[CH2:1]1[NH:9][CH2:8][CH2:7][NH:6][CH2:5][CH2:4][NH:3][CH2:2]1.[CH2:10]1[CH2:21][NH:20][CH2:19][CH2:18][CH2:17][NH:16][CH2:15][CH2:14][CH2:13][NH:12][CH2:11]1.[P:22](O)([OH:24])[OH:23]>>[CH2:1]1[NH:9][CH2:8][CH2:7][NH:6][CH2:5][CH2:4][NH:3][CH2:2]1.[CH2:7]([O:24][PH:22]([CH2:19][CH:18]=[CH2:17])=[O:23])[CH3:8].[CH2:18]1[CH2:17][NH:16][CH2:15][CH2:14][CH2:13][NH:12][CH2:11][CH2:10][CH2:21][NH:20][CH2:19]1It appears however that the HI3 salts of the monomethylenesulfonic acids of [9]aneN3 and [12]aneN3 can be used directly. When these trilodide salts are added to melted phosphorous acid at 80° C., at 25° C., HP(=O)Et(OEt), or HP(=O)(OEt)2, a very exothermic reaction occurs whereby the respective monomethylenephosphonate, the monomethylene(ethyl)-phosphinate ethyl ester and the monomethylenephosphonate diethyl ester of [9]aneN3 (FIGS. 31A, 31B, and 31C) and the monomethylenephosphonate diethyl ester and the monomethylene(ethyl)-phosphinate ethyl ester of [12]aneN3 (FIGS. 32A and 32B) are formed almost quantitatively within a few seconds.
Loading…
