535-15-9Relevant articles and documents
Alkyl Halides via Visible Light Mediated Dehalogenation
Rathnayake, Manjula D.,Weaver, Jimmie D.
supporting information, p. 9681 - 9687 (2019/11/28)
Net selective bromination and chlorination of activated C-H bonds can be effected in generally high yield via a simple perhalogenation/dehalogenation sequence. The photochemical reductions require no photocatalyst, relying instead on the formation of an electron donor-acceptor complex of the substrate and reductant, or alternatively autophotocatalysis. Some reactions proceed despite any apparent photon absorption, serving as a cautionary tale for other photochemical reactions involving amines. Mechanistic experiments provide an explanation for this observation.
Mixed-ligand complexes of paddlewheel dinuclear molybdenum as hydrodehalogenation catalysts for polyhaloalkanes
Tsurugi, Hayato,Hayakawa, Akio,Kando, Shun,Sugino, Yoshitaka,Mashima, Kazushi
, p. 3434 - 3439 (2015/05/27)
We developed a hydrodehalogenation reaction of polyhaloalkanes catalyzed by paddlewheel dimolybdenum complexes in combination with 1-methyl-3,6-bis(trimethylsilyl)-1,4-cyclohexadiene (MBTCD) as a non-toxic H-atom source as well as a salt-free reductant. A mixed-ligated dimolybdenum complex Mo2(OAc)2[CH(NAr)2]2 (3a, Ar = 4-MeOC6H4) having two acetates and two amidinates exhibited high catalytic activity in the presence of nBu4NCl, in which [nBu4N]2[Mo2{CH(NAr)2}2Cl4] (9a), derived by treating 3a with ClSiMe3 and nBu4NCl, was generated as a catalytically-active species in the hydrodehalogenation. All reaction processes, oxidation and reduction of the dimolybdenum complex, were clarified by control experiments, and the oxidized product, [nBu4N][Mo2{CH(NAr)2}2Cl4] (10a), was characterized by EPR and X-ray diffraction studies. Kinetic analysis of the hydrodehalogenation reaction as well as a deuterium-labelling experiment using MBTCD-d8 suggested that the H-abstraction was the rate-determining step for the catalytic reaction. This journal is
Efficient partial hydrogenation of trichloromethyl to gem-dichloromethyl groups in platinum on carbon-catalyzed system
Sawama, Yoshinari,Imanishi, Takahiro,Nakatani, Ryosuke,Fujiwara, Yuta,Monguchi, Yasunari,Sajiki, Hironao
supporting information, p. 4540 - 4546 (2014/06/10)
While gem-dichloromethyl groups can be directly synthesized by the mono-dechlorination of the corresponding trichloromethyl groups, the suppression control of the over-reduction to form chloromethyl or methyl functionalities is quite difficult. We have established the efficient and widely applicable mono-dechlorination method of the trichloromethyl groups to form the corresponding gem-dichloromethyl groups using platinum on carbon in dimethylacetamide as a specific solvent at 25 °C under a hydrogen atmosphere. The mono-dechlorination of the α,α,α- trichloromethylcarbonyl groups smoothly proceeded by the use of platinum on carbon as a catalyst in a highly chemoselective manner, while the efficient mono-dechlorination of the alkyl- and aryl-trichloromethyl groups required the combined use of Bu3SnH.
SNAAP sulfonimidate alkylating agent for acids, alcohols, and phenols 1
Maricich, Tom J.,Allan, Matthew J.,Kislin, Brett S.,Chen, Andrea I-T.,Meng, Fan-Chun,Bradford, Christine,Kuan, Nai-Chia,Wood, Jeremy,Aisagbonhi, Omonigho,Poste, Alethea,Wride, Dustin,Kim, Sylvia,Santos, Therese,Fimbres, Michael,Choi, Dianne,Elia, Haydi,Kaladjian, Joseph,Abou-Zahr, Ali,Mejia, Arturo
, p. 3361 - 3368 (2014/01/06)
Stable, crystalline ethyl N-tert-butyl-4-nitrobenzenesulfonimidate has been prepared in high yield by direct O-ethylation of N-tert-butyl-4- nitrobenzenesulfonamide with iodoethane and silver(I) oxide in dichloromethane. This sulfonimidate directly ethylates various acids to esters; the stronger the acid, the faster it alkylates and in higher yield. It readily ethylates alcohols and phenols to ethers at room temperature in the presence of tetrafluoroboric acid catalyst without molecular rearrangements or racemization. We have defined these reactions as SNAAP alkylations: [substitution, nucleophilic of acids, alcohols and phenols]. The hard sulfonimidate alkylating agent is chemoselective, preferring oxygen > nitrogen > sulfur. The sulfonamide byproduct of alkylation is readily recycled to the sulfonimidate. Georg Thieme Verlag Stuttgart . New York.
Platinum on carbon-catalyzed precise reduction control of trichloromethyl to Geminal-dichloromethyl groups
Imanishi, Takahiro,Fujiwara, Yuta,Sawama, Yoshinari,Monguchi, Yasunari,Sajiki, Hironao
supporting information; experimental part, p. 771 - 776 (2012/06/30)
Geminal-dichloromethyl derivatives could be efficiently synthesized by the highly chemoselective platinum on carbon-catalyzed mono-dechlorination of trichloromethyl substrates in dimethylacetamide (DMA) as a specific solvent at 25 °C under a hydrogen atmosphere. Copyright
Reactions of α-chloro β-oxo aldehydes with CH-acid anions
Guseinov, F. I.
, p. 743 - 745 (2007/10/03)
The reactions of α-chloro and α,α-dichloro β-oxo aldehydes with carbanions are accompanied by the cleavage of the carbon-carbon bond in the chloro aldehydes and result in formylation of CH-acids. These electrophiles react with carbanions, which are generated in situ from CH-acids in the presence of AcONa in aprotic solvents, to form polyfunctional hydroxy compounds.
Kinetics and mechanism of oxidation of aliphatic acetals with peroxomonosulphate
Janakiram,Venkataraman,Basheer Ahamed
, p. 339 - 341 (2007/10/03)
The oxidation of fifteen aliphatic acetals of normal aliphatic aldehydes and substituted aliphatic aldehydes with aliphatic and substituted aliphatic as well as with aromatic alcohols by peroxomonosulphate in aqueous acetic acid medium is first order each in [oxidant] and [acetal] and yields the corresponding esters as the main product. The oxidation reaction is independent of change in dielectric constant of the medium. The activation enthalpies and entropies of the reactions are linearly related. A mechanism involving hydride ion shift is proposed.
Kinetics and mechanism of oxidation of aliphatic acetals with N-chlorobenzamide
Basheer Ahamed
, p. 222 - 224 (2007/10/03)
The oxidation kinetics of thirteen aliphatic acetals of normal aliphatic aldehydes and substituted aliphatic aldehydes with aliphatic and substituted aliphatic as well as with aromatic alcohols by N-chlorobenzamide (NCB) in aqueous acetic acid medium follows first order and zero order dependence in [NCB] and [acetal] respectively and yields the corresponding esters as the main product of oxidation. (H2OCl)+ has been postulated as the oxidizing species.
Reactions of α-Chloro-β-oxoaldehydes with Dialkyl Phosphites
Guseinov,Burangulova,Moskva
, p. 1564 - 1567 (2007/10/03)
Sodium dialkyl phosphites react with α-chloro- and α,α-dichloro-β-oxoaldehydes exclusively at the aldehyde carbonyl group with rupture of the C-CHO bond. The primary products are corresponding α-chloro- and α,α-dichloroenolates and unstable phosphinoylformaldehydes; the latter decompose into dialkyl hydrogen phosphites and carbon monoxide. Condensation products of α-halo-β-oxoaldehydes with dialkyl hydrogen phosphites in the presence of sodium hydride undergo similar transformations.
Reactions of α-Chloro- and α,α-dichloro-β-oxoaldehydes with Anionic Nucleophiles
Guseinov, F. I.,Tagiev, S. Sh.,Moskva, V. V.
, p. 86 - 89 (2007/10/03)
The reaction of α-chloro and α,α-dichloro-β-oxoaldehydes with anionic nucleophiles (NaOH, MeONa, PhONa, MeCOOK) proceeds mainly via haloform splitting with elimination of the formyl group; only with the most nucleophilic sodium methoxide, the reaction at the β-carbon atom partially occurs.The intermediate anions react with benzaldehyde to give difficulty accessible polyfunctional compounds.
