765-03-7Relevant articles and documents
AGRICULTURAL PHEROMONE COMPOSITIONS COMPRISING POSITIONAL ISOMERS
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Paragraph 0368, (2017/06/12)
The present disclosure provides pheromone compositions. In some aspects, the compositions taught herein comprise a pheromone chemically corresponding to the pheromone naturally produced by a given insect, along with at least one positional isomer of said pheromone. In various aspects, pheromone compositions of the present disclosure are able to modulate the response of the insect based on the ratio of natural pheromone to its positional isomer.
SYNTHESIS OF OLEFINIC ALCOHOLS VIA ENZYMATIC TERMINAL HYDROXYLATION
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Paragraph 0281; 0282, (2016/01/30)
In certain aspects, the present invention provides methods for producing terminally hydroxylated alkenes and alkynes by contacting an unsaturated or saturated hydrocarbon substrate with a hydroxylase enzyme. Exemplary terminal hydroxylases useful for carrying out the methods of the invention exhibit strong selectivity towards one terminal carbon of a hydrocarbon substrate and include, but are not limited to, non-heme diiron alkane monooxygenases, cytochromes P450 (e.g., cytochromes P450 of the CYP52 and CYP153 family), as well as long chain alkane hydroxylases. In some embodiments, the terminally hydroxylated alkene or alkyne is further converted to a terminal alkenal. In certain embodiments, terminally hydroxylated alkenes and alkynes are useful as insect pheromones which modify insect behavior. In other embodiments, terminally hydroxylated alkenes and alkynes are useful intermediates for producing pheromones via acetylation or oxidation of the alcohol moiety.
Silver(I)-catalysed protiodesilylation of 1-(Trimethylsilyl)-1-alkynes
Carpita, Adriano,Mannocci, Luca,Rossi, Renzo
, p. 1859 - 1864 (2007/10/03)
A procedure for protiodesilylation of 1-(trimethylsilyl)-1-alkynes that involves the use of catalytic amounts of AgNO3 and does not require the employment of KCN is described. This procedure allows for chemoselective deprotection of 1-(trimethylsilyl)-1-alkynes containing α-(trimethylsilyl) benzyl moieties, tert-butyldiphenylsilyl alkyl ethers or tert-butyldimethylsilyl aryl ether groups. However, it causes complete desilylation of l-(trimethylsilyl)-1-alkynes characterised by a primary alcoholic group protected as a tert-butyldimethylsilyl ether. Interestingly, compounds that contain this last functional group can also furnish the corresponding alcohols by treatment with a catalytic amount of aqueous HNO3. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.
Parallel synthesis of terminal alkynes using a ROMPgel-supported ethyl 1-diazo-2-oxopropylphosphonate
Barrett, Anthony G. M.,Hopkins, Brian T.,Love, Andrew C.,Tedeschi, Livio
, p. 835 - 837 (2007/10/03)
ROMPgel-supported ethyl 1-diazo-2-oxopropylphosphonate has been prepared, and the supported reagent has been effectively employed in the conversion of a variety of aldehydes into terminal alkynes under mild reaction conditions. The influence of cross-link structure, comonomers, and polymer structure on reaction efficiency has been examined.
Reaction of Grignard compounds with 4-chloro-2-methyl-3-butyn-2-ol in Diethyl Ether equivalents
Shchelkunov,Sivolobova,Mataeva,Minbaev,Muldakhmetov
, p. 5 - 8 (2007/10/03)
Reactions of RMgX · THF complexes with 4-chloro-2-methyl-3-butyn-2-ol in aromatic hydrocarbons were studied. The complexes formed by arylmagnesium halides require the presence of anisole for the reaction to occur. 4-Chloro-2-methyl-3-butyn-2-ol can be synthesized by reaction of 2-methyl-3-butyn-2-ol with sodium hypochloride in the two-phase system water-benzene.
Insertion of 1-chloro-1-lithioalkenes into organozirconocenes. A versatile synthesis of stereodefined unsaturated systems
Kasatkin, Aleksandr,Whitby, Richard J.
, p. 7039 - 7049 (2007/10/03)
Hydrozirconation of alkenes and alkynes, followed by insertion of 1- halo-1-lithio-1-alkenes, generated in situ by lithium tetramethylpiperidide deprotonation of vinyl halides, affords vinylzirconocene species which may be further elaborated. The method provides easy access to many structures including terminal (3E)- and (3Z)-1,3-dienes and (3E,5E)- and (3Z,5E)-1,3,5- trienes, and internal (E,Z)-dienes,(E,Z,E)-trienes, and (1E, 3Z)1,3-dien-5- ynes. Insertion of 2-monosubstituted 1-halo-1-lithio-1-alkenes occurs with clean inversion of configuration of the sp2-carbenoid carbon. Carbenoids derived by deprotonation of 2,2-disubstituted 1-halo-1-alkenes gave poor stereocontrol probably due to isomerization before insertion into the organozirconium species. Insertion of vinyl carbenoids into alkynylzirconocenes affords terminal (3E)- or (3Z)-1,3-dien-5-ynes, internal (1E,3Z)-1,3-dien-5-ynes, and (Z)-3-en-1,5-diynes.
PROTOTROPIC ISOMERIZATION OF ACETYLENIC HYDROCARBONS AND ALCOHOLS UNDER THE INFLUENCE OF LITHIUM 2-AMINOETHYLAMIDE IN ETHYLENEDIAMINE
Remizova, L. A.,Kryukov, A. V.,Balova, I. A.,Favorskaya, I. A.
, p. 909 - 912 (2007/10/02)
The system containing lithium 2-aminoethylamide in ethylenediamine is an effective system for the production of acetylenic hydrocarbons and alcohols with a terminal triple bond.As a result of prototropic isomerization in this system 5-dodecyne, 4-tridecyne, 7-tetradecyne, 2-heptyn-1-ol, 2-nonyn-1-ol, and 2-undecyn-1-ol gave high yields of the corresponding isomers with a terminal triple bond, i.e., 1-dodecyne, 1-tridecyne, 1-tetradecyne, 6-heptyn-1-ol, 8-nonyn-1-ol, and 10-undecyn-1-ol.The synthesis of the long-chain alcohol 8,10-heneicosadiyn-1-ol was realized from the compounds containing a triple bond.
Photochemistry of Alkenes. 9. Medium-sized cycloalkenes
Kropp, Paul J.,Mason, J. Derek,Smith, Gardiner F. H.
, p. 1845 - 1849 (2007/10/02)
The behavior of three medium-sized cycloalkenes cyclooctene (10), cyclodecene (17) and cyclododecene (21) on direct irradiation in pentane and methanol solution has been studied.The results are summarized in Tables 1-3.Irradiation of medium-sized cycloalkenes is a convenient procedure for the preparation of bicyclic products (cf. 13, 14, 19, 20 and 23) through transannular insertion reactions of carbene intermediates (cf. 11, 18, and 22) thought to arise from rearrangement of the 1 state via a 1,2-hydrogen shift.The formation of trans-decalin (20) is in contrast to the reported formation of the cis isomer on base-initiated decomposition of the corresponding tosylhydrazone.None of the three cycloalkenes 10, 17, or 21 underwent competing nucleophilic trapping of the 1 state in methanol, in contrast with other alkenes previously studied.However, cyclododecene (21) afforded the methyl ether 25, which apparently resulted from protonation of the 1(?,?*) state, and the epoxide 26, which is thought to arise from electron transfer to oxygen by the 1 state followed by protonation of the resulting superoxide ion and oxidation of unreacted cyclododecene (21).
CLEAVAGE OF VINYL CARBON-SILICON BOND WITH TETRABUTYLAMMONIUM FLUORIDE
Oda, Hiroji,Sato, Mitsuyoshi,Morizawa, Yoshitomi,Oshima, Koichiro,Nozaki, Hitoshi
, p. 3257 - 3268 (2007/10/02)
Dimethylphenylsilyl group is removed from a vinyl carbon with tetrabutylammonium fluoride.The presence of phenyl group on silicon atom plays a critical role.The cleavage of allyldimethylsilyl- and alkoxydimethylsilyl groups also proceeds very easily.
Synthesis of Lipophilic 18-Crown-6 Diacids for the Membrane Transport of Alkaline-Earth Cations
Fyles, Thomas M.,McGavin, Cynthia A.,Whitfield, Dennis M.
, p. 753 - 761 (2007/10/02)
The synthesis of three different types of lipophilic 18-crown-6 diacids is described.A didecyl crown ether 2,3-diacid (1) was prepared as a minor product from a diiodide precursor (12) and threo-11,12-docosanediol by thallous ethoxide cyclization.The major nonpolymeric products resulted from elimination followed by cyclization to give 15-crown-5-derivatives.A crown ether 11,12-diamide 2,3-diacid (4) was prepared by a similar route involving cyclization of a benzyl protected precursor (26) and N,N,N',N'-tetramethyltartaramide (9).Isomeric syn and anti 2,11(12)-diamide 3,12(11)-diacid derivatives 6 and 7 were prepared from the known crown ether bisanhydride 8 and alkylamines.The product mixture was separated by chromatography, and the isomers were identified by comparison of acidity and stability constants for complexation with those of closely related syn/anti crown ether acids.
