- Method for synthesizing cylopropylmethyl chloride by using cyclopropanemethanol
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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.
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Paragraph 0038; 0047; 0055-0059
(2017/11/29)
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- A mild method for the replacement of a hydroxyl group by halogen. 1. Scope and chemoselectivity
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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.
- 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
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p. 420 - 430
(2015/12/31)
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- Ni-catalyzed cascade cyclization-kumada alkyl-alkyl cross-coupling
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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
- Guisan-Ceinos, Manuel,Soler-Yanes, Rita,Collado-Sanz, Daniel,Phapale, Vilas B.,Bunuel, Elena,Cardenas, Diego J.
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supporting information
p. 8405 - 8410
(2013/07/25)
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- Electrophilic cleavage of cyclopropylmethystannanes: An experimental comparison of σ-σ and σ-π conjugation
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(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.
- Lucke, Andrew J.,Young, David J.
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p. 3579 - 3583
(2007/10/03)
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- Rearrangements concerted with fragmentation of cyclopropylmethoxychlorocarbene and cyclobutoxychlorocarbene in hydrocarbon solvents and Ar matrices
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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.
- Moss, Robert A.,Sauers, Ronald R.,Zheng, Fengmei,Fu, Xiaolin,Bally, Thomas,Maltsev, Alexander
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p. 8466 - 8476
(2007/10/03)
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- Fragmentation of alkoxychlorocarbenes in the gas phase
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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
- Blake, Michael E,Jones Jr., Maitland,Zheng, Fengmei,Moss, Robert A
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p. 3069 - 3071
(2007/10/03)
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- Fragmentation of cyclobutoxychlorocarbene: The cyclopropylcarbinyl/cyclobutyl cations revisited
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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.
- Moss, Robert A.,Zheng, Fengmei,Johnson, Lauren A.,Sauers, Ronald R.
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p. 400 - 406
(2007/10/03)
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- Absolute rate constants for abstraction of chlorine from three chlorinating agents by alkyl radicals
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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).
- Tanko, James M.,Blackert, Joseph F.
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p. 1775 - 1780
(2007/10/03)
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- Method for the production of substituted or unsubstituted chloromethyl cyclopropane and bromomethyl cyclopropane
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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.
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- FRAGMENTATION OF CYCLOPROPYLMETHOXYCHLOROCARBENE: FORMATION OF CYCLOPROPYLCARBINYL/CHLORIDE ION PAIRS
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The decomposition of cyclopropylmethyloxychlorodiazirine in MeCN proceeds via N2 and CO loss, mainly to tight cyclopropylcarbinyl cation-chloride anion pairs that collapse to C4 chlorides with substantial skeletal and label retention; the ion pairs can be intercepted by ethanol with less skeletal retention.
- Moss, Robert A.,Ho, Guo Jie,Wilk, Bogdan K.
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p. 2473 - 2476
(2007/10/02)
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- ON THE REACTION OF ALCOHOLS WITH HALOCARBENES. ARE CARBOCATIONS INTERMEDIATES?
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There is no evidence for hydride shift in the reaction of alcohols 1 and 2 with dichlorocarbene.Accordingly, the intermediate cannot be a free carbocation.It is suggested that the products are formed through a combination of SNi and direct displacement reactions in which tight ion pairs are involved.
- Likhotvorik, Igor R.,Jones, Maitland,Yurchenko, Alexander G.,Krasutsky, Pavel A.
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p. 5089 - 5092
(2007/10/02)
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- REACTIVITY OF TRIETHYL PHOSPHITE WITH TETRACHLOROMETHANE : ELECTRON TRANSFER VERSUS IONIC SUBSTITUTION ON "POSITIVE" HALOGEN
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The reaction of triethyl phosphite (1) with tetrachloromethane (2) has been studied from a mechanistic point of view. 1 reacts at 80 deg C with 2 to form diethyltrichloromethanephosphonate (3) (85-90percent yield) and chloroethane (4) (80percent yield).Several results hint at a radical chain mechanism (like SRN1).Trichloromethyl radical is trapped by 2,6-di-t-butyl-4-cresol (BHT), the reaction may be initiated with UV radiation (254 nm) and a charge transfer complex (CTC) is formed between 1 and 2 ; furthermore, the reaction is inhibited by 7,7',8,8' tetracyanoquinodimethane (TCNQ).Tris(cyclopropylmethyl)phosphite (12a) and tri(1-hexene-6-yl) phosphite (7a) are used as potential radical clocks in these reactions.The first leads inter alia to 3-chloro-1-butene (17) and the second to 5-chloro-1-hexene (11), the first therefore suggests a radical mechanism but not the second.However in this particular case even the results obtained with the tris(cyclopropylmethyl)phosphite may be rationalized also by an ionic mechanism.For the photostimulated reaction , the overall quantum yield is 0.1.The electrochemical oxidation of 1 with added CCl4 does not account for a radical chain process as the main pathway.Furthermore, the application of Marcus analysis to reaction viewed as an electron transfer leads to a calculated rate constant in the range of 10-20 M-1s-1.The synergy of the techniques that we used lead us to conclude that the thermal reaction is in fact an SNCl+ substitution.The radical intermediates would mainly be derived from the electron-transfer reaction between CCl3- and CCl4 the importance of which increases when special conditions such as hν activation are applied.Reaction therefore provides an example where the observed paramagnetic species during a D/A interaction could deceptively suggest an electron-transfer between D and A whereas they originate from an interaction between A and an electron donor formed after or during the first step of the reaction.
- Bakkas, Salem,Julliard, Michel,Chanon, Michel
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p. 501 - 512
(2007/10/02)
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- Regioselective Route to Sterically Hindered Cyclopropylcarbinyl Halides
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Reaction of cyclopropylcarbinyl alcohols 1 with hexachloroacetone and triphenylphosphine resulted in 80 - 90 percent yields of the corresponding cyclopropylcarbinyl chlorides 4 regioselectively, with no trace of the homoallylic chloride 2 or the chlorocyclobutane derivative 6a.Similar reaction of 1 with bromine and triphenylphosphine, in dimethylformamide, gave 65 - 80 percent yields of the cyclopropylcarbinyl bromide 5 with trace amounts of the homoallylic bromide 3 but no detectable bromocyclobutane derivative 6b.These reactions are amenable to the preparation of very sterically hindered cyclopropylcarbonyl halides, heretofore inaccessible, regioselectively and in a facile manner.
- Hrubiec, Robert T.,Smith, Michael B.
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p. 431 - 435
(2007/10/02)
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- PREPARATION OF SOME ALKYL CHLORIDES BY DECOMPOSITION OF ALKOXYPHOSPHONIUM CHLORIDES AND BICHLORIDES
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A number of alkoxyphosphonium chlorides and bichlorides have been prepared as stable intermediates or transient species.The thermal decompositions of these salts have been studied under a variety of conditions.The salts decompose by SN2 and SN1 processes in a fairly predictable manner.There are two decided advantages to using these salts as precursors to alkyl halides.The first is that in systems that are normally prone to rearrangements under substitution conditions, the products of decompositions of the salts are often formed with less rearrangement than is often found in other systems.The second is that the phosphates and phosphine oxides are excellent leaving groups and thus substitutions can be effected at centers that normally react very slowly.
- Denney, Donald B.,Garth, Bruce H.,Hanifin, J. William Jr.,Relles, Howars M.
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p. 275 - 280
(2007/10/02)
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- Reactions of cyclopropylcarbinol in dilute hydrochloric acid
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The treatment of cyclopropylcarbinol (1-OH) with dilute HCl has been used as a method for the preparation of cyclobutanol (2-OH).While 2-OH is the major product in this reaction, a careful investigation showed the presence of a total of 13 products, namely the alcohols 1-OH, 2-OH, and allylcarbinol (3-OH), cyclopropylcarbinyl, cyclobutyl and allylcarbinyl chlorides (1-Cl, 2-Cl and 3-Cl, respectively), dicyclopropylcarbinyl, cyclobutyl cyclopropylcarbinyl, allycarbinyl cyclopropylcarbinyl, dicyclobutyl and allylcarbinyl cyclobutyl ethers (1-O-1, 2-O-1, 3-O-1, 2-O-2, and 3-O-2, respectively), as well as butyraldehyde and isobutyraldehyde.The alcohols, chlorides, and ethers likely arose from reactions of the bicyclobutonium ion with available nucleophiles in the reaction mixture.The minor amounts of the two aldehydes may be due to a ring opening isomerization of 2-methylcyclopropanol, the latter in turn resulted from a net 1,3-hydride shift in the cyclopropylcarbinyl cation, probably via an edge-protonated cyclopropane-type of species.Treatment of cyclopropylcarbinol (1-OH-α-14C) with dilute HCl gave samples of 1-OH-x-14C, 2-OH-x-14C, and 3-OH-x-14C the degradation of which showed that all three methylene groups in these alcohols have become equivalent, indicating a complete equilibration between isotope-position labeled bicyclobutonium ions.
- Lee, Choi Chuck,Cessna, Allan J.
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p. 1075 - 1079
(2007/10/02)
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