression in cultured skin fibroblasts. (Korean J Dermatol 2003;41(4) : 416∼422)

Cyanate를 처치한 흰쥐에서 승압제에 대한 심맥관계 반응

최지용,양은경,서준형,박재식,안동국 慶北大學校 醫科大學 1995 慶北醫大誌 Vol.36 No.4

목적 : 숫컷 흰쥐에 cyanate를 섭취케 하여 나타나는 산소-혈색소 결합력의 증가가 동맥압, 심박수, 압감수성 반사 및 동맥압 증가율에 미치는 영향을 관찰하며, 또한 승압제인 angiotensin Ⅱ (AngⅡ) 및 norepinephrine (Norepi) 그리고 칼슘 통로 차단제인 nifidipine(Nif)이 산소-혈색소 결합력이 증가된 상태에서 심맥관계에 미치는 영향을 평가 하고자 하였다. 대상 및 방법 : Wistar 숫쥐를 3주간 cyanate를 섭취하도록 한 실험군과 물을 먹도록 한 대조군으로 나누었다. 먼저 채혈하여 pH와 산소 및 탄산가스 분압을 측정하였다. 이어서 승압제인 Ang Ⅱ와 Norepi을 정맥 주입하여 심맥관계에 변화를 조사하였다. 또한 Nif를 전처치한 후 역시 Ang Ⅱ와 Norepi의 승압 반응을 관찰하였다. 결과 : 동정맥 산소분압은 유의하게 낮았으며 pH는 알칼리증을 나타내었다. 평균동맥압은 유의한 차이는 아니지만 높은 경향을 보였다. 심박수 변화는 일관성은 발견할 수 없었지만 동맥압의 변화에 대한 심박수의 변화 비로 계산한 압감수성 반사는 더욱 둔화되는 경향을 보였다. 승압제를 주입하면 농도 증가에 따라 동맥압 증가 현상을 볼 수 있었고, 동량의 Ang Ⅱ나 Norepi에 대해 대조군보다 동맥압 증가가 더 컸다. Nif를 전처치한 후 승압제를 주입한 경우 승압작용을 더 많이 차단하였다. 동맥압 상승률은 동맥압의 변화와 반대로 상승률이 적었다. 결론 : cyanate는 산소-혈색소 결합력을 증가시켜 동정맥 산소 분압을 감소시켜서 알칼리가 되게 하며, 승압제에 의해 심장 부하가 커지면 동맥압 상승률을 감소시켰다. 산소-혈색소 결합력 증가에 의한 조직의 산소 부족 현상을 극복하기 위하여 압감수성 반사 둔화를 포함한 몇가지 기전으로 동맥압이 더 증가하는 것으로 생각이 된다. This study was aimed to elucidate the cardiovascular responses to angiotensin Ⅱ (Ang Ⅱ) and norepinephrine (Norepi) together with blood gas profiles during elevated oxygen-hemoglobin binding affinity caused by ingestion of cyanate in rats. Male Wistar rats were divided into an experimental group that were fed cyanate in drinking water and a control group that were supplied with tap water for 3 weeks. On the experimental day, arterial and venous blood was sampled for measurement of pH, PO_2 and PCO_2. After 6.25, 12.5 and 25 ng/100g of Ang Ⅱ, or 0.1, 0.25 and 0.5 g/100g of Norepi was administered intravenously cardiovascular responses were recorded. The cardiovascular responses to pressor agents were also monitored in pretreatment with nifedipine. Arterial and venous blood had significantly low PO_2 and alkaline pH values in the cyanate group. Mean arterial pressure tended to be higher, though not significant. Arterial pressure was increased by pressor agents dose-dependently, and the magnitude of increase at given doses of Ang Ⅱ or Norepi was higher in the cyanate group than in the control group. The pressor effects blocked by pretreatment with nifedipine in the cyanate group was greater than in the control. No consistent change was observed in heart rate, but the baroreceptor sensitivity tended to be more compromised. The rate of increase in arterial pressure was lower in contrast to its absolute level. These results indicate that, during elevated oxygen-hemoglobin binding affinity caused by cyanate, arterial and venous blood becomes alkaline with lowered PO_2, and the rate of increase in arterial pressure is diminished under a condition when cardiac afterload is elevated by pressor agents. It seems that the arterial pressure is increased to a higher level by several mechanisms including lowered baroreceptor sensitivity to compensate for the relative tissue hypoxia induced by elevated oxygen-hemoglobin binding affinity.

시안산에 의한 신장 혈관간세포의 자멸사

김지열,김양수,홍기연,어완규,최영식 고신대학교의과대학 2007 고신대학교 의과대학 학술지 Vol.22 No.1

To investigate the mechanism of cyanate-induced apoptosis in kidney mesangial cells, mesangial cells were treated with 0.01-40 mmol/L cyanate. There was a dose-dependent decrease in cell viability by cyanate. Substantial morphological changes were observed in mesangial cells when they were treated with cyanate. Mesangial cells were detached and floated to the top of the culture dish and monolayer was not formed. Although cyanate had no effect on the DNA fragmentation, cyanate induced PARB fragmentation, and activation of caspase-3 and caspase-8 And cyanate induced the decrease of Bcl-2 and cIAP expression under the Western blot analysis. These results suggest that cyanate can induce apoptosis by activating pro-apoptotic signals. Apoptosis in kidney mesangial cells induced by cyanate may play a role pathogenesis of renal diseases. According to these results, cyanate form urea must be viewed as a strong uremic toxin, rather than a surrogate. Early targeting dialysis doses specifically to cyanate and urea concentrations may be more important in patients with renal diseases.