Odile Ruel

A direct synthesis of olefins by reaction of carbonyl compounds with lithio derivatives of 2-[alkyl- or (2′-alkenyl)- or benzyl-sulfonyl]-benzothiazoles.

Abstract During the title reaction, the lithium alkoxides formed as intermediates undergo an intramolecular addition to the neighboring CN group followed an S to 0 benzothiazole transfer and simultaneous extrustion of sulfur dioxide and ejection of 2(3H)-benzothiazolone anion.

Reactivity of the 1-t.butylthio-3-methoxy-1-alkenes towards metalating agents. I: Regioselective deprotonation at either one of the two olefinic sites of the Z-isomers

Abstract THF solutions of the title Z-isomers (with the exception of the propenyl compound) at −78° produce either (i) the 1-metalated derivatives when treated with potassium t.butoxide and n.butyllithium or (ii) the 2-lithiated derivatives when sec.butyllithium is the metalating agent. Both metalated derivatives become new equivalents of the hypothetical anions I and II respectively.

N-aryl-ethenesulphenamides; thermal transformation of two N-)1-naphthyl)-ethenesulphenamides into 1H-benz[g]indoles

Abstract Reaction of vinylmagnesium bromide with morpholine or piperidine-N-sulphenyl chlorides 3a , b affords the N-ethenylthio-morpholine and -piperidine 4a , b . When treated with stoichiometric amounts of an arylamine and methanesulphonic (or trifluoroacetic) acid, the sulphenamides 4 are converted into N-aryl-ethenesulphenamides 6a - e . On heating in toluene, two of these sulphenamides 6d and 6e undergo [3.3]-sigmotropic rearrangements followed by cyclisation of the intermediate amino-thioaldehydes yielding the corresponding 1H-benz[g]indoles 8a , b .

New non-dipolar structures with significant quadratic hyperpoiarizabilites

Abstract ‘Octupolar’ molecules are of particular interest in the field of nonlinear optics due to their potentially large quadratic nonlinearities. Within this framework, we have designed organic chromophores of tetrahedral symmetry and investigated their quadratic nonlinearities by performing harmonic light scattering (HLS) experiments in solutions. Issues related to the molecular engineering of the nonlinearity-transparency trade-off have been addressed. As a result, molecules combining significant quadratic hyperpolarizabilities and excellent transparency have been identified.

Reactivity of the 1-t.butylthio-3-methoxy-1-alkenes towards metalating agents. II: Allylic deprotonation of the E-isomers and of the Z-propenyl derivative

Abstract Deprotonation of the title compounds with a lithiating agent and subsequent alkylation furnish the 1-substituted products 4 . The 1-t.butylthio-3-methoxy-1-lithio-1-alkenes 3 become new equivalents of the hypothetical anions I.

On a sulfurated grignard reagent equivalent to that of 2-chloromethyl-1,3-butadiene. New syntheses of ipsenol (2-methyl-6-methylene-7-octen-4-OL) and of (E)-β-farnesene ((E)-7,11-dimethyl-3-methylene-1,6,10-dodecatriene)

Abstract Experiments on the synthesis of (3-methylene-4-chloro)butylphenyl sulfide, which is the precursor of the corresponding Grignard reagent, are described. With two typical electrophiles, namely isovaleraldehyde and geranyl chloride, this reagent provides the title terpenes in two further simple steps (oxidation to sulfoxides and thermolysis).

Unusual lithiation of 4-(1′,2′-alkadienesulphinyl)-morpholines. Preparation of substituted propargylic sulphinamides and their hydrolytic desulphinylation into the corresponding allenes

Abstract By deprotonation with methyllithium and reaction with water, deuterium oxide or alkyl halide, the γ-monosubstituted allenic sulphinamides 3 have been converted into the substituted propargylic sulphinamides 4 which were hydrolysed or deuterolysed with loss of sulphur dioxide to provide the corresponding allenes 5 .

Preparation and Thermal Properties of N-Alkylidene-Ethenesulfenamides

Abstract A convenient preparation of N,N-bis(trimethylsilyl)-ethenesulfenamides is describe, together with its fluoride-catalysed reaction with aldehydes or ketones to provide several N-alkylidene-ethenesulfenamides. On mild heating, two of these S-vinylthiooximes can be converted into the corresponding substituted pyrroles.

Etude de l'addition nucleophile de quelques thiols sur les alcyn-1 ols-3; additions regio- et stereo-selectives du methyl-2 propanethiol-2.

Resume The ⩾ 92 % regioselective nucleophilic trans -addition of 2-methyl-2-propanethiol to primary, secondary and tertiary 1-alkyn-3-ols, catalyzed by 0,1 equiv. of potassium hydroxide powder, affords good yields of anti -Markovnikoff products.

Reaction of 1, 1-Bis(Methylthio)-3-Methyl-1, 3-Butadiene with Lithiated 3-Methyl-2-Butenyl Phenyl Sulfide. A Special Case of Cyclopropane Formation

Abstract The conjugated ketene dithioacetal 2 is now available by three different procedures1. This electrophilic isoprene compound has been shown to add smoothly some simple lithio derivatives, but the addition of 3-methyl-2-butenyl-lithium gave a product with total inversion of the starting allylic chain1a.