1120-36-1Relevant articles and documents
Fluorination of secondary and primary alcohols by thermal decomposition of electrochemically generated alkoxy triphenylphosphonium tetrafluoroborates
Maeda, Hatsuo,Koide, Takashi,Matsumoto, Sayaka,Ohmori, Hidenobu
, p. 1480 - 1483 (1996)
Replacement of hydroxyl groups in secondary and primary alcohols (1) with a fluorine atom arising from tetrafluoroborate anion has been performed by the electrochemical formation of alkoxy triphenylphosphonium tetrafluoroborates (2) from 1, followed by their thermal decomposition. The procedure is quite simple, involving: (1) constant-current electrolysis of a mixture of 1, Ph3P, and Ph3PH·BF4 in CH2Cl2 in an undivided cell; (2) refluxing a tetrahydrofuran or dioxane solution of the residue afforded by evaporation of the solvent in vacuo after the electrolysis. Cyclic secondary alcohols such as 3β-hydroxy steroids and 2-adamantanol are transformed into the corresponding fluorides in satisfactory yields when the geometry of the leaving group in 2 is suitable for the substitution or an elimination process for 2 to give an alkene is stereochemically forbidden. The fluorination of steroidal alcohols and 4-phenyl-1-cyclohexanol proceeded with complete inversion, demonstrating that a fluorine atom from the tetrafluoroborate anion attacks from the side opposite to the phosphonium moiety in 2 via an SN2 mechanism rather than an SN1 mechanism. The fluorination of acyclic secondary and primary alcohols was performed by the present method in reasonable yields, although the reaction for the latter required more forcing conditions, such as refluxing in dioxane.
Synergistic sex pheromone components of white-spotted tussock moth, Orgyia thyellina
Gries, Gerhard,Clearwater, John,Gries, Regine,Khaskin, Grigori,King, Skip,Schaefer, Paul
, p. 1091 - 1104 (1999)
In 1996, the exotic white-spotted tussock moth (WSTM), Orgyia thyellina (Lepidoptera: Lymantriidae), was discovered in Auckland, New Zealand. Because establishment of WSTM would threaten New Zealand's orchard industry and international trade, eradication of WSTM with microbial insecticide was initiated. To monitor and complement eradication of WSTM by capture of male moths in pheromone-baited traps, pheromone components of female WSTM needed to be identified. Coupled gas chromatographic-electroantennographic detection analysis of pheromone gland extract revealed several compounds that elicited responses from male moth antennae. Mass spectra of the two most EAD-active compounds suggested, and comparative GC-MS of authentic standards confirmed, that they were (Z)-6-heneicosen-11-one (Z6-11-one) and (Z)-6-heneicosen-9- one, the latter termed here 'thyellinone.' In field experiments in Japan, Z6- 11-one plus thyellinone at a 100:5 ratio attracted WSTM males, whereas either ketone alone failed to attract a single male moth. Addition of further candidate pheromone components did not enhance attractiveness of the binary blend. Through the 1997-1998 summer, 45,000 commercial trap lures baited with 2000 μg of Z6-11-one and 100 μg of thyellinone were deployed in Auckland towards eradication of the residual WSTM population.
Iron-catalyzed cross-coupling of alkenyl sulfides with grignard reagents
Itami, Kenichiro,Higashi, Shohei,Mineno, Masahiro,Yoshida, Jun-Ichi
, p. 1219 - 1222 (2005)
(Chemical Equation Presented) The iron-catalyzed cross-coupling reaction of alkenyl sulfides with Grignard reagents is described. While the cross-coupling proceeds efficiently at alkenyl-S bonds, almost no cross-coupling takes place at aryl-S bonds, attesting to a unique selectivity of iron catalysis. The beneficial effect of potentially coordinating 2-pyrimidyl group on sulfur is also described.
Reduction of fatty acid methyl esters to fatty alcohols to improve volatility for isotopic analysis without extraneous carbon.
Corso,Lewis,Brenna
, p. 3752 - 3756 (1998)
Carbon in derivatization groups cannot be distinguished from analyte carbon by chromatography-based high-precision compound-specific or position-specific isotope analysis. We report the reduction of fatty acid methyl esters to fatty alcohols to facilitate high-quality chromatographic separation, without addition of extraneous carbon, with subsequent high-precision position-specific isotope analysis. Methyl palmitate is quantitatively reduced to 1-hexadecanol by LiAlH4 in a one-step reaction. Gas-phase pyrolysis of 1-hexadecanol results in a series of monounsaturated alcohols and alpha-olefins analogous to fragmentation found for methyl palmitate, as well as an additional peak corresponding to the pyrolytic dehydration product, 1-hexadecene. Carbon isotope analysis of the fragments yielded precision of SD (delta 13C) 0.4/1000. Results of position-specific analysis of very low enrichment [1-13C]-1-hexadecanol (delta 13C = -4.00/1000) showed no evidence of scrambling of the C1 position, and isotope ratios in accord with expectations. The pyrolysis product 1-hexadecene was isotopically enriched relative to 1-hexadecanol, which may cause minor depletion of other pyrolysis products that can be taken into account by routine calibration. The procedure is general and can be extended to compound-specific and position-specific analysis of moderate molecular weight, low-volatility analytes containing acid groups that would otherwise be blocked with methyl, ethyl, acetyl, or trimethyl silyl groups containing extraneous carbon.
REDUCTION OF THIIRANES TO ALKENES AND ALKANES
Schauder, J.R.,Denis, J.N.,Krief, A.
, p. 1657 - 1660 (1983)
Various reagents were tested in order to reduce thiiranes to alkanes or olefins.The results of this investigation is presented in this letter.
THERMODYNAMIC PARAMETERS OF DEHYDROGENATION REACTIONS OF NORMAL PARAFFINS WITH A C10-C15 HYDROCARBON COMPOSITION TO OLEFINS
Eliseev, N. A.,Sterligov, O. D.,Isagulyants, G. V.
, p. 674 - 677 (1987)
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Palladium-Catalyzed Oxidative Dehydrosilylation for Contra-Thermodynamic Olefin Isomerization
Butcher, Trevor W.,Hanna, Steven,Hartwig, John F.,Wills, Tyler
, p. 8736 - 8741 (2020/09/23)
We report a newly developed, palladium-catalyzed dehydrosilylation of terminal alkylsilanes that combines with chain-walking hydrosilylation to create a one-pot isomerization of internal olefins to terminal olefins. This catalytic dehydrosilylation is one of the few examples of thermal catalytic functionalizations of unactivated alkylsilanes. The reaction involves transmetalation of an alkylsilane, β-hydride elimination, release of the terminal olefin, and reoxidation of the palladium catalyst. A variety of linear internal olefins underwent the overall isomerization to terminal olefins in good yields and in good regioselectivities. Particularly noteworthy, isomerizations occurring over seven carbon units proceeded in yields that are comparable to those of isomerizations occurring over one carbon unit.
Re-catalyzed deoxydehydration of polyols to olefins using indoline reductants
Jefferson, Alana,Srivastava, Radhey S.
, p. 268 - 271 (2019/01/23)
A rhenium (CH3ReO3, MTO) catalyzed deoxydehyradration (DODH) of glycols to alkenes has been achieved using hydroaromatic compounds as H-transfer reductants. Of the hydroaromatics examined, indoline was the most efficient and proved to be better potential hydrogen donor. The yield of the products is moderate to excellent and the reaction is very clean with the only indole, the oxidized byproduct of indoline detected.[Figure presented]
