Radical Interchange on the Part of Certain Alkyl Orthoformates¹

Abstract

Early work on aliphatic ortho esters, while outlining their preparation and properties, has mentioned as well their instability. Triethyl orthoformate for example is not as stable as are the orthoformates of the higher aliphatic alcohols, but no further suggestions have been advanced on this point to date. Compounds of this type have been prepared from the '1) Presented at the Spring Meeting,

Ortho Esters

“…The transesterification of ethyl orthoformate was earlier reported by Hunter [34], Post [35], and Mkhitaryan [36] and was developed later into a general synthesis by Alexander and Busch [37] (see Table V). [37] /CH 3 HC(OC 2 H 5 ) 3 …”

“…R' = Η [35,[82][83][84][85][86][87][88], alkyl [89][90][91][92], aryl [25,[93][94][95][96][97], halogen [98][99][100] R = alkyl [85, 101a], chloroalkyl [101b], aryl [102][103][104][105] actions are thought to occur via carbene intermediates and are a field of active investigation.…”

“…(36) Formation of mixed ortho esters by a disproportionation reaction between two ortho esters [35].…”

STUDIES IN SILICO-ORGANIC COMPOUNDS. III. THE PREPARATIONS AND REACTIONS OF SILICON ANALOGS OF CERTAIN ALIPHATIC ORTHOESTERS1

“…In order to devise and propose a mechanism that would take into consideration the known facts concerning the exchange reaction, it is necessary to consider the work of Post and Erickson on the carbon orthoformates and orthoacetates (6). With the orthoformates, exchange of alkoxyl groups with the homologous alcohols would be expected to take place through a mechanism involving the acidic character of the alcohol.…”