Preparation and Polymerization of Alkenylsilanes

김정균,최순규,박은미,정인경,Kim, Chung Kyun,Choi, Soon Kyu,Park, Eun Mi,Jung, In Kyung Korean Chemical Society 1997 대한화학회지 Vol.41 No.2

The silyltriflates$(Ph_{3-n}SiH(OTf)_n)$have been produced by the reaction of triphenylsilane and triflic acid$(CF_3SO_3H)$at low temperature. These highly reactive compounds are a valuable reagent for the synthesis of numerous new functional substituted silane derivatives. The reaction of silyltriflates with alkenyl- and alkynylmagnesium bromide as well as organolithium compounds gave new silanes$Ph_2SiHR(R=\;C(CPh,\;CH=CH_2,\;CH_2CH=CH_2,\; (CH_2)_2CH=CH_2,\;(CH_2)_3CH=CH_2)$in high yields. The hydrosilation of prepared alkenyl- and alkynylsilanesPh_2SiHR$in the presence of a platinum catalyst(Pt/C) at high temperature$(200{\circ}C)$gave carbosilane polymers$((Ph_2SiCH=CPh)_n$and$(Ph_2Si(CH_2)m)n;\;m=2∼4, n{\ge}10)$along with five- and six-membered silaalkane ring compounds derived from intramolecular hydrosilation reactions. All of the prepared compounds are confirmed by NMR, UV, IR and mass spectroscopy as well as elemental analysis. 실릴트리플레이트$(Ph_{3-n}SiH(OTf)_n))$는 낮은 온도에서 트리펜일실란과 트리플산$(CF_3SO_3H)$의 반응에 의해 형성되며 이러한 화합물은 새로운 기능성 실란 유도체의 제조에 이용되고 있다. 실릴트리플레이트와 알캔일-, 알킨일마그네슘 브롬아이드 그리고 유기리티움 화합물과의 반응에 의해 새로운 실란 화합물 Ph_2SiHR(R=C{\equiv}(CPh,\;CH=CH_2,\;CH_2CH=CH_2,\;(CH_2)_2CH=CH_2,\;(CH_2)_3CH=CH_2)$을 높은 수율로 얻었다. 합성된 알켄일-, 알킨일실란은 백금촉매 하에서 카보실란 고분자$((Ph_2Si(CH_2)m)n;\;m=2∼4,\;n\le10)$5~6환고리 화합물을 형성하였다. 모든 생성물들은 NMR, UV, IR, 질량분석, 그리고 원소분석법에 의해 확인되었다.

Beckmann Rearrangement of Ring A Steroidal Oxime Using the Carbon tetrachloride-triphenylphosphine

김정균,최순규,박원우,이용태,Kim Jack C.,Choi Soon-Kyu,Park Won-Woo,Lee Yong-Tae Korean Chemical Society 1979 대한화학회지 Vol.23 No.1

벡크만 자리옮김반응의 실험조건은 대부분이 센산 (HCl, $H_2SO_4$, $PCl_5$등)이나, 고온과 같은 격렬한 반응조건을 사용하므로 이러한 조건은 자주 전위보다는 케토옥심의 이성질화를 일으킨다. $5{\alpha}$-cholestan-3-one oxime의 벡크만 전위에 온화하고 중성의 조건인 사염화탄소와 트리페닐포스핀을 사용하여 3-aza-A-homo-5${\alpha}$-cholestan-4-one을 얻었다. 이러한 새롭고, 온화하며 쉽고 빠른 베그만 전위를 소개하고 이러한 방법을 고전적인 벡크만 전위 시약인 폴리인산을 사용한 방법과 비교하였다. The experimental procedures of Beckmann rearrangement mostly involve the use of vigorous conditions such as strongly acidic reagents (conc. HCl, $H_2SO_4$, $PCl_5$, etc.) or elevated temperatures, which frequently cause isomerization of ketooximes prior to rearrangement.We have effected the Beckmann rearrangement on $5{\alpha}$-cholestan-3-one oxime using the carbon tetrachloride-triphenylphosphine reagent under mild, neutral conditions to give 3-aza-A-homo-$5{\alpha}$-cholestan-4-one. This new, mild, facile and rapid general method of Beckmann rearrangement is presented, and compared with the classical (more conventional) Beckmann reagent of polyphosphoric acid.

Preparation of 3-Aza-A-homo-cholest-4-one-4a-ene from the Cholest-4-ene-3-one Oxime Using the Triphenylphine-Carbon Tetrachloride Combinations

김정균,최순규,Jack C. Kim,Soon-Kyu Choi Korean Chemical Society 1981 대한화학회지 Vol.25 No.5

N-메틸-N'-치환페닐우레아화합물들의 니트로소화 반응에 있어서 니트로소화 화학종의 반응성 및 위치화학적 영향

김정균,조인섭,최순규,Jack C. Kim,In-Seop Cho,Soon-Kyu Choi 대한화학회 1991 대한화학회지 Vol.35 No.3

비대칭우레아화합물, N-메틸-N'-치환페닐우레아화합물들 ($CH_3NHCONHC_6H_4-G$; G = H, p-$CH_3,\;m-CH_3,\;m-CH_3O$, p-F, m-F, m-Br) 7종 합성하고 이들을 NaN$O_2$와 4종류의 산(d-HCl, HCOOH, C$H_3$COOH, CF$_3$COOH)을 사용하여 니트로소화시킬 때 이 니트로소화 반응의 위치선택성을 조사하였다. 이들 반응 모든 경우에서 두 가지 위치이성질체생성물, N-니트로소-N-메틸-N'-치환페닐우레아생성물(A)들과 N'-니트로소-N-메틸-N'-치환페닐우레아생성물(B)들이 주생성물로 생성되었으며, 이들 생성몰비 B/A를 이들 반응혼합물의 $^1$H-NMR에서의 메틸피이크의 면적을 측정하여 이를 결정하였다. 전자공급체치환기(ㅎ)가 우레아화합물의 페닐기에 치환된 경우 일반적으로 B/A의 비가 증가되었다. 이들 위치이성체 생성물비 B/A로부터 니트로소화 화학종(HONO, HCOONO, CH$_3$ COONO, CF$_3$ COONO)의 페닐치환기에 의한 질소원자 위의 전자밀도변화에 대한 반응민감도를 얻었으며 반응민감도의 상대적 크기는 1.00 : 0.93 : 0.78 : > ∼ 0.7(HONO : HCOONO : CH$_3$ COONO : CF$_3$ COONO)로 나타났다. The regioselectivity in the nitrosation of seven N-methyl-N'-substituted phenylureas ($CH_3NHCONHC_6H_4-G$; G = H, p-CH$_3$, m-CH$_3$, m-CH$_3$O, p-F, m-F, m-Br) was examined using NaNO$_2$ and 4 different acids (diluted HCl, HCOOH, CH$_3$COOH, CF$_3$COOH). In all cases, the two regioisomeric products, N-nitroso-N-methyl-N'-substituted phenylureas (A) and N'-nitroso-N-methyl-N'-substituted phenylureas (B) were observed to be formed as major products and product ratios were determined by the integration of their methyl peaks in $^1$H-NMR. Electron donating substitutent(G) on phenyl of the ureas generally led to increase the ratio of B to A. The data have revealed that the relative sensitivity of the nitrosonium species (HONO, HCOONO, CH$_3$COONO, CF$_3$COONO) toward the change of electron density on nitrogen with phenyl substitutents are 1.00 : 0.93 : 0.78 : > ∼ 0.7.

Synthesis of 2-Bromo, and 2-Nitro-3,4-dihydro-5,6-dimethoxy-1(2H)-naphthalenones

김정균,한석규,최순규,Jack C. Kim,Suk-kyu Han,Soon-Kyu Choi Korean Chemical Society 1976 대한화학회지 Vol.20 No.1

An Alternate Synthesis of 2-Amino-5,6-dimethoxy-1,2,3,4-Tetrahydronaphthalene Hydrochloride

김정균,이석기,김창배,한석규,최순규,이경희,Jack C. Kim,Suk-kee Lee,Chang-bae Kim,Suk-kyu Han,Soon-kyu Choi,Kyung-hee Lee Korean Chemical Society 1977 대한화학회지 Vol.21 No.3

2-amino-5,6-dimethoxy-1,2,3,4-tetrahydronaphthalene hydrochloride를 2-nitro-3,4-dihydro-5,6-dimethoxy-(2H)-naphthalenone으로부터 합성하여서 Neber rearrangement로부터 얻은 2-amino-3,4-dihydro-5,6-dimethoxy-1(2H)-naphthalenone hydrochloride로부터 합성한 방법과 수득률 및 실업적인 조작을 비교 설명하였다. An alternate synthesis of 2-amino-5,6-dimethoxy-1,2,3,4-tetrahydronaphthalene hydrochloride from 2-nitro-3,4-dihydro-5,6-dimethoxy-1(2H)-naphthalenone,was described and compared the overall yields and experimental procedures with the previous synthetic routes obtained from Neber rearrangement product, 2-amino-3,4-dihydro-5,6-dimethoxy-1(2H)-naphthalenone hydrochloride.

1,3-Acetonedicarboxylic acid와 2,5-dimethoxytetrahydrofuran에 의한 diamine들의 반응에 관한 연구

정대일,송주현,이도훈,이용균,최순규,박유미,한정태,Jung Dai-Il,Song Ju-Hyun,Lee Do-Hun,Lee Yong-Gyun,Choi Soon-Kyu,Park Yu-Mi,Hahn Jung-Tai 한국생명과학회 2006 생명과학회지 Vol.16 No.2

본 연구를 통해 항 경련 활성을 보이는 8-aza-bicyclo[3,2,1]octan-3-one 구조를 모체로 하여 생리활성 및 구조적 특이성을 가진 8-aza-bicyclo[3,2,1]octan-3-one 화합물을 합성하고자 하였다. 본 논문에서는 ethylenediamine 1을 2,5-dimethoxyte-trahydrofuran과 1,3-acetonedicarboxylic acid을 반응시켜 8-(2-pyrrol-1-yl-ethyl)-8-aza-bicyclo[3,2,1]octan-3-one 2(yield ; 5.0%)와 1,2-di-8-aza-bicyclo[3,2,1]octan-3-onyl)ethane 3(yield ; 17.0%)을 합성하였다. 1,3diaminopropane 4의 경우에는, 8-(3-pyrrol-1-yl-propyl)-8-aza-bicyclo[3,2,1]octan-3-one 5(yield ; 6.0%)와 1,3-di-8-aza-bicyclo[3,2,1]octan-3-onyl)propane 6 (yield; 21.0%)을, 그리고 1,8-diaminooctane 7의 경우에는 8-(-8-pyrrol-1-yl-octyl)-8-aza-bicyclo[3,2,1]octan-3-one 8(yield; 2.6%)과 1,8-di-8-aza-bicyclo[3,2,1]octan-3-onyl)octane 9(yield; 24.9%)를 합성할 수 있었다. Diaminoalkanes(1,.4, 7)의 반응에서 보면 실온에서 반응을 진행시켰기에 pyrrole 유도체보다는 8-aza-bicyclo[3,2,1]octan-3-one 유도체의 합성이 보다 유리한 결과를 나타냈다. 그리고 탄소 chain이 길수록 N 원자에 전자를 잘 밀어주어 활성이 더 좋았으며 탄소 steric effect도 작기 때문에 생성물의 yield가 더 높았다. Diaminobenzene(10, 14) 역시 diaminoalkane의 반응과 같이 p-phenylenediamine 10을 2,5-dimethoxytetrahydrofuran, 그리고 1,3-acetonedicarboxylic acid과 반응시켜 p-dipyrrolylbenzene 11(yield; 4.0%), 8-(4-pyrrol-1-yl-phenyl)-8-aza-bicyclo[3,2,1]octan-3-one 12(yield; 12.0%), 1,4-di-(8-aza-bicyclo[3,2,1]octan-3-onyl)-benzene 13(yield; 59.0%)을 합성하였고, m-phynylenediamine 14의 경우에도 8-(3-pyrrol-l-yl-phenyl)-8-aza-bicyclo[3,2,1]octan-3-one 15(yield; 2.0%)와 1,3-di-(8-aza-bicyclo[3,2,1]octan-3-onyl)-benzene 16(yield; 28.0%)을 합성할 수 있었다. 그러나 o-phynylenediamine 17의 경우에는 8-aza-bicyclo[3,2,1]octan-3-one ring들의 steric hindrance의 영향에 의해 1,3-di-8-aza-bicyclo[3,2,1]octan-3-onyl)benzene은 합성되지 않았다. In order to synthesize novel anticonvulsants, we researched that the reactions of diamines with 2,5-dimethoxytetrahydrofuran and 1,3-acetonedicarboxylic acid. The reaction of ethylenediamine with 2,5-dimethoxytetrahydrofuran and 1,3-acetonedicarboxylic acid afforded 8-(2-pyrrol-1-yl-ethyl)-8-aza-bicyclo[3,2,1]octan-3-one (yield; 5.0%) and 1,2-di-(8-aza-bicyclo[3,2,1]octan3-onyl)ethane (yield; 17.0%). In case of 1,3-diaminopropane, 8-(3-pyrrol-1-yl-propyl)-8-aza-bicyclo[3,2,1]octan-3-one(yield; 6.0%) and 1,3-di-(8-aza-bicyclo[3,2,1]octan-3-onyl)propane (yield; 21.0%) were obtained. In case of 1,8-diaminooctane, 8-(8-pyrrol-1-yl-octyl)-8-aza-bicyclo-[3,2,1]octan-3-one (yield; 2.6 %) and 1,8-di-(8-aza-bicyclo[3,2,1]octan-3-onyl)octane (yield; 24.9%) were obtained. In diaminobenzene reactions, synthetic yields of 8-aza-bicyclo-[3,2,1]octan-3-one derivatives were higher than those of pyrrole derivatives because re actions were done under room temperature. The longer the carbon chain of diaminoalkane is, the more reactive N atom is due to more electron donating effect, and the less steric hindrance around the carbon gave the higher chemical yields. The reaction of p-phenylenediamine as a diaminobenzene with 2,5-dimethoxyte-trahydrofuran and 1,3-acetonedicarboxylic acid produced p-dipyrrolylbenzene (yield; 4.0%), 8-(4-pyrrol-1-yl-phenyl)-8-aza-bicyclo[3,2,1]octan-3-one (yield; 12.0%), and 1,4-di-(8-aza-bicyclo[3,2,1]octan-3-onyl)benzene (yield; 59.0%). In case of m-phenylenediamine, 8-(3-pyrrol-1-yl-phenyl)-8-aza-bicyclo[3,2,1]octan-3-one(yield; 2.0%) and 1,3-di-(8-aza-bicyclo[3,2,1]octan-3-onyl)benzene (yield ; 28.0%) were obtained. But, synthesis of 1,2-di-(8-aza-bicyclo[3,2,l]octan-3-onyl)benzene by treatment of o-phenylenediamine was not successful, presumably due to the steric hindrance of 8-aza-bicyclo-[3,2,1]octan-3-one rings.

N-Alkyl-N-Nitrosocarbamoyl-3alpha-Amino-와 3beta-Amino-5alpha-Cholestane 유도체들의 합성 및 항암작용 평가

김정균(Jack C. Kim),최순규(Soon Kyu Choi),조인섭(In Seop Cho),유동식(Dong Sik Yu),류성호(Sung Ho Ryu),문경호(Kyung Ho Moon) 대한약학회 1985 약학회지 Vol.29 No.2

The isomeric intermediates, 3alpha- and 3beta-amino-5alpha-cholestane required for the synthesis of N-nitrosoureas, N-(2-chloroethyl)-N-nitrosocarbamoyl-3alpha-amino-5alpha-cholestane (9), N-methyl-N-nitrosocarbamoyl-3alpha-amino-5alpha-cholestane (10), N-(2-chloroethyl)-N-nitrosocarbamoyl-3beta-amino-5alpha-cholestane (7), and N-methyl-N-nitrosocarbamoyl-3beta-amino-5alpha-cholestane (8) were obtained through the LiAlH4 reduction of 5alpha-cholestan-3-one oxime, followed by the chromatographic separation: the assignment of the stereochemistry of both isomers were based on the shape and chemical shift of C3-proton resonances on their NMR spectra and on the elution mobility on the TLC. The urea intermediates, N-(2-chloroethyl)carbamoyl-3alpha-amino-5alpha-cholestane (13), N-methylcarbamoyl-3alpha-amino-5alpha-cholestane (14), N-(2-chloroethyl)carbamoyl-3beta-amino-5alpha-cholestane (11) and N-methyl-3beta-amino-5alpha-cholestane (12) were prepared by the treatment of each isomers (3alpha-amino- and 3beta-amino-5alpha-cholestane) with alkyl isocyanates in anhydrous CHCl3, and the corresponding nitrosoureas, 7~10 were obtained by the nitrosation of the ureas, 11~14, with AcOH (or HCOOH)/NaNO2 in ice-cold condition. The inhibitory activity of the nitrosoureas, 7~10, and their intermediates, 12~14 towards the growth of L1210 murine leukemia cells, were examined. Among them, the compounds 9 and 10 exhibited high activity having ED50 to be 5.5g/ml and 6.1g/ml, respectively.

1-Phenylindole Ester류의 합성과 반응성 연구

정대일,김윤영,유병국,이용균,최순규,Dai-Il Jung,Yun-Young Kim,Byoung-Guk Yoo,Young-Gyun Lee,Soon-Kyu Choi 대한화학회 1993 대한화학회지 Vol.37 No.11

Synthesis and Reaction of 1,5,3,7-Diazadiphosphocine-1,5-Dicarboxylic Acids

조승환,송주현,이도훈,이용균,박유미,최순규,한정태,정대일,Cho, Seung-Hwan,Song, Ju-Hyun,Lee, Do-Hun,Lee, Yong-Gyun,Park, Yu-Mi,Choi, Soon-Kyu,Hahn, Jung-Tai,Jung, Dai-Il Korean Society of Life Science 2007 생명과학회지 Vol.17 No.7

본 연구는 MRI 조영제나 새로운 생리활성 물질을 개발키 위해 paraformaldehyde와 hypophosphorous acid를 아미노산인 glycine 혹은 glutamic acid와 함께 반응시켜 3,7-dihydroxy-3,7-dioxoperhydro-1,5,3,7-diazadiphos-phocme-1,5-diacetic acid 1 와 3,7-dihydrexy-3,7-dioxoperhydre-1,5,3,7-diazadiphos-phocme-1,5-di- (2-glutaric acid)3을 합성하였다. 그러나 aspartic acid에 의한 2-[5-(1,2-dicarboxy-ethyl)-3,7-dihydroxy-3,7-dioxo-315.715-[1,5,3,7]diazadiphosphocan-1-yl]-succinic acid 2는 얻지 못했다. 합성 된 3,7-dihydroxy-3,7-dioxoperhydro-1,5,3,7-dia-zadiphosphocine-1,5-diacetic acid 1을 산 촉매에 의한 에스테르화반응시켜 화합물 3,7-dihydroxy-3,7-dioxoper-hydro-1,5,3,7-diazadiphosphocine-1,5-diacetic acid methyl ester 4, 3,7-dihydroxy-3,7-dioxoperhydro-1,5,3,7-dia-zadiphosphocine-1,5-diacetic acid ethyl ester 5, 그리고 3,7-dihyoxy-3,74dioxoperhyo-1,5,3,7-diazadiphosphocine-1,5-diacetic acid propyl ester 6을 합성하였다. 계속해서 다양한 반응을 통해 새로운 화합물을 합성할 것이며 생리활성검색도 실시할 예정이다. In order to synthesize new bioactive compounds and contrasting agents, reactions of glycine and glutamic acid as an animo acid with paraformaldehyde and hypophosphorous acid were executed. Products are 3,7-dihydroxy-3,7-dioxoperhydro-1,5,3,7-diazadiphosphocine-1,5-diacetic acid 1 and 3,7-dihydroxy-3,7- dioxoperhydre-1,5,3,7-diazadiphosphocine-1,5-di-(2-glu taric acid) 3. 2-[5-(1,2-Dicarboxyethyl)-3,7-dihydroxy-3,7-dioxo-315.715-[1,5,3,7] diazadiphosphocan-1-yl]-succinic acid 2 by using aspartic acid was not obtained. Esterification of 3,7- dihydroxy-3,7-dioxoperkydro-1,5,3,7-diaza-diphosphocine-1,5-diacetic acid 1 by treatment of methanol, ethanol, and propanol were executed. 3,7-Dihydroxy-3,7-dioxoperhydro-1,5,3,7-diazadiphosphocine-1,5-diacetic acid methyl ester 4, 3.7-dihydroxy-3,7-dioxoperhydro-1,5,3,f-diazadiphosphocine-1.5-diacetic acid ethyl ester 5, and 3,7-dihydroxy-3,7-dioxoperhydro-1,5,3,7-diazadiphosphocine-1,5-diacetic acid propyl ester 6 were respectively synthesized in good yields. Continuously, we will try synthesis of novel compounds and evaluation of biological activity.