Cyclic Phosphinates by the Alkylation of a Thermally Unstable 1-Hydroxy-1,2- Dihydrophosphinine 1-Oxide and A 3-Hydroxy-3-Phosphabicyclo[3.1.0]Hexane 3-Oxide

Abstract

P O OR 56 °C P O OH K 2 CO 3 acetone RX R 1 R 2 Me Me H H = Cl Cl Me R 1 R 2 Cl , R = n Bu, n Pr, i Pr, EtAbstract 1-alkoxy-1,2-dihydrophosphinine oxides 4 may be prepared by the reaction of 1-hydroxy-1,2-dihydrophosphinine 1-oxide 3 with alkyl halides. The best results were obtained in boiling acetone in the presence of K 2 CO 3 . The outcome of the alkylation of 3-hydroxy-6,6-dichloro-3-phosphabicyclo[3.1.0]hexane 3-oxide 5 was dependent on temperature. Butylation at 56 • C in acetone using K 2 CO 3 afforded mainly the expected phosphinate 6, but an increase in the temperature led to opening of the cyclopropane ring, resulting in the formation of 1-butoxy-1,2-dihydrophosphinine oxide 4a as the major product.

Application of Microwave Irradiation in the Synthesis of P-Heterocycles

“…However, in the case of thermally unstable cyclic phosphinic acids, such as 3-hydroxy-3-phosphabicyclo[3.1.0]hexane 3-oxide and 1-hydroxy-1,2-dihydrophosphinine 1-oxide derivatives, the MW-assisted method was not preferred due to side reactions [46].…”

Six-Membered Rings With One Phosphorus Atom

“…49 In an alternative approach, using K 2 CO 3 in acetone under reflux enabled effective alkylation of several phosphinic acids 76a-c (Scheme 33). 51 phobanes, 52 are widely used for ROMP, RCM and CM of alkenes, 18 for ethenolysis of long chain oleates, and in isomerizing olefin metathesis. 53 Numerous structural modifications have been made on these alkyl-phosphine ligands to tailor the activity and stability of the ruthenium complex.…”

The Impact of Microwaves on Organophosphorus Chemistry

“…During O‐alkylations of phosphinic acids, as in that of phenols, the joint application of MW irradiation and PTC was found to be synergistic . Sensitive esters were prepared in another way . The cyclic phosphinates were utilized in the synthesis of other derivatives ,…”