Some alkali metal alkyl amides as alkyne isomerization reagents: selective isomerization of one triple bond of a diynol

The lithium and sodium salts of 1,2-diaminoethane, 1,3-diaminopropane, n-butylamine, and the lithium salt of isobutylamine were studied as potential reagents for isomerization of triple bonds in alkyn-1-ols. The sodium salts of the diamines afforded high yields of the ω-alkyn-1-ol. Somewhat surprisingly, the sodium salt of n-butylamine also effects isomerization to the terminal position. The lithium salt of 1,3-diaminopropane gave the highest conversion of 2- to 3-alkyn-1-ol. A novel, selective rearrangement of one triple bond of a diynol, a 2, ω- to 3, ω-diyn-1-ol isomerization, was incorporated into a synthesis of the insect sex pheromone 3,13-octadecadienol acetate.

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Isomerization of acetylenic acids with sodium salt of 1,2-diaminoethane: a one step synthesis of megatomoic acid

Canadian Journal of Chemistry ◽

10.1139/v82-182 ◽

1982 ◽

Vol 60 (10) ◽

pp. 1238-1243 ◽

Cited By ~ 8

Author(s):

S. R. Abrams

Keyword(s):

Sex Pheromone ◽

Sodium Salt ◽

Triple Bond ◽

Carboxyl Group ◽

One Step ◽

Acetylenic Acids ◽

Black Carpet Beetle ◽

Megatomoic Acid

A number of isomeric tetradecynoic acids were isomerized with the sodium salt of 1,2-diaminoethane. Isomers having the triple bond near the carboxyl group rearranged to E,Z-3,5- and E,E-3,5-tetradecadienoic acids (1 and 2), the former compound being the sex pheromone of the black carpet beetle. Isomers having the triple bond closer to the terminus of the chain afforded some 13-tetradecynoic acid along with 1 and 2. Delocalized anions 12 and 13 are thought to contribute to the formation of 1 and 2.

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Configuration of sodium salt and preparation of sulphonates and carboxylates of (E)- and (Z)-3-(hydroxymethylene)dihydro-2(3H)-furanone

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19841907 ◽

1984 ◽

Vol 49 (8) ◽

pp. 1907-1913 ◽

Cited By ~ 5

Author(s):

Jaroslav Jonas

Keyword(s):

Solid State ◽

Sodium Salt ◽

Nmr Spectra ◽

Sulphonic Acid ◽

Sodium Salts ◽

Acyl Chlorides ◽

Acid Anhydrides ◽

High Yields ◽

C Nmr

The sodium salt of 3-(hydroxymethylene)dihydro-2(3H)-furanone (I) can be obtained in solid state in the form of (Z)-isomer, or their mixture, whereas in solutions it only exists in the form of (E)-isomer. Reactions of these sodium salts with sulphonyl or acyl chlorides or sulphonic acid anhydrides give the respective (E)- and (Z)-sulphonates or carboxylates of 3-(hydroxymethylene)dihydro-2(3H)-furanone in high yields and purity. Configuration of the sodium salt isomers has been confirmed by their IR and 12C NMR spectra in solid state, that of the isomeric sulphonates and carboxylates has been confirmed by their 1H and 13C NMR spectra in solution.

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Intramolecular Addition of a Dimethylamino C(sp3)–H Bond across C–C Triple Bonds using IrCl(DTBM-SEGPHOS)(ethylene) Catalyst: Synthesis of Indoles from 2-Alkynyl-N-methylanilines

Synthesis ◽

10.1055/a-1511-1025 ◽

2021 ◽

Author(s):

Toshimichi Ohmura ◽

Kaito Yagi ◽

Takeru Torigoe ◽

Michinori Suginome

Keyword(s):

Double Bond ◽

Triple Bond ◽

Iridium Complex ◽

Dimethylamino Group ◽

Catalyst Synthesis ◽

Double Bond Isomerization ◽

Triple Bonds ◽

High Yields

Intramolecular addition of a C(sp3)–H bond of a dimethylamino group across a C–C triple bond in 2-alkynyl-N,N-dimethylanilines was effectively catalyzed by a new iridium complex IrCl(DTBM-SEGPHOS)(C2H4) in mesitylene at 150 °C. The intramolecular C(sp3)–H addition was followed by double bond isomerization to afford 3-substituted indoles in good to high yields.

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Faculty Opinions recommendation of Insect sex-pheromone signals mediated by specific combinations of olfactory receptors.

Faculty Opinions – Post-Publication Peer Review of the Biomedical Literature ◽

10.3410/f.1024004.284826 ◽

2005 ◽

Author(s):

John Ngai

Keyword(s):

Sex Pheromone ◽

Olfactory Receptors ◽

Insect Sex Pheromone ◽

Insect Sex

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Convenient Synthesis of (Z)-7- and (E)-9-dodecene-1-yl Acetate, Components of Some Lepidoptera Insect Sex Pheromone

Revista de Chimie ◽

10.37358/rc.17.1.5415 ◽

2017 ◽

Vol 68 (1) ◽

pp. 180-185

Author(s):

Adriana Maria Andreica ◽

Lucia Gansca ◽

Irina Ciotlaus ◽

Ioan Oprean

Keyword(s):

Sex Pheromone ◽

Coupling Reaction ◽

Coupling Scheme ◽

Lithium Aluminium Hydride ◽

Terminal Alkyne ◽

Mercury Derivative ◽

Lithium Aluminium ◽

Convenient Synthesis ◽

Practical Synthesis ◽

Insect Sex

Were developed new and practical synthesis of (Z)-7-dodecene-1-yl acetate and (E)-9-dodecene-1-yl acetate. The routes involve, as the key step, the use of the mercury derivative of the terminal-alkyne w-functionalised as intermediate. The synthesis of (Z)-7-dodecene-1-yl acetate was based on a C6+C2=C8 and C8+C4=C12 coupling scheme, starting from 1,6-hexane-diol. The first coupling reaction took place between 1-tert-butoxy-6-bromo-hexane and lithium acetylide-ethylendiamine complex obtaining 1-tert-butoxy-oct-7-yne, which is transformed in di[tert-butoxy-oct-7-yne]mercury. The mercury derivative was directly lithiated and then alkylated with 1-bromobutane obtaining 1-tert-butoxy-dodec-7-yne. After acetylation and reduction with lithium aluminium hydride of 7-dodecyne-1-yl acetate gave (Z)-7-dodecene-1-yl acetate with 96 % purity. The synthesis of (E)-9-dodecene-1-yl acetate was based on a C8+C2=C10 and C10+C2=C12 coupling scheme, starting from 1,8-octane-diol. The first coupling reaction took place between 1-tert-butoxy-8-bromo-octane and lithium acetylide-ethylendiamine complex obtaining 1-tert-butoxy-dec-9-yne, which is transformed in di[tert-butoxy-dec-9-yne]mercury. The mercury derivative was directly lithiated and then alkylated with 1-bromoethane obtaining 1-tert-butoxy-dodec-9-yne. After reduction with lithium aluminium hydride of 1-tert-butoxy-(E)-9-dodecene and acetylation was obtained (E)-9-dodecene-1-yl acetate with 97 % purity.

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Wechselwirkungen in Molekülkristallen, 160 [1,2]. Kristallzüchtung und Strukturbestimmung der verschiedenartigen Polyphenyl-Kontaktionenmultipel [p-Quaterphenylee⊖⊖][Na⊕(DME)3]2, [p-Quaterphenyl⊖⊖(Na⊕(THF)3)2] und [p-Terphenyl⊖⊖Na⊕(DME)2Na⊕(DME)]2 / Interaction in Molecular Crystals, 160 [1, 2]. Crystallization and Structure Determination of the Different Polyphenyl Contact Ion Multiples [p-Quaterphenylee⊖⊖][Na⊕(DME)3]2, [p-Quaterphenyl⊖⊖(Na⊕(THF)3)2] und [p-Terphenyl⊖⊖Na⊕(DME)2Na⊕(DME)]2

Zeitschrift für Naturforschung B ◽

10.1515/znb-2000-1201 ◽

2000 ◽

Vol 55 (12) ◽

pp. 1103-1113 ◽

Cited By ~ 3

Author(s):

Hans Bock ◽

K. Gharagozloo-Hubmann ◽

M. Sievert

Keyword(s):

Crystal Structure ◽

Single Crystal ◽

Sodium Salt ◽

Structure Determination ◽

Metal Cation ◽

Molecular Crystals ◽

Sodium Salts ◽

Structure Determinations ◽

Cation Coordination

The π-hydrocarbons p-terphenyl and p-quaterphenyl are reduced to their dianions in aprotic solutions of different ethers at sodium metal mirrors. Single crystal structure determinations of the solvent-separated or solvens-shared contact ion multiples, [p-terphenyl⊖⊖ Na⊕(DME)2Na⊕DME]2, p-quaterphenyl⊖⊖ ][Na⊕(DME)3]2 and [p-quaterpheny⊖⊖( Na⊕(THF)3)2], prove the essential cation solvation by the chelating dimethoxyethane (DME) versus the bulky tetrahydrofuran (THF) ligands: The solution network of equilibria between solvent separated and solvent shared ion aggregates can be considerably and transparently modified by the ether solvent selected. In addition, the structures of the monomeric sodium salts reveal partly novel details of metal cation coordination by contacts Na⊕ ··· O as well as Na⊕ ··· Cπ such as in the dimeric sodium salt of p-terphenyl dianion, [(DME)2Na⊕ (terphenyl⊖⊖)(Na⊕ DME)(terphenyl⊖⊖)Na⊕ (DME)2].

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Stereoselective Synthesis of Insect Sex Pheromone Analogues Having a Fluorine Atom on Their Double Bonds.

ChemInform ◽

10.1002/chin.200550202 ◽

2005 ◽

Vol 36 (50) ◽

Author(s):

Tong Guan ◽

Masanori Yoshida ◽

Daisuke Ota ◽

Tsuyoshi Fukuhara ◽

Shoji Hara

Keyword(s):

Sex Pheromone ◽

Fluorine Atom ◽

Stereoselective Synthesis ◽

Double Bonds ◽

Insect Sex Pheromone ◽

Insect Sex

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A Convenient Preparation of Anhydrous Alkali Metal Thiocarboxylates

Zeitschrift für Naturforschung B ◽

10.1515/znb-1983-1210 ◽

1983 ◽

Vol 38 (12) ◽

pp. 1585-1590 ◽

Cited By ~ 11

Author(s):

Shinzi Kato ◽

Motohiro Oguri ◽

Masaru Ishida

Keyword(s):

Alkali Metal ◽

Physical Properties ◽

Metal Hydrides ◽

High Yields ◽

Convenient Preparation

A series of alkali metal thiocarboxylates (1-5) were found to be readily obtained in high yields by the reaction of thiocarboxylic acids with metal hydrides (LiH, NaH, KH), and rubidium or caesium acetates, respectively. Their physical properties were disclosed

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