- Preparation method of alkyl nitrile compound
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The invention discloses a preparation method of an alkyl nitrile compound shown as formula I. The preparation method comprises the following step: in a solvent, in the presence of an additive and a catalyst, Zn (CN) 2 and an alkyl halide shown as formula II are subjected to a coupling reaction as shown in the specification to obtain the alkyl nitrile compound as shown in the formula I, wherein theadditive comprises an alkali, the catalyst comprises a nickel compound and a phosphine ligand; the nickel compound is one or more of zero-valent nickel, monovalent nickel salt and divalent nickel salt; when the nickel compound contains zero-valent nickel or divalent nickel salt, the catalyst further comprises a reducing agent. According to the preparation method disclosed by the invention, cyanation of an alkyl halide can be simply, conveniently and efficiently realized by using a cheap catalytic system, and the preparation method also has good functional group compatibility and substrate universality.
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Paragraph 0180-0182
(2020/05/14)
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- Method for hydrogenolysis of halides
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The invention discloses a method for hydrogenolysis of halides. The invention discloses a preparation method of a compound represented by a formula I. The preparation method comprises the following step: in a polar aprotic solvent, zinc, H2O and a compound represented by a formula II are subjected to a reaction as shown in the specification, wherein X is halogen; Y is -CHRR or R; hydrogenin H2O exists in the form of natural abundance or non-natural abundance. According to the preparation method, halide hydrogenolysis can be simply, conveniently and efficiently achieved through a simple and mild reaction system, and good functional group compatibility and substrate universality are achieved.
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Paragraph 0117-0119
(2021/01/11)
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- Dehalogenative Deuteration of Unactivated Alkyl Halides Using D2O as the Deuterium Source
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The general dehalogenation of alkyl halides with zinc using D2O or H2O as a deuterium or hydrogen donor has been developed. The method provides an efficient and economic protocol for deuterium-labeled derivatives with a wide substrate scope under mild reaction conditions. Mechanistic studies indicated that a radical process is involved for the formation of organozinc intermediates. The facile hydrolysis of the organozinc intermediates provides the driving force for this transformation.
- Xia, Aiyou,Xie, Xin,Hu, Xiaoping,Xu, Wei,Liu, Yuanhong
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p. 13841 - 13857
(2019/10/17)
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- The effect of ring size on reactivity: The diagnostic value of 'rate profiles'
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The rates of cycloalkyl phenyl sulfide formation of a series of homologous bromocycloalkanes upon treatment with sodium benzenethiolate have been determined to ascertain the effect of ring size on reactivity. The 'rate profile', i.e., reaction rate vs. ring size, for these nucleophilic substitutions (SN2) was determined. A linear free-energy relationship could be derived from computed hydride affinities of cycloalkanes and rates of typical SN1 reactions, whereas rates of SN2 reactions exhibited a strong discrepancy from the seven- up to the twelve-membered rings. This discrepancy was rationalized by a careful examination of the geometry of the intermediates and transition states involved in these reactions.
- Masson, Eric,Leroux, Frederic
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p. 1375 - 1386
(2007/10/03)
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- The functionalization of saturated hydrocarbons. Part 23. Gif-type bromination and chlorination of saturated hydrocarbons: A non-radical reaction
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The bromination of saturated hydrocarbons was studied in the GoAggIII system using CBrCl3 and other polyhaloalkanes. This bromination reaction was compared to free radical processes by (i) evaluating the rates of reactions for a series of polyhaloalkanes, by (ii) measuring the selectivity of the different systems towards various saturated hydrocarbons and by (iii) analyzing the product distribution arising from the bromination of cyclohexyl bromide under both the GoAggIII type conditions and from known processes for alkyl radical generation. Some chlorine containing reagents were also examined for C - Cl bond formation in the GoAggIII system. All the experimental findings support a mechanism for the reaction that is different from one involving free radicals. This non-radical pathway is common in all Gif-type systems, as seen in common patterns of selectivity, conditions is in agreement with a non-radical reaction pathway for the Gif-type bromination and chlorination reactions.
- Barton, Derek H. R.,Csuhai, Eva,Doller, Dario
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p. 9195 - 9206
(2007/10/02)
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- Comparison of gif-type reactivity towards alkanes with standard radical reaction selectivity. Gif oxidation of n-butane and propane
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A precise comparison has been made between radical bromination of a series of saturated hydrocarbons using BrCCl3 and the bromination of the same series with the same reagent under Gif-type (GoAggIII) conditions. The relative reactivities in the two series are completely different and confirm a difference in mechanism. Experiments with n-butane and with propane have shown that these gases react with the usual Gif selectivity to furnish 2-butanone and acetone respectively.
- Barton, Derek H. R.,Csuhai, Eva,Doller, Dario,Ozbalik, Nubar,Senglet, Nathalie
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p. 3097 - 3100
(2007/10/02)
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- BASE-PROMOTED ELIMINATION OF HYDROGEN FLUORIDE FROM ALKYL FLUORIDES: REACTIVITY AND STEREOCHEMISTRY
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- The alcoholate-promoted dehydrohalogenation of 5-nonyl fluoride and cyclododecyl fluoride, typical straight-chain and, respectively, medium-size cyclic substrates, leads to cis- and trans-alkenes in an approximate ratio of 1:3.With bulky bases such as lithium diisopropylamide the trans isomer may be obtained almost exclusively.In general, the elimination of hydrogen fluoride proceeds very slowly.Increase of the base strength has only a moderate effect on the rates.Electrophilic assistance as provided by lithium cations in media of low polarity can, however, considerably accelerate the reaction. - Cyclododecyl fluoride cannot be prepared from cyclododecanol.It is, however, readily accessible by bromofluorination of cyclododecene and subsequent reduction of the adduct with stannane.
- Matsubara, Seijiro,Matsuda, Hiroyuki,Hamatani, Takeshi,Schlosser, Manfred
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p. 2855 - 2864
(2007/10/02)
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