2009-83-8Relevant articles and documents
Method for synthesizing 6-chloro-1-hexanol by taking 1,6-hexanediol and cyanuric chloride as raw materials
-
Paragraph 0035-0062, (2021/01/29)
The invention relates to the field of organic synthesis, and discloses a method for synthesizing 6-chloro-1-hexanol by using 1,6-hexanediol and cyanuric chloride as raw materials, wherein the method comprises the following steps: 1) dissolving cyanuric chloride in a solvent A, stirring to react, and obtaining a solution for later use after the reaction is finished; 2) preparing 1,6-hexanediol or asolution thereof; 3) slowly dropwise adding the solution obtained in the step (1) into the 1,6-hexanediol or the solution thereof obtained in the step (2), carrying out heat preservation reaction after dropwise adding is finished, filtering reaction liquid after the reaction is finished, rinsing a filter cake by using a solvent B, and collecting filtrate; 4) rectifying the filtrate obtained in the step 3 to prepare the finished product. According to the method, 1,6-hexanediol and cyanuric chloride are used as raw materials to synthesize 6-chloro-1-hexanol, the raw materials are cheap and easyto obtain, the purity of the obtained product can reach 99% or above, the yield can reach 95% or above, the reaction condition is mild, aftertreatment is simple, and the method is more suitable for large-scale industrial application.
A highly active and air-stable ruthenium complex for the ambient temperature anti-markovnikov reductive hydration of terminal alkynes
Zeng, Mingshuo,Li, Le,Herzon, Seth B.
supporting information, p. 7058 - 7067 (2014/06/09)
The conversion of terminal alkynes to functionalized products by the direct addition of heteroatom-based nucleophiles is an important aim in catalysis. We report the design, synthesis, and mechanistic studies of the half-sandwich ruthenium complex 12, which is a highly active catalyst for the anti-Markovnikov reductive hydration of alkynes. The key design element of 12 involves a tridentate nitrogen-based ligand that contains a hemilabile 3-(dimethylamino) propyl substituent. Under neutral conditions, the dimethylamino substituent coordinates to the ruthenium center to generate an air-stable, 18-electron, κ3-complex. Mechanistic studies show that the dimethylamino substituent is partially dissociated from the ruthenium center (by protonation) in the reaction media, thereby generating a vacant coordination site for catalysis. These studies also show that this substituent increases hydrogenation activity by promoting activation of the reductant. At least three catalytic cycles, involving the decarboxylation of formic acid, hydration of the alkyne, and hydrogenation of the intermediate aldehyde, operate concurrently in reactions mediated by 12. A wide array of terminal alkynes are efficiently processed to linear alcohols using as little as 2 mol % of 12 at ambient temperature, and the complex 12 is stable for at least two weeks under air. The studies outlined herein establish 12 as the most active and practical catalyst for anti-Markovnikov reductive hydration discovered to date, define the structural parameters of 12 underlying its activity and stability, and delineate design strategies for synthesis of other multifunctional catalysts.
Regioselective reductive hydration of alkynes to form branched or linear alcohols
Li, Le,Herzon, Seth B.
supporting information, p. 17376 - 17379,4 (2020/09/16)
The regioselective reductive hydration of terminal alkynes using two complementary dual catalytic systems is described. Branched or linear alcohols are obtained in 75-96% yield with ?25:1 regioselectivity from the same starting materials. The method is compatible with terminal, di-, and trisubstituted alkenes. This reductive hydration constitutes a strategic surrogate to alkene oxyfunctionalization and may be of utility in multistep settings.
