22544-42-9Relevant academic research and scientific papers
Method of preparing beta-d2 alkyl acid compounds
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Paragraph 0059; 0061; 0062; 0063; 0075-0085; 0091-0101, (2018/06/26)
The invention provides a method of preparing beta-d2 alkyl acid compounds. The method includes steps of: 1) performing a reduction reaction to a compound A with LiAlD4 to obtain a compound B; 2) performing -OD group protective reaction to the compound B to obtain an intermediate C; 3) performing a bromination reaction to the intermediate C to obtain a compound D; 4) under alkaline condition, performing a substitution reaction to the compound D and acetic acid to obtain the beta-d2 alkyl acid compounds. In the method, the alkyl acid, which is low in cost and is easy to obtain, is used as the initial raw material and is subjected to LiAlD4 reduction reaction, the -OD group protective reaction, the bromination reaction and the acetic acid substitution reaction to prepare the beta-d2 alkyl acid compounds. The method has simple process route and is free of expensive catalysts and the like during the reactions, is low in cost, and is high in total yield of the beta-d2 alkyl acid compounds. The method, when being amplified to gram-scale, has stable yield and good repeatability and is practicable and available.
Nickel-Mediated Stepwise Transformation of CO to Acetaldehyde and Ethanol
Zhang, Ailing,Raje, Sakthi,Liu, Jianguo,Li, Xiaoyan,Angamuthu, Raja,Tung, Chen-Ho,Wang, Wenguang
, p. 3135 - 3141 (2017/09/05)
The insertion of CO into the Ni-C bond of synthetic Ni(II)-CH3 cationic complex ([1-CH3]+) affords a nickel-acetyl complex ([1-COCH3]+). Reduction of resultant [1-COCH3]+ by borohydrides produces CH3CHO, CH3CH2OH, and an Ni(0) compound ([1]0), which can react with CH3I to regenerate [1-CH3]+. By conducting deuterium labeling experiments, we have demonstrated that CH3CHO is the primary product from CH3CH2OH in such CO transformation reactions. In the reduction of [1-COCH3]+, the formation of CH3CHO competes with the loss of CH4, which leads to a Ni(0)-CO compound ([1-CO]0) as a minor product. Our results establish fundamental steps in the exploration of nickel-mediated CO transformation to valuable chemicals.
Pincer Ru and Os complexes as efficient catalysts for racemization and deuteration of alcohols
Bossi, Gianluca,Putignano, Elisabetta,Rigo, Pierluigi,Baratta, Walter
experimental part, p. 8986 - 8995 (2011/10/31)
The pincer complexes [MX(CNN)(PP)] (M = Ru, Os; X = Cl, OTf; HCNN = 1-(6-arylpyridin-2-yl)methanamine; PP = diphosphine) have proven to efficiently catalyze both racemization and deuteration of alcohols in the presence of a base. Chiral alcohols have been racemized at 30-50 °C using 1 mol% of Ru or Os pincer complexes and 5 mol% of KOtBu in 2-propanol. Primary and secondary alcohols are efficiently deuterated at the α position, with respect to the OH group, using 2-propanol-d8 as solvent with Ru or Os pincer complexes and KOtBu at 30-50 °C. For secondary alcohols incorporation of deuterium at the β position has also been observed. In 2-propanol-d 8 the pincer complexes catalyze the simultaneous deuteration and racemization of (S)-1-phenylethanol, the two processes being strictly correlated. For both reactions much the same activity has been observed with the Ru and Os complexes. The pincer complexes display a superior activity with respect to the related compounds [MCl2(NN)(PP)] (NN = bidentate amine or pyridine ligand). The synthesis of the new complexes [MCl(CNN)(PP)] (M = Ru, 2, 4 and Os, 6, 7; PP = dppb, dppf) and [Ru(OTf)(CNN)(dppb)] (3) is also reported. The Royal Society of Chemistry 2011.
Ion-Neutral Complexes as Intermediates in the Decompositions of C5H10O2.+ Isomers
McAdoo, David J.,Hudson, Charles E.,Skyiepal, Mark,Broido, Ellen,Griffin, Lawrence L.
, p. 7648 - 7653 (2007/10/02)
Ionized pentanoic acid, 3-methylbutanoic acid, and the enol isomer of ionized isopropyl acetate are shown to pass in part through common intermediates before decomposing to CH3C.HC(OH)2+ (7) and the "McLafferty + 1" ion CH3C(OH)2+ (10).The H transfer to form the methyl of CH3C(OH)2+ and the joining of two CH2 groups to form the C-C bond in the ethylene eliminated to produce CH3C.HC(OH)2+ are both attributed to reactions of the ion-neutral complex .H2C(OH)2+>.The McLafferty + 1 ion is also formed, especially from ionized esters, by another pathway in which complexes may or may not be intermediates.The intermediacy of the ion-neutral complexes is supported by energetic considerations, isotope effects, and the decomposition patterns of labeled ions.The latter correlate with a preference for hydrogen transfer from the end carbons of the C3 partner in other reactions proposed to be complex-mediated.Unification of the McLafferty rearrangement, the McLafferty + 1 rearrangement, and the McLafferty rearrangement with charge reversal by a common initial γ-hydrogen rearrangement followed by dissociation or isomerization in ion-neutral complexes is proposed.Group migration by 1,2-shifts, possibly by dissociation to form a double bond in one partner in an ion-neutral complex followed by addition at the opposite end of the double bond, is shown to be a general reaction of ions in the gas phase.
