General methodology for the synthesis of conjugated dienic insect sex pheromones

A general methodology for the synthesis of various types of dienic insect sex pheromones (Z-E, E-Z, Z-Z) is based on the carbocupration of acetylene by functionalised or non-functionalised lithium dialkyl cuprates, followed by the coupling of the resulting Z dialkenyl cuprates with functionalised or non-functionalised E or Z alkenyl iodides under Pd° catalysis. The following compounds were efficiently synthesized with a high degree of stereoisomeric purity: (E-Z)7, 9-dodecadien,-l-yl acetate 1 (Lobesia botrana), (E-Z)10, 12-hexadecadien,-l-ol 2 (Bombyx mori), (Z-E)9, 11-tetradecadien,-l-yl acetate 3Spodoptera littoralis), (Z-E)5, 7-dodecadien-l-ol 4 (Malascoma disstria), (Z-Z)11, 13-Hexadecadien-l-al 5 (Amyelois transitella), (Z)9,ll-dodecadien-l-yl acetate 6 (Diparopsis castanea) and (Z-Z)9,11-tridecadien-l-yl acetate 22 (a known “pseudo-pheromone”).     

Alkylation des carbenoides par des nucleophiles. : II. Substitution nucleophile de l'halogene de carbenoides α phosphonates catalysee par le cuivre(I)

The addition of a catalytic amount (12%) of a copper(I) salt to a mixture of an α-lithio-α-chloroalkylphosphonate and an alkyllithium RLi or a Grignard reagent RMgX leads to the formation of a new organometallic reagent in which the R group has replaced the chlorine atom of the carbenoid. This nucleophilic alkylation of carbenoids can be performed with secondary-alkyl Grignard reagents, and with aryllithium, alkenyllithium and alkynyllithium reagents in good yields (60–80%).     

Substitution des halogéno-1 alcynes-1 par les dérivés organométalliques du cuivre. accès à une nouvelle classe de synthons: application à

1-Bromo- and 1-iodo-1-alkynes are alkylated by organocopper(I) compounds. Alkenylcopper(I) derivatives undergo substitution with retention of configuration leading to conjugated and functional enynes, from which conjugated dienes can be obtained.     

A spectrometric study of a 40-MHz inductively coupled plasma—IV. Assessment of this source in oscillator strength measurements of Ta I and Ta II

An inductively coupled argon plasma was evaluated as a source for the determination of oscillator strength values of several lines of Ta I and Ta II. Although there is a departure from LTE, a partial LTE between excited states of injected elements was assumed. This allowed the authors to consider an excitation temperature of 4800 K in the determination of ?-values of tantalum.     

Preparation d'acides β-amino-ethyl-phosphoniques

We describe a new, practical, synthesis of β-amino ethyl phosphonic acids. Organolithium reagents generated from nitriles are condensed with bis(dimethyl amino) chlorophosphates, followed by alkylation using phase transfer catalysis, reduction of nitrile group, and acid hydrolysis.     

Reactivity of RCu,BF3 and R2CuLi,BF3 towards the ether linkage. Epoxides,acetals and orthoformates

The association of BF₃ to organocopper and cuprate reagents increases dramatically their reactivity towards epoxides. The same reagents cleave acetals to afford the product of substitution of one alkoxy group, whereas orthoformates lead to acetals under conditions where no further attack occurs.     

Vinyl-copper derivatives XII : Stereospecific synthesis of allylic amines by aminomethylation of organocopper reagents

the carbocupration or hydroalumination of alkynes followed by amino-methylation yields allylic amines. The stereochemical integrity of the alkenyl moiety is completely retained in both cases.     

Recherches sur les alcoylamidures de lithium : VI. Étude de la rupture de quelques éthers aryliques

The amides R₂NLi prepared and used in hexamethylphosphorotriamide (HMPT) cause the cleavage of arylic ethers.The cleavage of ethers ArOR′ leads to ArNR₂ amines or to ArOH phenols depending on the aliphatic group R'.The influence of the nature of the amide R₂NLi and of its concentration is studied.The cleavage of oxides ArOR′ and ArOAr′ is examined in relation with the effect of the substituents of the aromatic nucleus. It is noticed that the mechanism of these cleavages do not involve any arynic character. The possibility of a direct nucleophilic substitution is considered.Finally, the ethers ArOCH₂Ar lead predominantly to the alcohols

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