Complexation de l'anion fluorure par des tetramines cycliques protonees.

The $\text{s}$ynthesis of the new tetraazamacrocycle [20]N₄ is briefly described; complexation of F by the fully protonated [16]N₄, [18]N₄ and [20]N₄ macrocycles is investigated.     

Structure cristalline et expansion thermique de l'iodure de nickel hexahydrate

The structure of NiI₂, 6 H₂O has been determined by X-ray diffraction techniques. The dimensions of the hexagonal unit cell are: a = 7.638 ± 0.005 Å and c = 4.876 ± 0.005 Å, with Z = 1. The space group is $\text{P}\text{3}\text{m1}$. The structure was deduced from Patterson and Fourier syntheses and refined by least-squares method to a final R value of 0.09. It is almost a layer structure, each layer is composed by n complex ions [Ni(H₂O)₆]²⁺ surrounded by 2 n ions I^?; this is in agreement with the good cleavage of crystals and with the marked anisotropy in the thermal expansion. But the structure may also be regarded as a derivation of NiAs structure, with only $\text{1}\text{8}$ of octahedral holes occupied. A structural classification of compounds MX₂, 6 H₂O is proposed.     

Preparation de copolymères greffés par voie cationique-II. Étude du greffage cationique de L'indène sur des polymères troncs insaturés

Graft copolymers have been obtained through the polymerization of indene initiated with diethylaluminium chloride and tert, butyl chloride, in the presence of ethylene-propylene-diene terpolymers. In the case of polymers with unhindered unsaturated units, like those derived from 1,4-hexadiene and dicyclopentadiene, the increase of $\text{M}{}_{\mathrm{n}}$ is mainly due to backbone duplication, and grafting efficiencies are low. Terpolymers with sterically hindered units, like those derived from ethylidene norbornene, yield graft copolymers with high grafting efficiencies (up to 50%). In this case, an initiation mechanism involving the unsaturated unit is proposed in order to explain the difference between these two types of reactions.     

Préparation de copolymères greffés par voie cationique-1: Etude du greffage cationique de l'indene sur le caoutchouc butyl chlore

Cationic grafting of indene onto chlorinated butyl rubber (CBC), initiated with diethylaluminium monochloride in a mixture of methylene dichloride and methylcyclohexane, has been carried out at ?50°. Grafting efficiencies near 100% and complete conversion of indene were obtained. The polymerization rate is proportional to indene concentration and to $\text{(}\text{initiator concentration}\text{)}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$, as in reactions carried out in the presence alkyl halide cocatalysts. No simple dependence on cocatalytic chlorine could be found. Influence of the concentration of reagents on the nature of the reaction products, especially of the ratios

$\text{(CBC)}\text{(indene)}\text{(AlEt}{}_2\text{Cl)}\text{and}\text{(AlEt}{}_2\text{Cl)}$

has been measured. Since transfer reactions occur during polymerization, the high grafting efficiencies are attributed to grafting of transfered polyindene chains.     

Polymérisation cationique du chloro-1 butadiène et copolymérisation avec l'isobutène

The cationic homopolymerization of 1-chlorobutadiene and its copolymerization with isobutene have been carried out in dichloromethane solution. The catalyst-cocatalyst pairs used were AlEt₂Cl-(CH₃)₃CCl and AlEtCl₂-(CH₃)₃CCl. In the latter case, the use of (CH₃)₃CCl was not necessary. According to experimental conditions, high molecular weight copolymers ($\text{M}{}_{\mathrm{n}}\text{= 200,000}$) insoluble in CH₂Cl₂, or soluble low polymers ($\text{M}{}_{\mathrm{n}}\text{= 20,000}$) were obtained. Homopoly-1-chlorobutadienes were soluble low molecular weight polymers ($\text{M}{}_{\mathrm{n}}\text{= 10,000}$). The 1-chlorobutadiene units in the polymers are nearly exclusively 3,4 (mainly trans). Consequently, this method is not convenient to prepare elastomers with a 1,4 structure similar to that of chlorinated butyl rubber.     

Decarboxylation catalytique et quantitative d'acides arylacetiques en presence'de cuivre I

Copper(I) salts of arylacetic acids $\text{1}$ RCO₂H readily undergo a catalytic and quantitative decarboxylation in acetonitrile leading to hydrocarbons $\text{2}$ RH when the corresponding carbanions R are stabilized by resonance and/or electronwithdrawing substituents.     

Contribution à l'étude structurale de la wüstite solide de haute température

The structure of wüstite Fe_1?zO is studied by neutron diffraction on one polycrystalline sample under equilibrium conditions at high temperature. The mean isotrope temperature factor B is expressed as a sum of two parts, B_Th and B_St, which vary linearly with a single parameter, respectively temperature and z. A classification is established for clusters ($\text{m}\text{n}$) settled from m vacancies in octahedral sites and n Fe^III ions in interstitial sites. Sixteen values have been experimentally determined for the vacancies to interstitials ratio $\text{? =}\text{(z + t)}\text{t}\text{=}\text{m}\text{n}$. A constant value of ?, which is lower than 3, is observed. This result characterizes the short-range order. It eliminates several possibilities of clusters like those obeying the relation $\text{? =}\text{(1 + 3n)}\text{n}$. Other clusters, namely ($\text{16}\text{6}$) or ($\text{40}\text{14}$), might agree. The ($\text{8}\text{3}$) and ($\text{9}\text{4}$) clusters obtained from ($\text{4}\text{1}$) clusters joined by an edge would be the more likely. An analysis of diffuse scattering eliminates the hypothesis of large domains with inverse spinel structure. The structural differences between the three varieties W₁, W₂ and W₃ would not be found in a structural change of clusters.     

Etude cristallographique de l'arsénotellurure de zirconium quadratique

Single crystals of zirconium arsenotelluride (PbFCl type) have been prepared by direct synthesis from the elements. Chemical analysis gives: $\text{As}\text{Zr}\text{= 1.43 ± 0.02}$ and $\text{Te}\text{Zr}\text{= 0.46 ± 0.01}$, in atoms. Lattice constants are: a = 3.82 ± 0.01 Å and c = 8.17 ± 0.02Å. Experimental density is equal to 7.14 ± 0.05. Unit cell thus contains Zr_2.00As_2.86Te_0.92. The structure has been solved with 227 reflections of a single crystal recorded at room temperature. The final R factor is 0.081, excluding zero reflections. Part of the arsenic atoms fills a site and the remainder is located in a second site, the occupation of which is completed by a part of zirconium atoms. The third site is occupied, but not filled, by the tellurium atoms and the remainder of zirconium atoms.     

Reactions de photoaddition de benzo[b]selenophenes avec l'acetylene dicarboxylate de methyle et avec le dichloro-1,2 ethylene

Photoirradiated in presence of acetophenone, benzo[b]selenophene and its 3-methyl derivative add to dimethyl acetylenedicarboxylate. In each ease, the primary reaction product is unstable and has not been isolated. Photoexeited in its triplet state (the energy of which is in the neighbourhood of 69 $\text{kcal}\text{mole}$) benzo[b]selenophene and its 2- and 3-methyl, 2,3 dimethyl, 3 acetoxy and 2-methyl-3-acetoxy derivatives add to 1,2 dichloroethylene leading to cyclobutanes. Neither cyclo-addition occurs in absence of photosensitiser. Single-crystal X-ray analysis gave the structures of the two adducts of 3-acetoxybenzo[b]selenophene with trans-1,2-dichloroethylene. In both compounds the chlorine atoms are trans.     

A novel route to meta-aminobenzotrifluoride

Product patterns can be altered in reactions of $\text{m}$-nitrobenzotrichloride [VI] with [AHF]_x·NH₄F complex. Side-chain fluorination predominates under ‘mild’ conditions. In contrast. ‘forcing’ conditions affected unexpected $\text{in}$-$\text{situ}$ fluorination-reduction to give $\text{m}$-aminobenzotrifluoride [V] in high yield [75%] and purity [99.6%]. $\text{in}$-$\text{situ}$ reduction is probably initiated by a combination of iron from the stainless steel autoclave and trace amounts of moisture. The transformation of [VI] to [V] represents another type of $\text{in}$-$\text{situ}$ fluorination-reduction nitroaromatics, e.g. nitrobenzene [VII] to $\text{p}$-fluoroaniline [VIII]. $\text{o}$-Nitrobenzotrichloride [XI] degraded under ‘forcing’ conditions with [AHF]_x·NH₄F.     

Structure d'un nouvel heteroside d'isoflavone: le sarothamnoside

The structure of sarothamnoside (genistein 7,4′-di-O-[4-O-β-D-glucopyranosyl-β-D-apiofuranoside]), a new isoflavone glycoside from $\text{Sarothamnus scoparius}$ and $\text{S}$, patens, has been established by spectral analysis, mainly ₁₃C NMR.     

Cationic cyclocodimerization. 2. Syntheses of [3.3](1,4)naphthalenophane and [3.3]paracyclo(1,4)naphthalenophane derivatives

1,3-bis(4-vinylnaphthyl)propane and 1-(4-vinylnaphthyl)-3-($\text{p}$-vinylphenyl)propane, were cyclocodimerized with indene to afford indenyl-substituted [3.3](1,4)naphthalenophanes and [3.3]paracyclo(1,4)naphthalenophanes.     

Reactivite d'alcynes fluores vis-a-vis de methylthiolates [(η5-C5H5)M(SMe)(CO)3] et d'hydrures [(η5-C5H5)MH(CO)3] de molybdene et de tungstene

The electron deficient acetylene, hexafluorobut-2-yne, reacts with molybdenum and tungsten methanethiolate derivatives (prepared in situ) to give vinyl and three-, five-, or six-membered heterocyclic derivatives: [Cp(OC)- $\text{MoC(O)C(CF}{}_3\text{)C(CF}{}_3\text{)C(O)S}$Me], [Cp(OC)₂$\text{MC(CF}{}_3\text{)C(CF}{}_3\text{)C(CF}{}_3\text{)C(O)S}$Me], [CpW(CO)₃C(CF₃C(CF₃)SMe], [CpW{η³-$\text{C(CF}{}_3\text{)C(CF}{}_3\text{)C(SMe)OC}$(O)}-(CO)₂]. These reactions contrast with those of trifluoropropyne where no organometallic species are obtained. On heating or irradiation with CF₃CCCF₃ [CpMH(CO)₃] gives known bridged species and in the presence of dimethyl disulphide the vinyl derivative [CpM(CO)₃C(CF₃)C(CF₃)H]and an isomer of undetermined structure.     

Etude par rmn de31p de la reaction de l'hexamethylphosphotriamide avec le trichlorure de phosphoryle

The reaction of HMPT with POCl₃ was studied by ³¹P NMR at various temperatures and stoechiometries. Progressive substitution of chlorine atoms of phosphoryl chloride by HMPT molecules was observed. Six new species were involved in the system. The main produce was the $\text{1}\text{1}$ adduct, (Me₂N)₃P⁺Cl, O₂PCl₂^?, analogous to Vilsmeier complex.     

Conversion directe des phospholes en dihydro-6,7 phosphepines dans la sphere de coordination du tungstene

In the presence of AlCl₃, [1-β-chloroethyl-3,4-dimethylphosphole]pentacarbonyltungsten($\text{1}$) rearranges into [1-chloro-3,4-dimethyl-6,7-dihydrophosphepin]pentacarbonyltungsten ($\text{3}$).     

Cationic copolymerization of indene with styrene derivatives: Synthesis of random copolymers of indene with high molecular weight

Random copolymers with high molecular weights of indene and p‐methylstyrene (pMeSt) were synthesized by cationic polymerization with trichloroacetic acid/tin tetrachloride in CH₂Cl₂ at low temperatures. When indene and pMeSt (1:1 v/v), for example, were polymerized at ?40 °C, both monomers were consumed at very similar rates to give a copolymer with high molecular weight [number‐average molecular weight (M_n): 8–9 × 10⁴]. This is indeed quite unexpected behavior for the combination of these two monomers because pMeSt polymerized over 1000 times faster than indene in the homopolymerization under the reaction conditions previously described. The product copolymer of indene and pMeSt had a random monomer sequence in it that was confirmed by NMR analyses and thermal‐property measurements. In sharp contrast with pMeSt, styrene and p‐chlorostyrene, which have no electron‐donating groups on the phenyl ring, led to low molecular weight polymers (M_n < 10,000) in the copolymerization with indene (1:1 v/v). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2449–2457, 2002     

Participation d'un groupe amide a la formation de sels de dioxolanne-1,3 ylium-2; Modele biomimetique de reaction de peptidation

An amide group is shown to be capable of intramolecular participation in the formation of an 1,3-dioxolan 2-ylium cation giving a tricyclic organic cation of a new type $\text{5a}$,$\text{b}$. This cation may be considered as a model of an electrophilic intermediate which might be formed from a peptidyl t-RNA during protein biosynthesis.The tricyclic salt $\text{5a}$,$\text{b}$ reacts with water and methanol like a classical dioxolenium salt. An amide acetal $\text{18}$ can be obtained from dimethylamine and 5a; hydrolysis of $\text{18}$ does not lead to the corresponding amide $\text{20}$ but to the cleavage of the CN. bond.     

Influence des associations moleculaires sur la copolymerisation de l'acide acrylique avec l'acide methacrylique et avec l'acrylate de methyle

The copolymerization of acrylic acid with methacrylic acid in bulk is investigated at 40 and 60°. It is confirmed that a “matrix effect” occurs only for high contents of acrylic acid. The critical concentration beyond which the matrix effect disappears is shifted towards lower acrylic acid contents for higher temperatures. The copolymer composition is independent of temperature. The copolymerization of acrylic acid with methyl acrylate is investigated in a mixture which determines an “exaltation of the matrix effect” in the homopolymerization of acrylic acid (molar fractions: m_Monomers = 0.34; m_n-Hexane = 0.52; m_Methanol = 0.14). The resulting copolymers are found to contain a much larger fraction of acrylic acid residues than the copolymers formed in bulk or in toluene or DMF solutions.     

Alternating,gradient, block,and block–gradient copolymers of ethylene and norbornene by Pd–Diimine‐Catalyzed “living” copolymerization

We demonstrate, in this article, the facile synthesis of a broad class of low‐polydispersity ethylene–norbornene (E–NB) copolymers having various controllable comonomer composition distributions, including gradient, alternating, diblock, triblock, and block–gradient, through “living”/quasiliving E–NB copolymerization facilitated with a single Pd – diimine catalyst ( 1 ). This synthesis benefits from two remarkable features of catalyst 1 , its high capability in NB incorporation and high versatility in rendering E–NB “living” copolymerization at various NB feed concentrations ([NB]₀) while under an ethylene pressure of 1 atm and at 15 °C. At higher [NB]₀ values between 0.42 and 0.64 M, E–NB copolymerization with 1 renders nearly perfect alternating copolymers. At lower [NB]₀ values (0.11–0.22 M), gradient copolymers yield due to gradual reduction in NB concentration, with the starting chain end containing primarily alternating segments and the finishing end being hyperbranched polyethylene segments. Through two‐stage or three‐stage “living” copolymerization with sequential NB feeding, diblock or triblock copolymers containing gradient block(s) have been designed. This work thus greatly expands the family of E–NB copolymers. All the copolymers have controllable molecular weight and relatively low polydispersity (with polydispersity index below 1.20). Most notably, some of the gradient and block–gradient copolymers have been found to exhibit the characteristic broad glass transitions as a result of their possession of broad composition distribution. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Induction asymetrique lors de l'addition de Michael d'un ester α-sulfinyle chiral

During the Michael addition of chiral α-sulfinyl eser (+) $\text{1}$$\text{R}$ on αβ-unsaturated esters, an extent of 24% of asymmetric induction was observed. It is shown that the addition products can be transformed into optically active δ-lactones.