29552-15-6Relevant academic research and scientific papers
A versatile and highly efficient method for 1-chlorination of terminal and trialkylsilyl-protected alkynes
Gulia, Nurbey,Pigulski, Bartlomiej,Charewicz, Marta,Szafert, Slawomir
supporting information, p. 2746 - 2749 (2014/03/21)
A highly efficient one-pot procedure for the preparation of 1-chloroalkynes and 1-chlorobutadiynes from terminal and trialkylsilyl-protected precursors is reported. This convenient reaction, proceeding under mild conditions, utilizes N-chlorosuccinimide as the chlorinating agent and tolerates a range of functional groups. A general chlorination of alkynes: A highly efficient one-pot procedure for the preparation of 1-chloroalkynes and 1-chlorobutadiynes from terminal and trialkylsilyl-protected precursors is reported (see figure; TMS=trimethylsilyl, TES=triethylsilyl, TBDMS=tert-butyldimethylsilyl, TIPS=triisopropylsilyl). This convenient reaction, proceeding under mild conditions, utilizes N-chlorosuccinimide as the chlorinating agent and tolerates a range of functional groups.
Reaction of Grignard compounds with 4-chloro-2-methyl-3-butyn-2-ol in Diethyl Ether equivalents
Shchelkunov,Sivolobova,Mataeva,Minbaev,Muldakhmetov
, p. 5 - 8 (2007/10/03)
Reactions of RMgX · THF complexes with 4-chloro-2-methyl-3-butyn-2-ol in aromatic hydrocarbons were studied. The complexes formed by arylmagnesium halides require the presence of anisole for the reaction to occur. 4-Chloro-2-methyl-3-butyn-2-ol can be synthesized by reaction of 2-methyl-3-butyn-2-ol with sodium hypochloride in the two-phase system water-benzene.
1-Halo-1-acceptor-/1,1-diacceptor-substituted allenes, 9: Functionalized allenes, haloallenes, and bisallenes via [2,3]/[3,3]-sigmatropic rearrangements and their reactivity
Saalfrank, Rolf W.,Welch, Andreas,Haubner, Martin,Bauer, Udo
, p. 171 - 181 (2007/10/03)
Reaction of carbonyl compounds 1 with trimethylsilylacetylene 2 leads to the alkynols 3, which are excellent precursors of acceptor-substituted allenes. Compound 3 reacts with carbamoyl chloride 4, diethyl chlorophosphate 6, or hypohalite 8 to give the substituted alkynols 5, 7, 9. Reaction of 9 with sulfinyl chloride 10 leads to the sulfinic esters 11, which on heating undergo a [2,3]-sigmatropic shift to yield the halosulfonyl allenes 12. In the same manner the reaction of 7 and 9 with chlorophosphanes 13 or sulfenyl chlorides 15 gives rise to the generation of the phosphoryl allenes 14 and the haloallenyl sulfoxides 16, respectively. Alkynyl ketene acetal intermediates 18 are formed by starting from the alkynols 9 and orthoesters 17. Spontaneous [3,3]-sigmatropic rearrangement of 18 gives the haloallenyl esters 19. Reaction of alkynols 5 with sulfur dichloride leads to the alkynylsulfinyl esters 20, which on heating rearrange to the bisallenyl sulfones 21. Pyrolysis of 21 yields the thiophene 1,1-dioxides 22. Bisphosphorylbisallene 24 is synthesized from hexadiyndiol 23 by reaction with chlorodiethoxyphosphite. Halophosphoryl allenes 14 react with bromine to yield the oxaphospholenes 25 by cyclization and subsequent elimination of ethanol, or oxaphospholenes 26, if no appropriate leaving group is present in the molecule. Sulfonyl-1,3-dienes 27 can be synthesized by reaction of halosulfonylallenes 12 with bromine, followed by elimination of HBr. Haloallenyl ester 19a is converted in a non-generalizable reaction with bromine into the tribromo3,6-dihydro-2-pyranone 30. VCH Verlagsgesellschaft mbH, 1996.
Unsaturated ester-amides of halogenated alkenes
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, (2008/06/13)
This invention deals with new unsaturated ester-amides of α,β-unsaturated polycarboxylic acids derived from halogenated alcohols of the formula EQU1 wherein R is a divalent hydrocarbon moiety having at least one and no more than 10 carbon atoms, X is a member selected from the class of bromine and chlorine, and R' is a member selected from the class of hydrogen and a monovalent hydrocarbon containing at least one and no more than 20 carbon atoms. Typical ester-amides are the maleates, fumarates, itaconates and citraconates. These monomers possess fire-retardant properties and are useful for the synthesis of polymers and copolymers.
