917-92-0Relevant articles and documents
Hargrove,R.J.,Stang,J.S.
, p. 581 - 582 (1974)
Kocienski
, p. 3285 (1974)
Preparation method of 3, 3-dimethyl-1-butyne
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Paragraph 0028-0031; 0034-0043, (2021/04/17)
The invention discloses a preparation method of 3, 3-dimethyl-1-butyne, which comprises the following steps: by using tert-butyl alcohol and acetylene which are simple, readily available and cheap as initial raw materials and using transition metal salt which is readily available on the market as a catalyst, directly reacting in the presence of acid to obtain a product, and carrying out simple distillation separation to obtain a high-purity product. The method is simple and convenient to operate, less in environmental pollution, good in product quality, high in yield, low in cost and more suitable for industrial production.
Lanthanide-Catalyzed Reversible Alkynyl Exchange by Carbon–Carbon Single-Bond Cleavage Assisted by a Secondary Amino Group
Shao, Yinlin,Zhang, Fangjun,Zhang, Jie,Zhou, Xigeng
supporting information, p. 11485 - 11489 (2016/10/24)
Lanthanide-catalyzed alkynyl exchange through C?C single-bond cleavage assisted by a secondary amino group is reported. A lanthanide amido complex is proposed as a key intermediate, which undergoes unprecedented reversible β-alkynyl elimination followed by alkynyl exchange and imine reinsertion. The in situ homo- and cross-dimerization of the liberated alkyne can serve as an additional driving force to shift the metathesis equilibrium to completion. This reaction is formally complementary to conventional alkyne metathesis and allows the selective transformation of internal propargylamines into those bearing different substituents on the alkyne terminus in moderate to excellent yields under operationally simple reaction conditions.
Substituent effects on the photorearrangements of unsymmetrically substituted diazinobarrelenes
Hsieh, Hsing-Pang,Chen, Ann-Cheng,Villarante, Nelson R.,Chuang, Gary J.,Liao, Chun-Chen
, p. 1165 - 1178 (2013/03/14)
A series of diazinobarrelenes 8-15 engendered with alkyl functionalities at the barrelene skeleton were irradiated with 350 nm light under direct and acetone-sensitized reaction conditions. Under these conditions, all the barrelenes except barrelene 14 afforded semibullvalenes with varying degrees of regioselectivity and product distribution. Dicyanopyrazinobarrelenes 8-10 which furnished semibullvalenes 32-41via the aryl-vinyl initial bridging route were strongly controlled by the nitrile functionalities installed at the aromatic sites. Benzoquinoxalinobarrelenes 11-13 which afforded semibullvalenes 42-49, preferentially underwent photorearrangement via vinyl-vinyl bridging even if the compounds were excited at a wavelength where the quinoxaline moiety absorbed most of the light. Zimmerman's bridging hypothesis and the possibility for quinoxalines to undergo intramolecular triplet energy transfer could reasonably account for the observed regioselectivity. Barrelene 14 was insensitive to photorearrangement whereas benzo[f,h]quinoxalinobarrelene 15 preferentially underwent ADPM rearrangement affording semibullvalenes 50-52. Electronic and steric factors of alkyl substituents overwhelmingly controlled the product forming steps whereas localization and minimization of triplet energies greatly influenced the initial bridging interaction. The Royal Society of Chemistry 2013.