Ph. Miginiac

Addition reversible de l'organozincique CH2=CH-CH2ZnBr sur une cetone et sur un aldehyde

Abstract Under suitable conditions, the reaction of allylzinc bromide with a carbonyl compound can be reversible.

1,4-Addition of grignard reagents and 1,6-addition of lithium organocuprates to n,n-diethylsorbamide

Abstract When they react with N,N-diethylsorbamide, saturated and allylic Grignard reagents give γ,δ-ethylenic amides (1,4-addition) whereas saturated and allylic lithium organocuprates give β,γ-ethylenic amides (1,6-addition).

Etude de l'action d'organometalliques sur la cetone CH3COCHCHCHCHCH3. Application a la preparation de cetones β-ethyleniques a partir d'organocuprates lithiens

Abstract Lithium organocuprates, R 2 CuLi, react with the ketone CH 3 COCHCHCH CHCH 3 to give the β-ethylenic ketones CH 3 COCH 2 CHCHCH(R)CH 3 corresponding to an 1–6 addition reaction.

Synthese univoque d'amines tertiaires insaturees par voie organometallique a partir de sels d'immonium : II. Synthese d'amines β- et α-ethyleniques

In this work, the best method to prepare unequivocally and in good yields β-and α-ethylenic tertiary amines: RR′CHNR″2 (R unsaturated group, R′, R″ alkyl groups), from immonium salts, has been evaluated.

Sur la reactivite des organomagnesiens derivant de l'addition d'organomagnesiens allyliques sur l'isoprene

Abstract Contrary to a recent report, it is shown that allylic Grignard reagents prepared by treating allylic Grignard reagents with isoprene and a catalytic amount of Cp2TiCl2 react normally with carbon dioxide and carbonyl compounds: a complete allylic rearrangement is observed.

Activation du zinc par le trimethylchlorosilane: Preparation d'alcools β-ethyleniques a partir de bromures α-ethyleniques, de derives carbonyles et de zinc dans l'ether

Abstract δ-ethylenic alcohols can be prepared in ether fron an α-ethylenic bromide, a carbonyl compound and zinc, provided the metal is previously activated by addition of a small amount of trimethyl-chlorosilane.

Addition en 1,8 d'organocuprates lithiens saturés sur la cétone CH3 (CHCH)3COCH3 et sur l'ester CH3(CHCH)3COOC2H5

Abstract The reaction of saturated lithium organocuprates with the trienic ketone CH 3 (CHCH) 3 COCH 3 and with the trienic ester CH 3 (CHCH) 3 COOC 2 H 5 proceeds by a 1,8 conjugate addition to give a β,δ-diethylenic carboynl compound.

Action d'organometalliques n-C4H9CCCHCHCH2M(M = MgCl, ZnBr, Li) sur les cetones et les aldehydes. Etude de la reversibilite de la reaction

Abstract The reactivity of α-ethylenic γ-acetylenic organometallics n-C 4 H 9 CCCHCHCH 2 M (M = MgCl, ZnBr, Li) towards aldehydes and ketones has been studied in comparison with the reactivity of α, γ-biethylenic organometallics CH 2 CHCHCHCH 2 M. The reversibility of these reactions shows more difficulty with enynic organometallics than with biethylenic organometallics.

A Convenient Synthesis of 3-Butyn-1-OL and 2-Methyl-3-Butyn-1-OL

Abstract The method reported in literature for the synthesis of 3-butyn-1-ol involves the reaction of sodium1–7 or lithium8 acetylide with ethylene oxide. It needs liquid ammonia, dry ice and a rather long contact time. Moreover, yield is not consistent: 15–45%9.

Etude de la fixation du groupe tertiaire gem-diméthylpropynyle HCCC(CH3)2 par voie organométallique; applications

Organometallics (CH3)2CCCHM (M  MgBr, Al23Br, ZnBr) are easily prepared from the tertiary bromide (CH3)2C(Br)CCH. They often react to give only acetylenic products but, with some reagents, a mixture of acetylenic and allenic compounds is obtained.