19396-83-9Relevant articles and documents
On the Reaction of (Dibromomethyl)lithium with Bicyclic and Tricyclic Ketones
Teager, David S.,Ward, Harry D.,Murray, Roger K.
, p. 5493 - 5499 (1993)
Many literature examples show that the reaction of a simple cyclic ketone with (dibromomethyl)lithium at -78 deg C, followed by low-temperature hydrolysis of the resulting lithium alkoxide 33, gives the corresponding dibromomethyl alcohol.We have found that the reaction of a bicyclic or tricyclic ketone with (dibromomethyl)lithium under comparable conditions provides a dibromomethyl alcohol and/or an α-bromo aldehyde.The latter product appears to result from an intramolecular displacement reaction in 33 to give a bromo epoxide, which then rearranges stereospecifically to the α-bromo aldehyde.The product ratios obtained in all of these reactions seem to be determined by the steric interactions in 33 between the alkoxide and dibromomethyl groups and the hydrogens that are syn to them at the carbons which are β to the original carbonyl carbon.As these steric interactions increase, the proportion of α-bromo aldehyde in the product mixture increases.If 33 obtained from any cyclic ketone is warmed to 10 deg C before it is hydrolyzed, then the only product isolated is the α-bromo aldehyde.
Method for preparing aldehyde through hydroformylation of internal olefin
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Paragraph 0041-0042, (2020/04/29)
The invention provides a method for preparing aldehyde through hydroformylation of internal olefin. The preparation method is characterized by comprising the following steps: adding a water-soluble rhodium compound, a water-soluble diphosphine ligand, an additive, deionized water and internal olefin into a reaction kettle equipped with a stirrer and a thermocouple; carrying out replacing 3-5 timesby using synthesis gas formed by mixing hydrogen and carbon monoxide according to a volume ratio of 1: 1; carrying out pressurizing to 1.0-5.0 MPa; conducting a reaction for 2-10 hours at a temperature of 60-120 DEG C; and conducting cooling, taking out a reaction product, and performing separating to obtain the product aldehyde.
Ruthenium Catalyzed Selective α- And α,β-Deuteration of Alcohols Using D2O
Chatterjee, Basujit,Gunanathan, Chidambaram
supporting information, p. 4794 - 4797 (2015/10/12)
Highly selective ruthenium catalyzed α-deuteration of primary alcohols and α,β-deuteration of secondary alcohols are achieved using deuterium oxide (D2O) as a source of deuterium and reaction solvent. Minimal loading of catalyst (Ru-macho), base (KOtBu), and low temperature heating provided efficient selective deuteration of alcohols making the process practically attractive and environmentally benign. Mechanistic studies indicate the D-O(D/R) bond activations by metal-ligand cooperation and intermediacy of carbonyl compounds resulting from dehydrogenation of alcohols.
