67592-99-8

Upstream product

• 64-17-5 ethanol 
• 102697-42-7 4-(Cyano-trimethylsilanyloxy-methyl)-benzoic acid ethyl ester 
• 6287-86-1 p-ethoxycarbonylbenzaldehyde 
• 3516-89-0 ethyl 2-(4-(ethoxycarbonyl)phenyl)acetate 

Downstream Products

• 102697-43-8 ethyl 2-(4-ethoxycarbonylphenyl)-2-oxoacetate 
• 67593-07-1 3,4-Bis-ethoxycarbonylmethyl-benzoic acid ethyl ester 
• 67593-08-2 3-(1-Ethoxycarbonyl-ethyl)-4-ethoxycarbonylmethyl-benzoic acid ethyl ester 
• 102697-35-8 4-(1-Ethoxycarbonyl-2,2-dimethyl-3-methylene-cyclopropyl)-benzoic acid ethyl ester 

Relevant academic research and scientific papers

Boron-Catalyzed O-H Bond Insertion of α-Aryl α-Diazoesters in Water

A catalytic, metal-free O-H bond insertion of α-diazoesters in water in the presence of B(C6F5)3·nH2O (2 mol %) was developed, affording a series of α-hydroxyesters in good to excellent yields. The reaction features easy operation and wide substrate scope, and importantly, no metal is needed as compared with the conventional methods. Significantly, this approach further expands the applications of B(C6F5)3 under water-tolerant conditions.

Captodative Rate Enhancements in the Methylenecyclopropane Rearrangement

A series of 2-aryl-2-carbethoxy-3,3-dimethylmethylenecyclopropanes, 7, with substitution in the para position of the aromatic ring, have been prepared.These substrates rearrange thermally to 2-aryl-2-carbethoxyisopropylidenecyclopropanes, 8, by fragmentation of the cyclopropane bond which gives a biradical intermediate.Rates of this rearrangement are substituent-dependent.Electron-donor substituents such as p-OCH3 and p-SCH3 enhance the rearrangement rate to a greater extent than that predicted by their rate-enhancing effect on the "parent" system, 3-aryl-2,2-dimethylmethylenecyclopropane (4).This enhanced rearrangement rate is attributed to the captodative effect in which the acceptor carbethoxy group and the donor group on the aromatic ring exert a synergistic stabilizing effect on the benzylic portion of the biradical intermediate. p-Fluoro and p-methyl substituents are also capable of acting as true donor groups in captodative systems.Rearrangement rates of 7 containing electron-donor groups correlate with ?+ values, which are a measure of the donor abilities of various groups.The captodative effect has been used as a probe for the mechanism of stabilization of free radicals by the sulfinyl group, SOCH3.No captodative rate enhancement is observed when 7-p-SOCH3 is rearranged.This implies that stabilization of free radicals by the sulfinyl group does not involve utilization of the sulfur nonbonding electron pair in a donor fashion, but probably involves this group acting as an acceptor group.