Phosphonic Acids and Esters. XIII. Nylen and Arbuzov Reactions with Propargyl Bromide¹

Dependence of the long‐range phosphorus–hydrogen coupling constant nJP–H (n = 3,6,7) on the bond order between phosphorus and its substituents: preparation and spectroscopic characterization of several phosphoramidates

“…2 Griffin, 3 Stothers and Robinson 4 and Berry et al 5 have reported the correlation between the hybridization state of the phosphorus atom with proton shift and spin-spin coupling constant J P -H , which was interpreted by Hendrickson et al 6 The influence of benzene on the 1 H NMR spectra of mononuclear phosphorus(V) amides and dimethylamino cyclotriphosphazatrienes is described by Keat and Shaw. 7 Several other publications have described the short-and long-range J P -H in phosphorus compounds 3 -22 and four-and five-bond coupling constants ( 4 J P -H , 5 J P -H ) in allylic and homoallylic phosphorus compounds. 11,13,14,19,22 The observations of five, six, and seven bond couplings in isomeric methylbenzylphosphonium salts have been reported by Khaleeludin and Scott 15 and Gordon and Griffin 14,16 and some other studies have reported 3 J P -H spin-spin coupling too. 6,16 In the above-mentioned studies, several models have been put forward to explain the mechanism of long-range Ł Correspondence to: K. Gholivand, Department of Chemistry, Tarbiat Modarres University, PO Box 14155-4838, Tehran, Iran.…”

Dialkyl 1-Alkynylphosphonates: a Range of Promising Reagents

“…For example, from the reaction between triethyl phosphite 4 and propargyl bromide at 90°C only the diethyl 1-propynylphosphonate 18 (R = Et) was isolated in low yields (15%). [25,26] Early transformation of trialkyl phosphites 1 and haloalkynes 2 (R 1 C≡CX) into dialkyl 1alkynylphosphonates 3 was limited to haloalkynes in which R 1 was an electron-withdrawing group. [23,27] In 1990, two innovations worthy of merit were reported.…”

Phosphonic acid chemistry. 2. Studies on the Arbuzov reaction of 1-bromo-4,4-diethoxy-2-butyne and Rabinowitch method of dealkylation of phosphonate diesters using chloro- and bromotrimethylsilane

“…4-Bromo-l,l-diethoxy-2-butyne (2). The compound was prepared in the reported yield (65%) according to the method of Epsztein and Marszak7 by reacting propargyl bromide with triethyl orthofor-mate8 using zinc iodide as the catalyst: bp 117-121 °C (14 Torr) (lit.7 yield 65%, bp 113-115 °C (13 Torr)); NMR (CC14) 1.2 (t,J = 7 Hz, CH3CH20), 3.58 (ABq, CH20),22 3.9 (d, J = ~1.5 Hz, CH2C), 5.23 (t, J = -1.5 Hz, CH).…”

“…The phosphonate analyzed correctly for C, , P and was the same by IR and NMR as 3 derived from reaction lb. It was also the same (IR, NMR) as 3 prepared by reacting 2 and NaP(O)-(OMe)2 at -65 °C in THF (yield 17%). The aliene 11, obtained from the A1203 isomerization of 9, exhibited two aliene IR absorptions at 5.09 and 5.14 µ which was consistent with published findings14 on alienes having the structure R2C=C=CH2.…”

“…Arbuzov reactions of propargyl halides have been re-ported2-4 to give complex reaction mixtures from which 2-alkynylphosphonates are difficultly isolable in pure form and good yield. As part of our program5 to prepare new and novel analogues of pyridoxal phosphate (PPal), we undertook the synthesis of the phosphonate 1, using the Arbuzov reaction of 2 and trimethyl phosphite ((MeO)3P). This communication reports the chemistry of this reaction, the synthesis of 1 and 3, and the synthesis of the dicyclohexylamine (DCH) salt 4 which was of interest to us.…”