161869-75-6

Upstream product

• 98-88-4 benzoyl chloride 
• 41071-35-6 (Z)-N-methoxybenzenecarboximidoyl chloride 
• 2446-51-7 N-methoxybenzamide 
• 185197-15-3 phenylmethyl (Z)-N-methoxybenzimidate 
• 185197-24-4 phenylmethyl (E)-N-methoxybenzimidate 
• 593-56-6 N-methoxylamine hydrochloride 
• 119-53-9 2-hydroxy-2-phenylacetophenone 
• 594-19-4 tert.-butyl lithium 

Downstream Products

• 530-36-9 erythro-2-amino-1,2-diphenylethanol 
• 530-36-9 threo-1,2-diphenyl-2-aminoethan-1-ol 
• 701975-89-5 (Z)-2-[[(1,1-dimethylethyl)dimethylsilyl]oxy]-1,2-diphenylethanone O-methyloxime 

Relevant academic research and scientific papers

Imino 1,2-Wittig rearrangement of hydroximates and its application to synthesis of cytoxazone

The imino 1,2-Wittig rearrangement of hydroximates provides a novel method for the construction of 2-hydroxyoxime ethers. Upon treatment with LDA, Z-hydroximates smoothly underwent stereoselective rearrangement to give Z-2-hydroxyoxime ethers in good yield, which were converted into amino alcohols. On the other hand, the rearrangement of E-hydroximates gave a mixture of E- and Z-2-hydroxyoxime ethers. This method was successfully applied to a practical synthesis of cytoxazone.

α-Imino and α-oximino carbocations. A comparison with α-carbonyl and α-thiocarbonyl carbocations

The σ+ values for the groups m-CH=N-t-Bu and p-CH=N-t-Bu have been determined to be 0.16 and 0.078, respectively. The CH=N-t-Bu group is therefore cation-destabilizing relative to hydrogen when placed in the meta position of a cumyl cation. Although the p-CH=N-t-Bu group is still cation-destabilizing, the effect is reduced by a competing resonance effect when the imino group is placed in the para position. However, when attached directly to a cationic center, this imino group enhances rates relative to α-H. This is interpreted in terms of a cation-stabilizing conjugative effect. The σ+ value of the p-oximino group, p-CH=NOCH3, is -0.03 and indicates that a cation-stabilizing conjugative effect can essentially offset the inductive effect of this electron-withdrawing substituent in a cumyl cation. However, when attached directly to a developing cationic center, this oximino group greatly enhances cation formation rates relative to hydrogen. This group is even more cation-stabilizing than the methyl group. Studies on systems of type ArCH(OMs)C(NOCH3)Ph, where the oximino group can be syn or anti to the developing cationic center, indicate the existence of isomeric α-oximino cations, with the anti cations forming faster than the syn cations. Computational studies at the MP2/6-31G** level support the idea of extensive conjugative stabilization of α-oximino cations. Despite extensive mesomeric stabilization of α-oximimo cations, the primary cation +CH2CH=NOCH3 cannot be solvolytically generated since nucleophilic solvent displacement processes dominate. Stabilities of a series of cations of type +CH2X, where X is a formal electron-withdrawing group, have been evaluated by ab initia methods. Isodesmic reactions indicate a stability order of α-CHNOCH3 ～ CH=CH2 > CHNHCH3 > CHS > CHO ～ H > CN > NO2.