• Title/Summary/Keyword: rearrangement

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Sulfenic Acid Derived from 1,3-Oxathiolane-3-oxide (1,3-Oxathiolane-3-oxide로 부터 유도되는 술펜산)

  • Wha Suk Lee;Oee Sook Park
    • Journal of the Korean Chemical Society
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    • v.31 no.2
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    • pp.197-202
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    • 1987
  • Sigmatropic rearrangement of cis and trans-2-methyl-N-phenyl-1,3-oxathiolane-2-acetamide (b) and (c) gave unisolable sulfenic acids (d) and (f), respectively. These sulfenic acids were confirmed by deuterium exchange reactions involving 2-methylene and 2-methyl groups. The reactions also showed that no isomerization between the cis and trans sulfoxides (b) and (c) occurred under neutral conditions. However, the isomerization took place in the presence of acid catalyst. Stereospecific recyclization of sulfenic acids to the sulfoxides is attributable to possible hydrogen bonding between sulfenyl oxygen and NH proton or it arises from the geometrical requirements of the reacting bond and atoms in the reverse sigmatropic rearrangement. In the oxidation of 1, 3-oxathiolane, cis sulfoxide (b) could be obtained selectively in high yield by using $H_2O_2$-benzene seleninic acid.

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Gametophytic Abortion in Heterozygotes but Not in Homozygotes: Implied Chromosome Rearrangement during T-DNA Insertion at the ASF1 Locus in Arabidopsis

  • Min, Yunsook;Frost, Jennifer M.;Choi, Yeonhee
    • Molecules and Cells
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    • v.43 no.5
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    • pp.448-458
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    • 2020
  • T-DNA insertional mutations in Arabidopsis genes have conferred huge benefits to the research community, greatly facilitating gene function analyses. However, the insertion process can cause chromosomal rearrangements. Here, we show an example of a likely rearrangement following T-DNA insertion in the Anti-Silencing Function 1B (ASF1B) gene locus on Arabidopsis chromosome 5, so that the phenotype was not relevant to the gene of interest, ASF1B. ASF1 is a histone H3/H4 chaperone involved in chromatin remodeling in the sporophyte and during reproduction. Plants that were homozygous for mutant alleles asf1a or asf1b were developmentally normal. However, following self-fertilization of double heterozygotes (ASF1A/asf1a ASF1B/asf1b, hereafter AaBb), defects were visible in both male and female gametes. Half of the AaBb and aaBb ovules displayed arrested embryo sacs with functional megaspore identity. Similarly, half of the AaBb and aaBb pollen grains showed centromere defects, resulting in pollen abortion at the bi-cellular stage of the male gametophyte. However, inheritance of the mutant allele in a given gamete did not solely determine the abortion phenotype. Introducing functional ASF1B failed to rescue the AaBb- and aaBb-mediated abortion, suggesting that heterozygosity in the ASF1B gene causes gametophytic defects, rather than the loss of ASF1. The presence of reproductive defects in heterozygous mutants but not in homozygotes, and the characteristic all-or-nothing pollen viability within tetrads, were both indicative of commonly-observed T-DNA-mediated translocation activity for this allele. Our observations reinforce the importance of complementation tests in assigning gene function using reverse genetics.

Recent Advances in Di-$\pi$-methane Processes. Novel Reactions of 1,4-Unsaturated Compounds Promoted by Triplet Sensitization and Photoelectron Transfer

  • Armesto, Diego;Ortiz, Maria J.;Agarrabeitia, Antonia R.
    • Journal of Photoscience
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    • v.10 no.1
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    • pp.9-20
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    • 2003
  • Recent studies on the photoreactivity of l,4-unsaturated systems have changed some ideas that were firmly established in this area of research for many years. Thus, we have described the first examples of 2-aza-di-$\pi$-methane (2-ADPM) rearrangements promoted by triplet-sensitization and by single electron transfer (SET) using electron-acceptor sensitizers. These reactions afford N-vinylaziridine and cyclopropylimine photoproducts in the first examples of di-$\pi$-methane processes that yield three-membered ring heterocycles. l-Aza-1,4-dienes also undergo SET-promoted l-aza-di-$\pi$-methane (l-ADPM) rearrangements via radical-cation intermediates using electron acceptor sensitizers. In some cases, alternative cyclizations yielding different carbocycles and heterocycles have been observed. The l-ADPM and di-$\pi$-methane (DPM) reactions also occur via radical-anion intermediates on irradiation using electron donor sensitizers. On the other hand, the photoreactivity reported for $\beta$,${\gamma}$-unsaturated aldehydes for many years was decarbonylation to the corresponding alkenes. However, our studies demonstrate that these compounds undergo the oxa-di-$\pi$-methane (ODPM) rearrangement with high chemical and quantum efficiency. A comparison of the photochemical reactivity of $\beta$,${\gamma}$-unsaturated aldehydes and corresponding methyl ketones has shown that the ketones do not undergo the ODPM rearrangement while the corresponding aldehydes are reactive by this pathway. Monosubstituted $\beta$,${\gamma}$-unsaturated aldehydes at C-2 undergo the ODPM rearrangement yielding the corresponding cyclopropane carbaldehydes diastereoselectively. Finally, we have described the first examples of reactions, similar to the well know Norrish Type I process, which take place in the triplet excited state of $\beta$,${\gamma}$-unsaturated carbonyl compounds by excitation of the C-C double bond instead of the carbonyl group.

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Gene Reangement through 151 bp Repeated Sequence in Rice Chloroplast DNA (벼 엽록체 DNA내의 151 bp 반복염기서열에 의한 유전자 재배열)

  • Nahm, Baek-Hie;Kim, Han-Jip
    • Applied Biological Chemistry
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    • v.36 no.3
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    • pp.208-214
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    • 1993
  • To investigate the gene rearrangement via short repeated sequences in chloroplast DNA, the pattern of heterologous gene clusters containing the 151 bp repeated sequence with the development of plastid was compared in rice and the homologous gene clusters from various plant sources were searched for comparative analysis. Southern blot analysis of rice DNA using rp12 gene containing 151 bp repeated sequence as a probe showed the presence of heterologous gene clusters. Such heterologous gene clusters varied with the development of plastid. Also it was observed that the heterologous gene clusters were observed in all of the rice cultivars used in this work. Finally the comparative analysis of DNA sequence of the homologous gene clusters from various plants showed the evolutionary gene rearragngement via short repeated sequence among plants. These results suggest the possible relationship between the plastid development and gene rearrangement through short repeated sequences.

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A Study on the Encrypted Scheme Using Key Management Method Based on the Random Number Rearrangement for the Effective E-Document Management (효율적인 전자문서 관리를 위한 난수 재배열 기반의 키 관리 방법을 이용한 암호화 기법에 관한 연구)

  • Kim, Tae-Wook;Sung, Kyung-Sang;Kim, Jung-Jae;Min, Byoung-Muk;Oh, Hae-Seok
    • The KIPS Transactions:PartC
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    • v.16C no.5
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    • pp.575-582
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    • 2009
  • With all merits of electronic documents, there exist threats to the security such as illegal outflow, destroying, loss, distortion, etc. The techniques to protect the electronic documents against illegal forgery, alteration, removal are strongly requested. Even though various security technologies have been developed for electronic documents, most of them are emphasized to prevention of forgery or repudiation. This paper presents some problems in cryptography technologies currently used in the existing electronic document systems, and offer efficient methods to adopt cryptography algorithms to improve and secure the electronic document systems. To validate performance of the proposed random rearrangement method comparing with the existing cryptographies, basic elements have been compared, and it has been proved that the proposed method gives better results both in security and efficiency.

Synthesis of Permethrin using Ester Enolate Claisen Rearrangement (에스테르엔올 음이온의 Claisen 자리옮김 반응에 의한 Permethrin의 합성)

  • In-Kyu Kim;Suk-Ku Kang;Jang-Hoo Hong
    • Journal of the Korean Chemical Society
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    • v.30 no.6
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    • pp.548-552
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    • 1986
  • 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.

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