6180-22-9Relevant articles and documents
Method for preparing 1-halogenated alkyne under catalysis of heterogeneous Ag catalyst at room temperature
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Paragraph 0023-0036; 0045, (2021/05/12)
The invention discloses a novel method for preparing 1-halogenated alkyne under the catalysis of a heterogeneous Ag catalyst at room temperature. The method comprises the steps of mixing terminal alkyne compounds containing different substituent groups, N
Silver-catalyzed synthesis of 1-chloroalkynes directly from terminal alkynes
Shi, Dunfa,Liu, Zhiwen,Zhang, Ziyu,Shi, Wei,Chen, Hao
, p. 1424 - 1426 (2015/06/10)
An efficient method to prepare 1-chloroalkynes was investigated. The method involved the use of readily available terminal alkynes and a catalytic amount of a silver salt with N-chlorosuccinimide as the chlorinating agent under mild conditions. Compared with the existing process, this method has a broad substrate scope: 19 examples were explored, and the products were obtained in excellent yields and were easily isolated by vacuum distillation. Moreover, recycling of the catalyst was achieved by simple filtration and desiccation, which made the method more economic and environmentally benign.
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.
