Strigol 유사체의 합성

김인규,홍영택,김성수,Kim In Kyu,Hong Young Tech,Kim Sung Soo 대한화학회 1992 대한화학회지 Vol.36 No.5

Strigol은 목화의 뿌리에서 추출된 천연물로서 벼, 옥수수, 사탕수수 등에 기생하는 피류(striga species) 등의 씨앗을 발아시키는데 월등한 효능을 보인다 $(10^{-12} ∼ 10^{-11}M, 80% 발아)$. 그런데 이러한 잡초는 오랜기간(15∼20년) 동안 흙속에서 휴면하고 있기 때문에 이들의 방제가 매우 어렵다. 이들을 방제할 수 있는 제초제 개발을 위해서 여러가지 strigol 유사체들인 3-methyl-4-(2-oxo-3,3a,6,6a-tetrahydro-2H-cyclopenta[b]furan-3-ylidenemethoxy)-but-2-en-4-olide(21), 4-(2-oxo-3,3a,6,6a-tetrahydro-2H-cyclopenta[b]furan-3-ylidenemethoxy)but-2-en-4-oilde(22), 3-methyl-4-(2-oxotetrahydrofuran-3-ylidenemethoxy)-but-2-en-4-olide(23), 4-(2-oxotetrahydrofuran-3-ylidenemethoxy)-but-2-en-4-olide(24)등을 합성하였다. Strigol, a natural product isolated from root exudates of cotton, was found to be an extremely potent seed germination stimulant for the parasitic plant, witchweed. Witchweed seeds can remain dormant in the soil for several years until favorable conditions prevail including exposure to some type of chemical germination stimulant. Several strigol analogues, 3-methyl-4-(2-oxo-3,3a,6,6a-tetrahydro-2H-cyclopenta[b]furan-3-ylidenemethoxy)-but-2-en-4-olide(21), 4-(2-oxo-3,3a,6,6a-tetrahydro-2H-cyclopenta[b]furan-3-ylidenemethoxy)but-2-en-4-oilde(22), 3-methyl-4-(2-oxotetrahydrofuran-3-ylidenemethoxy)-but-2-en-4-olide(23), and 4-(2-oxotetrahydrofuran-3-ylidenemethoxy)-but-2-en-4-olide(24), were synthesized.

우황 (Bezoar Bovis)의 성분연구

김인규,박선구,오현철,김규완,In Kyu Kim,Sun Ku Park,Hyun Cheol Oh,Kyu Wan Kim 대한화학회 1991 대한화학회지 Vol.35 No.3

남미산 시료 우황(Bezoar Bovis)으로부터 glycodeoxycholic acid, cholesterol, cholesteryl fatty acid ester, palmitic, stearic methyl ester 외에 새로운 성분으로 8-octadecenoic methyl ester 및 cholesta-3,5-diene을 분리하였다. Two new metabolites have been characterized from the methylene chloride extracts of Bezoar Bovis, a well known oriental drug : 8-octadecenoic methyl ester and cholesta-3,5-diene. Their structures were deduced from $^1$H-NMR and GC-mass spectra.

2-Mercaptobenzothiazole의 반응

김인규,김순일,유찬모,정일국,박준원,심상철,In Kyu Kim,Sun Il Kim,Chan Mo Yu,Il-Gook Chung,Joon Won Park,Sang Chul Shim 대한화학회 1984 대한화학회지 Vol.28 No.6

2-Mercaptobenzothiazole과 알코올로부터 여러가지 알킬유도체를 얻을 수 있었다. 이 방법은 알려진 다른 방법보다 간편하고 수율도 좋고 또 일반성이 있는 장점이 있다. 이렇게 해서 얻은 2-mercaptobenzothiazole에 염소화 반응을 시도한 결과 2-chloromethylthiobenzothiazole을 얻을 수 있었다. A highly efficient and general route to obtain the alkyl derivatives of 2-mercaptobenzothiazole is described. Depending on the reaction conditions 2-methylmercaptobenzothiazole gave various products with chlorinating agents probably due to the lability of the probable chlorosulfonium ion intermediate.

한국산 해면의 지질 성분 연구

김인규,박선구,박성혜,장성근,Kim In Kyu,Park Sun Ku,Park Sung Hye,Jhang Sung Keun 대한화학회 1991 대한화학회지 Vol.35 No.1

한국 남해안 소흑산도에서 채집한 해면 V.japonica H.로부터 통상적인tetradecanoic 및 hexadecanoic methyl ester 이외에 탄소가 홀수인 pentadecanoic, heptadecanoic methyl ester와 가지달린 12-methyltetradecanoic, 14-methylpentadecanoic, 15-methylhexadecanoic 및 14-methylhexadecanoic methyl ester가 발견되었으며, 주 sterol 성분으로는 cholesterol과 소량의 ergost-25-ene-3,5,6-triol이 검출되었다. 한편, 여수 돌산도에서 채집한 해면 H.sinapium의 주 sterol성분은 5${\alpha}$-cholestan-3${\beta}$-ol이었고 cholesterol은 소량으로 얻어졌다. 지방산으로는 팔미틴산, 팔미토레인산, 올레인산, 스테아린산 및 리놀레인산 에틸에스터 이외에 상당량의 arachidonic산 에틸에스터가 함유되어 있었다. 상기 지역에서 채집한 또 다른 해면에서는 상당량의 tetradecanoic tetradecyl 및 hexadecyl ester와 sterol 성분으로 cholesteryl acetic 및 fatty acid ester가 함유되어 있었다. Various sterols and uncommon fatty acids have been isolated from the three species of Korean marine sponges. Odd-numbered pentadecanoic, heptadecanoic methyl ester and branched 12-methyltetradecanoic, 14-methylpentadecanoic, 15-methylhexadecanoic and 14-methylhexadecanoic methyl ester were isolated along with common tetradecanoic and hexadecanoic methyl ester from Heteropiidae sponge Vosmaeropsis japonica Hozawa collected from Sohuksan island of the Korea sea. Futher elution with more polar solvent gave 5${\alpha}$-cholestan-3${\beta}$-ol along with minor amount of ergost-25-ene-3${\beta}$,5${\alpha}$,6${\beta}$-triol. On the other hand, marine sponge Hymeniacidon sinapium collected from Yesu Dolsan island of the Korea sea was shown to contain 5${\alpha}$-cholestan-3${\beta}$-ol, along with minor amount of cholesterol, palmitic, palmitoleic, oleic, stearic, linolenic, and arachidonic acid ethyl ester. Unknown marin sponge collected from the same region was shown to contain large amount of tetradecanoic tetradecyl and hexadecyl ester and cholesteryl acetic and fatty acid ester.

Acetoacetanilide 유도체 합성

김인규,In Kyu Kim 대한화학회 1981 대한화학회지 Vol.25 No.1

Acetoacetanilide를 브롬화한 결과 예상한 ${\alpha}$-bromo 유도체가 얻어지지 않고, r-bromo 유도체가 얻어졌다. 이것을 mercaptoethanol과 반응시켜 sulfide 유도체를 만든다음, 산성하에서 고리화시킨 결과 2-(N-phenylcarbamoyl)methylene-1,4-oxathiane이 좋은 수율로 얻어졌다. 이 물질은 살균제 농약으로 널리 사용되고 있는 carboxin과 그 구조가 매우 유사하므로 이 물질의 biological activity는 흥미있는 과제가 될 것이다. Bromination of acetoacteanilide in non-polar medium gives the r-brominated derivative. This unexpected result may be due to the steric hinderance during the enolization of the substrate. The structure of r-bromoacetoacetanilide can be assigned on the basis of its 1H NMR spectrum. Additional evidence is provided by making derivatives, whick proceed without skeletal rearrangements. Structural similarity of 2-(N-phenylcarbamoyl)methylene-1,4-oxathiane with carboxin which is used as a potent fungicide prompted our investigation of the 1,4-oxathiane synthesis. It is prepared from the reaction of r-bromoacetoacetanilide with mercaptoethanol followed by acidic dehydration in high yield.

에스테르엔올 음이온의 Claisen 자리옮김 반응에 의한 Permethrin의 합성

김인규,강석구,홍장후,In-Kyu Kim,Suk-Ku Kang,Jang-Hoo Hong 대한화학회 1986 대한화학회지 Vol.30 No.6

(${\pm}$)시스- 및 트란스-3-(2,2-디클로로비닐)-2,2-디메틸-1-시클로프로판 카르복시산 3-페녹시벤질을 2-메틸-3-부텐-2올($\underline{2}$)을 출발물질로하여 입체선택적으로 합성하였다. 아세트산과 무수아세트산의 존재하에서 2-메틸-3-부텐-2-올을 알릴자리옮김 반응에 의해 아세트산3-메틸-2-부텐-일($\underline{3}$)을 얻은 다음 이 아세트산 알릴($\underline{3}$)의 [3,3] 시그마 자리옮김 반응에 의해 ${\gamma},\;{\delta}$-불포화산($\underline{4}$)을 얻었다. 3,3-디메틸-4-펜텐산($\underline{4}$)을 SOCl$_2$로 처리하고 3-페녹시벤질알코올로 에스테르화 시켜 알코올 부분이 구축된 3,3-디메틸-4-펜텐산 3-페녹시벤질($\underline{6}$)을 얻어서 사염화탄소의 첨가 후 그리화에 의해 (+)시스-및 트란스-3-(2,2-디클로로비닐)-2,2-디메틸-1-시클로프로 판카르복시산 3-페녹시벤질을 합성하였다 A stereoselective synthesis of 3-phenoxybenzyl (${\pm}$)-cis and trans-3-(2,2-dichlorovinyl)-2,2-dimethyl-1-cyclopropanecarboxylic acid starting from readily available 2-methyl-3-buten-2-ol($\underline{2}$) is described. Allylic rearrangement of 2-methyl-3-buten-2-ol, in the presence of acetic acid and acetic anhydride gave 3-methyl-2-butenyl acetate($\underline{3}$). The [3,3] sigmatropic rearrangement of the allyl acetate($\underline{3}$), as the silylketene acetal, produced the ${\gamma},\;{\delta}$-unsaturated acid($\underline{4}$). Treatment of 3,3-dimethyl-4-pentenoic acid($\underline{4}$) with SOCl2 followed by esterification with 3-phenoxybenzyl alcohol yielded 3, 3-dimethyl-4-pentenoic acid ester($\underline{5}$). Addition of carbon tetrachloride to the olefin ester($\underline{6}$) furnished 4,6,6,6-tetrachloro-3,3-dimethylhexanoic acid ester ($\underline{7}$). Cyclization with potassium t-butoxide and elimination of hydrogen chloride afforded 3-phenoxybenzyl (${\pm}$) cis- and trans-3-(2,2-dichlorovinyl)-2,2-dimethyl-1-cyclopropanecarboxylic acid.

Bis(p-nitrophenyl) sulfide의 새로운 합성방법

김인규,노장숙,In Kyu Kim,Jang Sook Noh 대한화학회 1974 대한화학회지 Vol.18 No.6

Phase transfer catalyst를 사용하여 p-chloronitrobenzene으로부터 bis(p-nitrophenyl) sulfide를 수득율이 좋고, work-up이 간편하게 합성하였다. Using a phase transfer catalyst, a convenient route to bis(p-nitrophenyl) sulfide was investigated. The yield was higher than the known method, and the work-up was also much easier than the conventional method.

${\alpha}$-Bromophenylacetamide의 가수분해 반응연구

김인규,윤용진,Kim In Kyu,Yoon Young Jin 대한화학회 1978 대한화학회지 Vol.22 No.5

${\alpha}$-Bromophenylacetamide를 황산중에서 가수분해시키면 대개의 경우 mandelic acid와 ${\alpha}$-bromophenylacetic acid의 혼합물이 얻어지고, 염산의 경우에는 ${\alpha}$-chlorophenylacetic acid만이 얻어졌다. 그러나 조건을 잘 조절하면 mandelic acid와 ${\alpha}$-chlorophenylacetic acid는 각각 86, 95 % 이상의 좋은 수율로 순수하게 생성되지만, ${\alpha}$-bromophenylacetic acid만을 순수하게 생성시키는 최적 조건은 찾지 못하였다. 즉 이들 조건에서 ${\alpha}$-탄소의 브롬이 각각 $OH^{\Theta}$ 와 $Cl^{\Theta}$로 쉽게 치환되었다. The hydrolysis of ${\alpha}$-bromophenylacetamide in the acidic media has been studied. The reactions in sulfuric acid and p-toluenesulfonic acid afforded mainly mandelic acid ; on the other hand, in hydrochloric acid ${\alpha}$-chlorophenylacetic acid was the main product. In either case, it was difficult to obtain ${\alpha}$-bromophenylacetic acid without concomittant formation of mandelic acid and ${\alpha}$-chlorophenylacetic acid respectively from the hydrolysis of ${\alpha}$-bromophenylacetamide. Mandelic acid and ${\alpha}$-chlorophenylacetic acid were obtained in good yields (86, 95 %) in sulfuric and hydrochloric acid respectively; the reactions are therefore potentially useful processes for obtaining them.

Mechanism of the Reduction of Nitrobenzene in Basic Solution

김인규,황재수,In Kyu Kim,Jasoo Whang Korean Chemical Society 1976 대한화학회지 Vol.20 No.1

염기성 용액에서 니트로벤젠의 환원에 대한 새로운 메카니즘을 제안하였다. 페닐히드록실아민이 중간체로서 관여하지 않고, 니트로소벤젠이 이합화(dimerization)하여 아족시벤젠으로 변환한다. A new mechanism is proposed for the reduction of nitrobenzene in basic solution that does not involve hydroxylamine as an intermediate. This paper presents evidence that the azoxybenzene is not formed from the hydroxylamine, but formed instead from the dimerization of nitrosobenzene.

자기공명영상으로 분류한 소아 임파관종 주사 요법의 평가

김인규,문석배,신현백,서정민,이석구,Kim, In-Kyu,Moon, Suk-Bae,Baek, Sin-Hyen,Seo, Jeong-Meen,Lee, Suk-Koo 대한소아외과학회 2009 소아외과 Vol.15 No.2

Pediatric lymphangioma can occur at any site. However the neck is the most common site. There are two treatment modalities (surgical excision and intralesional injection) for lymphangiomas. But, the treatment guide line for lymphangioma has not been established, yet. The aim of this study is to establish the treatment guide line based on our experience with lymphangiomas. Medical records of 82 cases of lymphangioma were reviewed retrospectively. On MRI (magnetic resonance image) findings, lymphangiomas were divided into 4 groups by the proportion of the cyst bigger than 2 cm in diameter of the tumor; group A-proportion of cyst occupies more than 75%, group B-proportion of the cyst 50~75%, group C-25~50%, and D in less than 25%. All patients were treated with OK-432 intralesional injection as the initial treatment. The effective response rates of OK-432 in group A & B were 88.2% and 88.8%, respectively. Group C response was 38.0% and D only 20.0%. Twenty-three patients received surgical excision. The result of surgical excision was generally satisfactory. Surgical site infection occurred in 1 case and postoperative bleeding in 1 case. Theses results indicate that intralesional injection of OK-432 could be the first line therapy in group A & B. In group C, OK-432 would be better as the first line therapy than surgery. For the group D, surgical excision should be the first line of treatment.