DC Field | Value | Language |
---|---|---|
dc.contributor.advisor | Shim, Sang-Chul | - |
dc.contributor.advisor | 심상철 | - |
dc.contributor.author | Kim, Geon-Soo | - |
dc.contributor.author | 김건수 | - |
dc.date.accessioned | 2011-12-13T04:59:42Z | - |
dc.date.available | 2011-12-13T04:59:42Z | - |
dc.date.issued | 1994 | - |
dc.identifier.uri | http://library.kaist.ac.kr/search/detail/view.do?bibCtrlNo=69168&flag=dissertation | - |
dc.identifier.uri | http://hdl.handle.net/10203/32655 | - |
dc.description | 학위논문(석사) - 한국과학기술원 : 화학과, 1994.2, [ vi, 51 p. ] | - |
dc.description.abstract | 1-Phenyl-4-(2-pyridyl)-1,3-butadiyne (2-PPB) was prepared successfully with moderate yields by proper coupling methods from commercially available material in order to investigate the effect of pyridyl substituent on photochemical properties of butadiynes. Irradiation of 2-PPB with dimethyl fumarate (DMFu) in deaerated dichloromethane solution at 300 nm yields 1:1 photoadducts ($\underline{2}$, $\underline{3}$, $\underline{4}$ and $\underline{5}$) and 1:2 photoadducts ($\underline{1}$, $\underline{6}$, and $\underline{7}$). The 1:1 photoadducts (2 and 3) is initially formed and prolonged irradiation of the solution results in the formation of 1:2 photoadducts (1, 6, and 7). Photolysis of pure $\underline{2}$/$\underline{3}$ isolated with DMFu yields $\underline{1}$ and $\underline{6}$/$\underline{7}$, respectively, indicating that $\underline{2}$ and $\underline{3}$ are the primary photoadducts and $\underline{1}$, $\underline{6}$, and $\underline{7}$ are the secondary photoadducts. Triplet quenching effect on the photoreaction with oxygen shows that $\underline{2}$ and $\underline{3}$ are produced from triplet excited state of 2-PPB. Photoreaction of 2-PPB with 2,3-dimethyl-2-butene (DMB) in dichloromethane yields $\underline{8}$-$\underline{10}$, and photoreaction in neat DMB yields $\underline{8}$, $\underline{10}$, $\underline{11}$ and $\underline{12}$. All of these photoreactions proceeded from triplet excited states. 2-PPB in the photoreaction with some olefins is more reactive than 1,4-diphenyl-1,3-butadiyne (DPB) because intersystem crossing is enhanced by introducing $n-π^*$ state. Differently from DPB, photoreaction of 2-PPB with DMFu and DMB yields $\underline{6}$, $\underline{9}$, and $\underline{12}$. The formation of $\underline{6}$ may be affected by electron withdrawing effect of pyridyl group for excited state of $\underline{2}$. On the formation of $\underline{9}$, it looks as though the triplet state lifetime of 2-PPB-DMB were longer than t... | eng |
dc.language | eng | - |
dc.publisher | 한국과학기술원 | - |
dc.title | Photochemistry of 1-phenyl-4-(2-pyridyl)-1,3-butadiyne:photoreaction with some olefins | - |
dc.title.alternative | 1-페닐-4-(2-피리딜)-1,3-부타디인의 광화학: 몇가지 올레핀들과의 광반응 | - |
dc.type | Thesis(Master) | - |
dc.identifier.CNRN | 69168/325007 | - |
dc.description.department | 한국과학기술원 : 화학과, | - |
dc.identifier.uid | 000923039 | - |
dc.contributor.localauthor | Shim, Sang-Chul | - |
dc.contributor.localauthor | 심상철 | - |
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