F:Flammable;
624-65-7Relevant articles and documents
Isomerization and decomposition of chloromethylacetylene
Kumaran, Soundararajan S.,Lim, Kee P.,Michael, Joe V.,Tilson, Jeffrey L.,Suslensky, Aya,Lifshitz, Assa
, p. 223 - 232 (1996)
The isomerization and thermal decomposition of chloromethylacetylene (CMA) has been studied with two shock tube techniques. The first experiment (Jerusalem) utilizes single-pulse shock tube methods to measure the isomerization rate of CMA to chloroallene. In addition, equilibrium constants can be estimated at ～1200 K. The second experiment (Argonne) monitors Cl-atom formation at temperatures above ～1150 K. Absolute yield measurements have been performed over the 1200-1700 K range and indicate that two decomposition channels contribute to CMA destruction, namely, Cl fission and HCl elimination. The results show that the branching fraction between processes is temperature dependent. Therefore, direct Cl-atom fission is accompanied by molecular elimination, undoubtedly giving HCl and one or more isomers of C3H2. MP2 6-31G(d,p) ab initio electronic structure calculations have been used to determine vibration frequencies and moments of inertia for three C3H3Cl isomers. Using these quantities, the experimental equilibrium constants required that ΔH00(CH2Cl-C≡CH ? CHCl=C=CH2) = -0.24 kcal mole-1. A potential energy surface pertinent to the present system has been constructed, and RRKM calculations have been carried out in order to explain the isomerization rates. The isomerization data can be explained with E0 = 52.3 kcal mole-1 and 〈ΔEdown〉 = 225 cm-1. Subsequent semi-empirical Troe and RRKM-Gorin modeling of the Cl atom rate data require E0 = (67.5 ± 0.5) kcal mole-1 with a (ΔEdown) = (365 ± 90) cm-1. This suggests a heat of formation for propargyl radicals of (79.0 ± 2 5) kcal mole-1.
Reaction of tellurium tetrachloride with propargyl halides
Martynov,Makhaeva,Larina,Amosova
, p. 1249 - 1252 (2015)
The reaction of tellurium tetrachloride with propargyl bromide in boiling benzene regio- and stereoselectively afforded bis[(Z)-3-bromo-2-chloroprop-1-en-1-yl]tellurium dichloride which was readily reduced to bis[(Z)-3-bromo-2-chloroprop-1-en-1-yl] telluride. Propargyl chloride reacted with tellurium tetrachloride preliminarily stored for several months (and containing decomposition products) to give a mixture of bis[(Z)-2,3-dichloroprop-1-en-1-yl]tellurium dichloride and regioisomeric [(Z)-1,3-dichloroprop-1-en-2-yl]- [(Z)-2,3-dichloroprop-1-en-1-yl]tellurium dichloride at a ratio of 3: 2, whereas the latter was formed as the sole product in the reaction with freshly prepared tellurium tetrachloride. Reduction of the regioisomer mixture produced the corresponding tellurides. The structure of the isolated compounds was confirmed by 1H, 13C, and 125Te NMR spectra.
A mild method for the replacement of a hydroxyl group by halogen: 3. the dichotomous behavior of α-haloenamines towards allylic and propargylic alcohols
Munyemana, Fran?ois,Patiny, Luc,Ghosez, Léon
, (2021/06/07)
A study of the deoxyhalogenation of allylic and propargylic alcohols with tetramethyl-α-halo-enamines is reported. Primary allylic and primary and secondary propargylic alcohols gave the corresponding halides in high yields. Secondary allylic and propargylic alcohols yielded the corresponding secondary halides but the reaction also produced some rearranged primary halides (I > Br > Cl). The reactions with tertiary allylic and tertiary propargylic alcohols gave several products and was therefore of little synthetic value. However, the addition of triethylamine to the reaction mixture or the use of lithium alkoxide instead of alcohol brought about a major change of the course of the reaction which led to amides carrying an allyl or an allenyl group at C2. This was shown to result from a Claisen-Eschenmoser rearrangement of an intermediate α-allyloxy- or propargyloxy-enamine.
Novel synthesis method of propyzamide
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Paragraph 0020-0021; 0022-0023; 0024-0025; 0026-0031, (2021/04/17)
The invention relates to the technical field of pesticide synthesis, and provides a novel synthesis method of propyzamide, which comprises the following steps: S1, adding 3, 5-dichlorobenzoyl chloride, 3-amino-3-methyl-1-butyne and a solvent into a reaction kettle, and starting stirring; S2, heating to 20 DEG C, adding an acid-binding agent and a compound catalyst into the reaction kettle, and reacting for 4-6 hours; S3, after the reaction is finished, adding water, adding dichloroethane, and layering; S4, adding the layered organic phase into a sulfuric acid solution with the concentration of 2.0 mol/L-3. 0mol/L, regulating the pH value to 6-7, cooling to 5 DEG C, stirring for 2 hours, and centrifugally filtering to obtain the propyzamide product. Through the technical scheme, the problems of long reaction time and poor product quality in the prior art are solved.
METHOD OF CONVERTING ALCOHOL TO HALIDE
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Page/Page column 53; 113; 114, (2017/01/02)
The present invention relates to a method of converting an alcohol into a corresponding halide. This method comprises reacting the alcohol with an optionally substituted aromatic carboxylic acid halide in presence of an N-substituted formamide to replace a hydroxyl group of the alcohol by a halogen atom. The present invention also relates to a method of converting an alcohol into a corresponding substitution product. The second method comprises: (a) performing the method of the invention of converting an alcohol into the corresponding halide; and (b) reacting the corresponding halide with a nucleophile to convert the halide into the nucleophilic substitution product.
PROCESS FOR MANUFACTURING 4-PROPARGYLATED AMINO-BENZOXAZINONES
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Page/Page column 18, (2015/01/07)
The present invention relates to a process for manufacturing 4-propargylated amino- benzoxazinones of formula (I), comprising the following steps: step a) preparing propargyl chloride by reacting propargyl alcohol with thionyl chloride optionally in the presence of a catalyst; and step b) reacting the propargyl chloride prepared in step (a) with a NH-benzoxazinone of formula (II); wherein the variables are defined according to the description.
Copper(I)-catalyzed regio- and chemoselective single and double addition of nucleophilic silicon to propargylic chlorides and phosphates
Hazra, Chinmoy K.,Oestreich, Martin
supporting information; experimental part, p. 4010 - 4013 (2012/10/08)
Copper(I)-catalyzed propargylic substitution of linear precursors with (Me2PhSi)2Zn predominantly yields the γ isomer independent of the propargylic leaving group. The thus formed allenylic silane reacts regioselectively with another equivalent of (Me2PhSi) 2Zn, yielding a bifunctional building block with allylic and vinylic silicon groups. The reaction rates of both steps are well-balanced for chloride (γ:α ≥ 99:1) where the propargylic displacement occurs quantitatively prior to the addition step. Substitutions of α-branched propargylic phosphates are also reported.
Copper(I)-catalyzed regioselective propargylic substitution involving Si-B bond activation
Vyas, Devendra J.,Hazra, Chinmoy K.,Oestreich, Martin
supporting information; experimental part, p. 4462 - 4465 (2011/10/08)
The silicon nucleophile generated by copper(I)-catalyzed Si-B bond activation allows several γ-selective propargylic substitutions. The regioselectivity (γ:α ratio) is strongly dependent on the propargylic leaving group. Chloride is superior to oxygen leaving groups in linear substrates (γ:α > 99:1), and it is only the phosphate group that also shows promising regiocontrol (γ:α = 90:10). That leaving group produces superb γ-selectivity (γ:α > 99:1) in α-branched propargylic systems, and enantioenriched substrates react with excellent central-to-axial chirality transfer.
Reaction of N,N-dichloroarenesulfonamides with propargyl alcohol
Drozdova,Kozyreva,Mirskova
, p. 243 - 245 (2007/10/03)
The reaction of N,N-dichloroarenesulfonamides with propargyl alcohol gives 3-hydroxy-2,2-dichloro-1,1-di(N-arenesulfonamido)propanes and N-(3-hydroxy-2,2-dichloropropylidene)arenesulfonamides. The latter were obtained due to the transformation of intermediate products, N-chloro-N-(3-hydroxy-2-chloro1-propenyl)arenesulfonamides, by the 1,3-migration of the halogen atom. The addition of arenesulfonamides formed in the reaction to N-(3-hydroxy-2,2-dichloropropylidene)arenesulfonamides results in the formation of 3-hydroxy-2,2-dichloro-1,1-di(N-arenesulfonamido)propanes.
