624-95-3Relevant articles and documents
Production process 3 and 3 - dimethyl butyraldehyde
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Paragraph 0031; 0034; 0036; 0038; 0040; 0042, (2020/11/13)
The invention belongs to the technical field of chemical synthesis and particularly relates to a production technology of 3,3-dimethylbutyraldehyde. The production technology sequentially comprises the following steps: S1, taking tert-butyl alcohol and ethylene as raw materials, taking n-hexane as a reaction solvent, and catalyzing by using sulfuric acid to synthesize 3,3-dimethyl butyl sulfate; S2, under the action of the catalyst, controlling the temperature to be 30 to 50 DEG C and hydrolyzing to obtain 3,3-dimethylbutanol; S3, performing catalyzed oxidation on the 3,3-dimethylbutanol by using an inhibitor 701 and dimethylethyl nitrite to obtain the 3,3-dimethylbutyraldehyde. The production technology has the advantages of safety, reliability, low cost, good reproducibility and high purity of a final product.
Pd-Catalyzed intermolecular C-H bond arylation reactions: Effect of bulkiness of carboxylate ligands
Tanji, Yutaka,Hamaguchi, Ryo,Tsuji, Yasushi,Fujihara, Tetsuaki
supporting information, p. 3843 - 3846 (2020/04/15)
A bulky carboxylic acid bearing one 1-adamantylmethyl and two methyl substituents at the α-position is demonstrated to work as an efficient carboxylate ligand source in Pd-catalyzed intermolecular C(sp2)-H bond arylation reactions. The reactions proceeded smoothly under mild conditions, taking advantage of the steric bulk of the carboxylate ligands.
Failure and Redemption of Statistical and Nonstatistical Rate Theories in the Hydroboration of Alkenes
Bailey, Johnathan O.,Singleton, Daniel A.
supporting information, p. 15710 - 15723 (2017/11/14)
Our previous work found that canonical forms of transition state theory incorrectly predict the regioselectivity of the hydroboration of propene with BH3 in solution. In response, it has been suggested that alternative statistical and nonstatistical rate theories can adequately account for the selectivity. This paper uses a combination of experimental and theoretical studies to critically evaluate the ability of these rate theories, as well as dynamic trajectories and newly developed localized statistical models, to predict quantitative selectivities and qualitative trends in hydroborations on a broader scale. The hydroboration of a series of terminally substituted alkenes with BH3 was examined experimentally, and a classically unexpected trend is that the selectivity increases as the alkyl chain is lengthened far from the reactive centers. Conventional and variational transition state theories can predict neither the selectivities nor the trends. The canonical competitive nonstatistical model makes somewhat better predictions for some alkenes but fails to predict trends, and it performs poorly with an alkene chosen to test a specific prediction of the model. Added nonstatistical corrections to this model make the predictions worse. Parametrized Rice-Ramsperger-Kassel-Marcus (RRKM)-master equation calculations correctly predict the direction of the trend in selectivity versus alkene size but overpredict its magnitude, and the selectivity with large alkenes remains unpredictable with any parametrization. Trajectory studies in explicit solvent can predict selectivities without parametrization but are impractical for predicting small changes in selectivity. From a lifetime and energy analysis of the trajectories, "localized RRKM-ME" and "competitive localized noncanonical" rate models are suggested as steps toward a general model. These provide the best predictions of the experimental observations and insight into the selectivities.
