Alcohol Reaction conditions Product composition CHKHClCH=CHz SOCl2, no solvent 33% CHaCHClCH=CHs 6770 CH&H=CHCHICl CHaCH=CHCHzOH SOC12, no solvent 71% CHoCHClCH=CH* CHaCH=CHCHzOH SOC12 in Et20 99% CHsCHClCH=CHt CHaCHOHCH=CHz SOClz in Et20 100% CHsCH=CHCHzCl ( -)trans-CHsCH=CHCHOHCHa SOCl, in EtzO CHsCH=CHCHClCHs CsHsCH=CHCHzOH 0.1 M R O H + 0.1 MSOCl, in Et20 100% CeHsCHClCH=CHz CsHbCH=CHCH*OH 60% CsHrCHClCH=CHz 40% CeHsCH=CHCHzCl 29 7 0 CH,CH=CCH CHzCl 100% (-1 tram-show a-phenylallyl chloride is the product. This thermodynamically less stable secondary chloride is rearranged only very slowly in the reaction solution.Our present evidence is still insufficient to decide whether the SNi' mechanismZ involves a one-stage concerted process or ionization to an intimate, rigidly oriented carbonium chlorosulfinate ion pairI6 followed by internal returne of the chloride component of the chlorosulfinate anion to give rearranged chloride. It is very clear that the SNi' mechanisms does not involve a carbonium chloride ion pair of the type employed by Cram' in his preferred mechanism for the action of thionyl chloride on the 3-phenyl-2-butanols. A carbonium chloride ion pair in the a, y-dimethylallyl system would lead to a trans-chloride which is 100% racemic instead of the inverted chloride actually observed. Further, a carbonium chloride ion pair would not lead to the specific structural results obtained with the butenols and cinnamyl alcohol.The dominant role of the SNi' reaction is soinetimes difficult to preserve. In the case of cinnamyl alcohol, even the use of 1 M concentrations of reactants changes the polarity of the medium and results in the product ion of a mixture of 60% cinnamyl chloride and 40% a-phenylallyl chloride from the reaction itself since a-phenylallyl chloride is stable under the conditions used.

No abstract

The synthetic molecular sieves exhibit the order of catalytic activities for propene polymerization: 1 OX > 13X > 5A > 5P > 4A > 3A = 0. The order of olefin reactivities over sieves is (CH3)2C=CH2 > (CH3) HC==CH > CHz=CHz. The liquid polymers obtained are of the conjunct type reported for conventional acid catalysts. The solid-acid properties of sieves are unique: all these molecular sieves give net basic reactions with water; all except the 3A sieves give solid-acid titers with n-butylamine in anhydrous benzene. The k values for the propene polymerization reaction do not correlate directly with the solid-acid titers, but a good inverse correlation i s obtained between the log k values and the per cent reactive alumina.YNTHETIC MOLECLTLAR SIEVES, like certain clays and silica-s alumina cracking catalysts: have potentially inherent in

No abstract

Using standard microbiological techniques in a semi pilot plant-scalable fermenter, xanthan-specific culture techniques developed by the U.S. Dept of Agriculture's Northern Regional Research Laboratory (NRRL) were used at Marathon Oil Co.'s Denver Research Center (DRC) to obtain improved and reproducible high conversions and yields of xanthan biopolymer broth. Practical nutrients and fermenter parameters were studied to define and improve the viscosity performance and economics of xanthan broth production for thickening water in the Marafiood™ enhanced oil recovery process.