- Preparation method of dichloroalkane
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The invention discloses a preparation method of dichloroalkane, which comprises the following steps: mixing diol, a catalyst and a solvent, stirring and heating the components, introducing HCl gas into the mixture, and carrying out reflux reaction for 3-5 hours; and after the reaction is finished, treating the reaction solution to obtain dichloroalkane. According to the preparation method providedby the invention, the catalyst ammonium chloride is added, so that the reaction speed is obviously increased, and side reactions are reduced. In the invention, a large amount of solvent water is added in the reaction process, so that on one hand, the formation of monochloro ether by-products can be effectively inhibited, a water phase can be directly and repeatedly used, and basically no sewage is discharged; besides, by using the oil-water separator, the dichloroalkane product can be effectively separated, the product purity is high, and the yield is high.
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Paragraph 0018; 0022-0025
(2021/02/10)
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- Thiourea-Mediated Halogenation of Alcohols
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The halogenation of alcohols under mild conditions expedited by the presence of substoichiometric amounts of thiourea additives is presented. The amount of thiourea added dictates the pathway of the reaction, which may diverge from the desired halogenation reaction toward oxidation of the alcohol, in the absence of thiourea, or toward starting material recovery when excess thiourea is used. Both bromination and chlorination were highly efficient for primary, secondary, tertiary, and benzyl alcohols and tolerate a broad range of functional groups. Detailed electron paramagnetic resonance (EPR) studies, isotopic labeling, and other control experiments suggest a radical-based mechanism. The fact that the reaction is carried out at ambient conditions, uses ubiquitous and inexpensive reagents, boasts a wide scope, and can be made highly atom economic, makes this new methodology a very appealing option for this archetypical organic reaction.
- Mohite, Amar R.,Phatake, Ravindra S.,Dubey, Pooja,Agbaria, Mohamed,Shames, Alexander I.,Lemcoff, N. Gabriel,Reany, Ofer
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supporting information
p. 12901 - 12911
(2020/11/26)
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- Synthesis of new N-glycosides based on Valproic acid analogs tetrazole derivatives
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New N-glycosides based on valproic acid analogs tetrazole derivatives were synthesized. The bis-tetrazole derived from 1,6-hexandiol was also connected to acetylated glucose and formed bis-N-glycoside. Structures characterizations have been performed using FT IR, 1H and 13C NMR spectroscopy.
- Noroozi Pesyan, Nader,Ebrahimi, Marziyeh
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p. 1059 - 1067
(2017/03/11)
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- Aromatic cation activation: Nucleophilic substitution of alcohols and carboxylic acids
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A new method for the nucleophilic substitution of alcohols and carboxylic acids using aromatic tropylium cation activation has been developed. This article reports the use of chloro tropylium chloride for the rapid generation of alkyl halides and acyl chlorides under very mild reaction conditions. It demonstrates, for the first time, the synthetic potential of tropylium cations in promoting chemical transformations.
- Nguyen, Thanh V.,Bekensir, Alp
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supporting information
p. 1720 - 1723
(2014/04/17)
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- Method for Chlorinating Alcohols
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A process for preparing organic chlorides in which the chlorine atom is bonded to a CH2 group by reacting the corresponding alcohols with thionyl chloride in the presence of a triaylphosphine oxide at a temperature of from 20 to 200° C. and a pressure of from 0.01 to 10 MPa abs, which comprises using the triarylphosphine oxide in a molar ratio to the amount of OH groups to be chlorinated of from 0.0001 to 0.5.
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Page/Page column 5-6
(2008/12/07)
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- Method for producing haloalkanes from alcohols
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The invention relates to a process for preparing haloalkanes by reaction of alcohol with hydrogen halide, wherein the reaction of the alcohol with the hydrogen halide occurs in the presence of an ionic liquid at a temperature which is above 100° C. for at least part of the time and, at least at the time of the commencement of the reaction, the water content is not more than 25 mol % based on the amount of liquid, where the ionic liquid is not octyltrimethylammonium chloride.
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- METHOD FOR PRODUCING HALOALKANES FROM ALCOHOLS
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The invention relates to a method for producing haloalkanes by reacting alcohol with halogen hydracide. The inventive method is characterized in that the reaction of the alcohol with the halogen hydracide is carried out in the presence of an ionic liquid at least temporally at a temperature of more than 100 °C and that the water content, at least at the time when the reaction starts, is not more than 25 mol % based on the amount of ionic liquid, said liquid not being octyltrimethyl ammonium chloride.
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Page/Page column 20
(2008/06/13)
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- Solid-state chlorodecarboxylation of mono- and dicarboxylic acids with the Pb(OAc)4-MCl system
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Solid state reactions of acids RCOOH (R = n-C7H15, BuC(Et)H, n-C9H19, PhCH2, PhCH 2CH2, H2C=CH(CH2)8, or MeOOC(CH2)3) with Pb(OAc)4 combined with KCl, NaCl, CdCl2, or NH4Cl in the absence of a solvent and without mechanical activation afford chlorohydrocarbons RCl. The corresponding reactions of acids HOOC(CH2)nCOOH (n = 3-6) give dichloroalkanes Cl(CH2)nCl and γ-butyrolactone (n = 3).
- Nikishin,Sokova,Chizhov,Makhaev,Kapustina
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p. 2200 - 2204
(2007/10/03)
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- Solid-phase reactions of alkanedicarboxylic acids with the Pb(OAc) 4-NH4Cl system
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The title reactions of HOOC(CH2)nCOOH acids afford α,ω-dichloroalkanes (n = 3, 4, 6) and lactones (n = 3, 4) as the main products.
- Nikishin, Gennady I.,Sokova, Lyubov L.,Makhaev, Viktor D.,Kapustina, Nadezhda I.
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p. 264 - 265
(2007/10/03)
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- Should anionised benzylic sulfones be considered as carbenoids?
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Na·Hg reduction of benzyl sulfones 1c-e in aprotic solvent conditions affords stilbenes 4c-e, an olefination process best explained by assuming that the corresponding sulfone carbanion, which was formed under these conditions, is decomposed into a carbene species.
- Jolivet,Uguen
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p. 7907 - 7911
(2007/10/03)
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- A useful conversion of alcohols to alkyl fluorides
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A useful conversion of alcohols to alkyl fluorides via their fluoroformates is introduced. The fluoroformates are obtained in nearly quantitative yield from the alcohols by treatment with COF2 (generated in situ from bis(trichloromethyl) carbonate) in ether with KF as an added acid scavenger. The neat fluoroformates are cleaved to the fluorides by heating at 120-125°C using hexabutylguanidinium fluoride (HBGF) as the catalyst.
- Flosser, David A,Olofson, Roy A
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p. 4275 - 4279
(2007/10/03)
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- A safe and efficient procedure to prepare alkyl and alkoxyalkyl chlorides and dichlorides by catalytic decomposition of the corresponding alkyl and alkoxyalkyl chloroformates and bischloroformates with hexabutylguanidinium chloride
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Small amounts of hexabutylguanidinium chloride (0.01 mol%) decomposes pure chloroformates or bischloroformates with different lengths of carbon chains by a semicontinuous process to diminish run-away risk, leading to chloride compounds with high yield and purity.
- Violleau,Thiebaud,Borredon,Le Gars
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p. 367 - 373
(2007/10/03)
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- Preparation of alkyl, alkenyl, and alkynyl chlorides
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The preparation of an alkyl, alkenyl, or alkynyl chloride by the reaction of a corresponding alcohol with phosgene or thionyl chloride in the presence of a phosphine oxide acting as catalyst, wherein the catalyst used is an aliphatic, cycloaliphatic, or cyclic/aliphatic phosphine oxide.
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- MECHANISMS OF FREE-RADICAL REACTIONS. XXIV. QUANTITATIVE DESCRIPTION OF THE POLAR EFFECTS OF SUBSTITUENTS ON THE KINETICS OF THE FREE-RADICAL CHLORINATION OF ALIPHATIC COMPOUNDS BY N-CHLOROPIPERIDINE
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The free-radical chlorination of 1-substituted alkanes with electron-withdrawing substituents by N-chloropiperidine in trifluoroacetic acid was studied by the method of competing reactions, and the relative rate constants were obtained for all positions of the substrates.The data on the position selectivity can be described satisfactorily by means of an electrostatic model of the polar effect of the substituent, calculated according to the Kirkwood-Westheimer equation.The obtained characteristics of the electrostatic effect can be successfully applied to calculation of the substrate selectivity and the intermolecular relative rate constants for all the positions, beginning with the third.The Taft equation is unsuitable for description of the effect of substituents on the reaction rate.
- Dneprovskii, A. S.,Mil'tsov, S. A.,Arbuzov, P. V.
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p. 1826 - 1835
(2007/10/02)
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- Experimental evidence for AcO-7 neighboring group participation
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The reaction of diol diacetates with anhydrous aluminium chloride at ca 100° leads to displacement of only one of the acetoxy groups by chlorine. An oxygen-18 label study has shown that these displacements take place via acetoxonium intermediates and has provided direct evidence for the intervention of a seven-membered ring acetoxonium ion in the displacement of acetate by chlorine in 1,4-butanediol diacetate.
- Wilen, Samuel H.,Delguzzo, Luciano,Saferstein, Richard
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p. 5089 - 5094
(2007/10/02)
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- THE LONG-RANGE ACTION OF THE POLAR EFFECT OF SUBSTITUENTS ON THE ABSTRACTION OF HYDROGEN IN FREE-RADICAL CHLORINATION PROCESSES
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The free-radical chlorination of 1-chloroalkanes between C3 and C6 at 263 deg K was studied under conditions with wide variation in the concentrations of the substrates in benzene.By analysis of the products from chlorination of the pure substrates it was shown that the deactivating effect of the polar substituent does not extend beyond the third carbon atom and is mainly determined by the inductive effect.In the transition to an aromatic solvent the deactivating effect on the substituent extends to the fourth carbon atom.The results are substantiated in terms of a contribution from dipole-dipole interaction between the substituent and the polar form of the transition state to the polar effect of the substituents.
- Aver'yanov, V. A.,Ruban, S. G.,Klykova, M. B.,Golubev, V. E.
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p. 435 - 439
(2007/10/02)
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- MECHANISMS OF FREE-RADICAL REACTIONS. XIX. SELECTIVITY OF THE FREE-RADICAL CHLORINATION OF 1-CHLOROALKANES BY N-CHLOROPIPERIDINE
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The free-radical chlorination of 1-chloroalkanes ClH2l+1Cl (l = 4-7) by N-chloropiperidine was studied by the method of competing reactions, and the relative constants for all the positions of the investigated substrates were determined.The chlorination is a highly electrophilic process, and the effect of the substituents is transmitted through at least six C-C bonds.The results can be described satisfactorily by means of an electrostatic model of the polar effect of the substituents according to the Kirkwood-Westheimer equation.At the same time an attempt to describe the obtained data by means of the Taft equation led to unsatisfactory results.
- Dneprovskii, A. S.,Mil'tsov, S. A.
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p. 265 - 269
(2007/10/02)
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- SYNTHESIS OF HIGHER ACETYLENIC ALCOHOLS
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The alkylation of 1-alkynes in various solvents was investigated, and the optimum conditions for the production of acetylenic alcohols were obtained.
- Kovalev, B. G.,Matveeva, E. D.,Stan, V. V.,Vovk, G. A.,Yudin, L. G.,Kost, A. N.
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p. 1728 - 1733
(2007/10/02)
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