- Chemoselective Homologation-Deoxygenation Strategy Enabling the Direct Conversion of Carbonyls into (n+1)-Halomethyl-Alkanes
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The sequential installation of a carbenoid and a hydride into a carbonyl, furnishing halomethyl alkyl derivatives, is reported. Despite the employment of carbenoids as nucleophiles in reactions with carbon-centered electrophiles, sp3-type alkyl halides remain elusive materials for selective one-carbon homologations. Our tactic levers on using carbonyls as starting materials and enables uniformly high yields and chemocontrol. The tactic is flexible and is not limited to carbenoids. Also, diverse carbanion-like species can act as nucleophiles, thus making it of general applicability.
- Citarella, Andrea,Holzer, Wolfgang,Ielo, Laura,Langer, Thierry,Miele, Margherita,Pace, Vittorio,Urban, Ernst,Zehl, Martin
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supporting information
p. 7629 - 7634
(2020/10/12)
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- Facile and catalytic degradation method of DDT using Pd/C-Et3N system under ambient pressure and temperature
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The catalytic degradation method of p,p′-DDT [1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane] and its regioisomer o,p′-DDT [1,1,1-trichloro-2-(o-chlorophenyl)-2-(p-chlorophenyl)ethane] using the Pd/C-Et3N system under ambient hydrogen pressure and temperature was established. The presence of Et3N was necessary for the quick and complete breakdown of DDT. The independent degradation study of two intermediates, p,p′-DDD [2,2-bis(p-chlorophenyl)-1,1-dichloroethane] and p,p′-DDE [2,2-bis(p-chlorophenyl)-1,1-dichloroethylene] using GC-MS let us to speculate the degradation pathway of p,p′-DDT. In the initial phase of the reaction, p,p′-DDT degradation splits into two ways: a dehydrochlorination pathway and a hydrodechlorination pathway. In each pathway, reaction starts from an aliphatic moiety and subsequent hydrodechlorination from the benzene moieties takes place in a stepwise manner. The former pathway leads to the formation of 1,1-diphenylethane and the latter leads to the formation of 1,1-dichloro-2,2-diphenylethane. These diphenylethane analogs, which are less toxic compared with p,p′-DDT, are terminal degradation products in our system. The distinctive features of our catalytic degradation method of DDTs are reliability, simplicity, efficiency, and inexpensiveness.
- Monguchi, Yasunari,Kume, Akira,Sajiki, Hironao
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p. 8384 - 8392
(2007/10/03)
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- PULSE RADIOLYSIS AND PRODUCT ANALYSIS OF 1,1-DIPHENYLETHYLENE AND RELATED COMPOUNDS IN METHANOL
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Pulse radiolysis of 1,1-diphenylethylene (DPE) in methanol in the presence of oxygen, as well as of 1,1-diphenyl-2-chloroethylene (DPE-2-Cl), 1,1-diphenyl-1-chloroethane (DP-1-Cl-Et) and 1,1-diphenyl-2-chloroethane (DP-2-Cl-Et) in methanol saturated with argon, was performed.The products formed under pulse-radiolysis conditions were also analysed.Spectroscopic and kinetic data of the corresponding transiets are presented.The reaction rate constants determined in methanol are .It has been established that the solutes are primarily attacked by e-s and H, whereas the CH2OH species (or O2) react with the intermediates thus produced.Reaction mechanisms consistent with the spectroscopic and kinetic data are presented.
- Getoff, Nikola,Ritter, Alfred,Schwoerer, Friedrich
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p. 2389 - 2404
(2007/10/02)
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- PULSE MICROREACTOR PESTICIDES HYDRODECHLORINATION
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Catalytic hydrodechlorination of chlorinated pesticides and other environmentally chlorinated materials into lower chlorine content compounds has been studied in a pulse microreactor .Chlorine can be catalytically removed and replaced by hydrogen to prduce partially chlorinated intermediates as well as completely dechlorinated hydrocarbons.Intermediates are equivalent to some of those obtained by natural degradation.The pulse microreactor is a simple technique to predict both product composition and reaction severity required for laboratory scale preparation of such degradation products.
- Weiss, A. H.,LaPierre, R. B.
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p. 111 - 122
(2007/10/02)
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