5911-08-0Relevant articles and documents
Method for synthesizing cylopropylmethyl chloride by using cyclopropanemethanol
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Paragraph 0038; 0047; 0055-0059, (2017/11/29)
The invention relates to the field of organic synthesis and discloses a method for synthesizing cylopropylmethyl chloride by using cyclopropanemethanol. The method comprises the following steps: (A) dissolving cyanuric chloride into a solvent A to obtain a solution; (B) dropwise adding the cyclopropanemethanol into the prepared solution for reacting; (C) adding a reaction solution finished the reaction into an alkali solution for quenching; (D) extracting a target product by using a solvent B, drying and rectifying to obtain a product. According to the method, the cyclopropanemethanol and the cyanuric chloride are used as raw materials, and are easy to obtain, low in cost and less in pollution; in addition, the method has the advantages of mild reaction conditions, simple post treatment and suitability for industrial production.
A mild method for the replacement of a hydroxyl group by halogen. 1. Scope and chemoselectivity
Munyemana, Fran?ois,George, Isabelle,Devos, Alain,Colens, Alain,Badarau, Eduard,Frisque-Hesbain, Anne-Marie,Loudet, Aurore,Differding, Edmond,Damien, Jean-Marie,Rémion, Jeanine,Van Uytbergen, Jacqueline,Ghosez, Léon
, p. 420 - 430 (2015/12/31)
α-Chloro-, bromo- and iodoenamines, which are readily prepared from the corresponding isobutyramides have been found to be excellent reagents for the transformation of a wide variety of alcohols or carboxylic acids into the corresponding halides. Yields are high and conditions are very mild thus allowing for the presence of sensitive functional groups. The reagents can be easily tuned allowing therefore the selective monohalogenation of polyhydroxylated molecules. The scope and chemoselectivity of the reactions have been studied and reaction mechanisms have been proposed.
Ni-catalyzed cascade cyclization-kumada alkyl-alkyl cross-coupling
Guisan-Ceinos, Manuel,Soler-Yanes, Rita,Collado-Sanz, Daniel,Phapale, Vilas B.,Bunuel, Elena,Cardenas, Diego J.
supporting information, p. 8405 - 8410 (2013/07/25)
Suggesting novel disconnections: A powerful Ni-catalyzed cascade reaction involving cyclization followed by cross-coupling allows the formation of up to three alkyl-alkyl bonds in a single operation by using alkene-containing alkyl iodides and Grignard reagents (see scheme; acac=acetylacetonate; TMEDA=N,N′,N′-tetramethyl ethylenediamine). Mechanistic experimental and computational studies suggest a NiI-NiII-Ni III catalytic cycle and the intermediacy of radicals. Copyright
Electrophilic cleavage of cyclopropylmethystannanes: An experimental comparison of σ-σ and σ-π conjugation
Lucke, Andrew J.,Young, David J.
, p. 3579 - 3583 (2007/10/03)
(Chemical Equation Presented) Cyclopropylmethyltrimethylstannanes undergo electrophilic cyclopropane cleavage in chloroform with simple inorganic electrophiles (H+, SO2, I2) in a homologous reaction to the SE′ cleavage of allylic stannanes. The σ-σ conjugation between the carbon-tin bond and cyclopropane orbitals observed spectroscopically in the parent cyclopropylmethyltrimethylstannane is responsible for a rate enhancement of ca. 102 toward iodinolysis, relative to comparable alkyl stannanes. This acceleration is considerably less, however, than the ca. 109-fold rate enhancement provided by the corresponding σ-π conjugation in allylic stannanes. Methanol-tin coordination appears to reduce the activating influence of the metal, promoting methyl cleavage over cyclopropane fission with acid and iodine. Decreased σ-σ conjugation can also explain the decreased reactivity of cyclopropyltriphenylstannane compared with its trimethyltin counterpart. Cyclopropylmethylstannanes do not undergo the synthetically useful addition of aldehydes under conditions that facilitate the corresponding reaction of allylic stannanes.
Rearrangements concerted with fragmentation of cyclopropylmethoxychlorocarbene and cyclobutoxychlorocarbene in hydrocarbon solvents and Ar matrices
Moss, Robert A.,Sauers, Ronald R.,Zheng, Fengmei,Fu, Xiaolin,Bally, Thomas,Maltsev, Alexander
, p. 8466 - 8476 (2007/10/03)
Fragmentations of cyclopropylmethoxychlorocarbene (6) and cyclobutoxychlorocarbene (10) lead to rearrangments that afford mixtures of cyclopropylmethyl chloride (7), cyclobutyl chloride (8), and 3-butenyl chloride (9). Isotopic substitution studies show that these rearrangments are accompanied by partial exchange of the methylene groups within 6 and 10. Surprisingly, these processes that are typical of carbocations persist in hydrocarbon solvents such as pentane and cyclohexane-d12. Quantum chemical calculations reveal that the cis-conformers of the incipient oxychlorocarbenes C 4H7OCCl decay to C4H7Cl + CO via transient hydrogen bonded C4H7 σ+...Clσ- complexes which possess significant ion pair character, even in the gas phase or in nonpolar solvents. In contrast to benzyloxychlorocarbene, no free radicals are formed upon generation or photolysis of 6 or 10 in Ar matrixes, although acid chlorides (the recombination products of these radical pairs) are observed. The IR spectra obtained in these experiments show the presence of several conformers of the two C4H7OCCl.
Fragmentation of alkoxychlorocarbenes in the gas phase
Blake, Michael E,Jones Jr., Maitland,Zheng, Fengmei,Moss, Robert A
, p. 3069 - 3071 (2007/10/03)
In contrast to photolysis or thermal decomposition in solution, which is dominated by ionic reactions, flash vacuum pyrolysis of alkylchlorodiazirines in the gas phase generates radicals. The cyclopropylcarbinyl system is re-examined and the l-norbornylca
Fragmentation of cyclobutoxychlorocarbene: The cyclopropylcarbinyl/cyclobutyl cations revisited
Moss, Robert A.,Zheng, Fengmei,Johnson, Lauren A.,Sauers, Ronald R.
, p. 400 - 406 (2007/10/03)
Fragmentations of cyclobutoxychlorocarbene (13, kfrag= 7.1 × 105 s-1) and cyclopropylmethoxychlorocarbene (14, kfrag = 7.6 × 105 s-1) in MeCN proceed to tight and distinct [R+ OC Cl-] ion pairs, which collapse to different distributions of cyclopropylcarbinyl, cyclobutyl and allylcarbinyl chlorides. B3LYP/6-31G* calculations support these conclusions, affording computed fragmentation activation energies of 6.4 (13) and 3.0 (14) kcal mol-1.
Absolute rate constants for abstraction of chlorine from three chlorinating agents by alkyl radicals
Tanko, James M.,Blackert, Joseph F.
, p. 1775 - 1780 (2007/10/03)
Using the cyclopropylcarbinyl -> homoallyl free radical clock, absolute rate constants for the abstraction of chlorine from molecular chlorine (Cl2), tert-butyl hypochlorite (ButOCl) and N-chloro-3,3-dimethylglutarimide (NCG) have been determined (kCl2=3.0*1010, kButOCl=2.6*109 and kNCG=3.6*107, all in 1 mol-1s-1).
Method for the production of substituted or unsubstituted chloromethyl cyclopropane and bromomethyl cyclopropane
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, (2008/06/13)
The present invention relates to a method for the production of substituted or unsubstituted chloromethyl and bromomethyl cyclopropane having a degree of purity above 85%, particularly above 90%, by reacting a hydroxymethyl cyclopropane of the formula STR1 where R is H, or one or two R groups are alkyl of from 1 to 10 carbon atoms or phenyl, with methane sulfonic acid chloride or methane sulfonic acid bromide in the presence of a trialkylamine and, if necessary, an organic solvent, preferably an organic solvent containing oxygen, at a temperature of from -20° C. to +30° C. over a period of time of from 1 to 30 hours, then heating the reaction mixture to a temperature of from 40° to 80° C., or to reflux temperature, without isolating the intermediate mesylate.
