Reference

Catalytic hydroxylation of allyl chlorides with ascorbic acid and poly(methyl methacrylate)-supported copper(I) ion system

Catalytic hydroxylation of allyl chlorides with ascorbic acid and poly(methyl methacrylate)-supported copper(I) ion system. Matsubara, Yoshio; Uezawa, Shunji; Morisawa, Makoto; Yoshihara, Masakuni; Maeshima, Toshihisa (Fac. Sci. Eng. 591-97-9 and 13171-64-7 are also occured in this study., Kinki Univ., Higashi-Osaka 577, Japan). Kobunshi Ronbunshu, 49(2), 155-60 (Japanese) 1992. CODEN: KBRBA3. ISSN: 0386-2186. DOCUMENT TYPE: Journal CA Section: 23 (Aliphatic Compounds) Heterogeneous catalytic hydroxylation of allyl chlorides such as 1-chloro-2-propene, 1-chloro-2-butene and cinnamyl chloride was carried out with ascorbic acid and poly(Me methacrylate) (PMMA)-supported copper(I) as a polymeric catalyst at pH 4.0 under an argon atm. at 30°, and the turnover values were about 50 times higher than that in the absence of the polymeric support. Acylation of the allyl chlorides with the same catalytic system proceeded in an acetic acid buffer soln. efficiently as in the hydroxylation. The hydroxylation reaction in this system was investigated under varying reaction conditions to discuss the effects of aq. solvent ratios, substrates, ligands, and addn. of sodium chloride. The catalytic system showed very high activity as compared with that in the absence of the polymeric support. This was explained in term of an increase in the concn. of reaction substrate by hydrophobic micro atm. on the surface of the PMMA support and also of the p-allyl copper chloride intermediate formation. .

Pasteur-like resolution of quasi-racemates in solid and gas phases

Pasteur-like resolution of quasi-racemates in solid and gas phases. Kostyanovsky, Remir G.; Nikolaev, Eugene N.; Kharybin, Oleg N.; Kadorkina, Gul'nara K.; Kostyanovsky, Vasilii R. (N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow 119991, Russia). Mendeleev Communications, (3), 97-99 (English) 2003 Russian Academy of Sciences. CODEN: MENCEX. ISSN: 0959-9436. DOCUMENT TYPE: Journal CA Section: 21 (General Organic Chemistry) Section cross-reference(s): 75 Isotopomeric quasi-racemates (IQR), i.e., 1:1 mixts. of enantiomers one of which contains an isotopic label, can undergo crystn. as conglomerates or true quasi-racemates. In the former case, each single crystal contains, predominantly or exclusively, either labeled or non-labeled enantiomers, whereas in the latter case, it contains both enantiomers (1:1). Thus, an equimolar mixt. of (R)-(+)-Asn (Asn = asparagine) and (S)-(-)-Asn(15N-amide) underwent spontaneous resoln. on crystn. forming conglomerates, whereas an equimolar mixt. of (R,R)-(+)-dimethyl tartrate and (S,S)-(-)-dimethyl tartrate-d6 gave crystals contg. both labeled and non-labeled enantiomers in a ratio close to 1:1.In this experiment, several chemicals are used like 13171-64-7 and 291772-74-2 If soln. sputtering is used to ionize quasi-racemates, the formation of homochiral protonated and metalated enantiomers and their homochiral oligomers in the gas phase is detected in ion cyclotron resonance mass spectra; these compds. differ in their m/z values; hence, Pasteur-like "manual sorting" can be employed to catch them successively in the ion trap of the spectrometer. .