The reaction of phosphorus monoamides with formaldehyde was monitored electrochemically by following the con centration of formaldehyde. Equilibrium measurements show that the methylol derivative is formed in low concentration in aqueous solution. Furthermore, dissolution of the solid methylol derivative of diethylphosphoramidate in water caused essentially complete release of formaldehyde. Phosphorus diamides qualitatively appear to react to a greater decree with formaldehyde, but it was impossible to make quantitative measurements due to successive or competitive reactions.
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References
1.
Badische Anilin and Soda Fabrik Aktiengesellschaft, "New Halomethylphosphonic Acid Bisamides and Process for Flameproofing Cellulosic Fibrous Material Therewith," Brit. Pat. 1,126,259, 1968.
2.
Constant, L.A. , Pepperman, A.B., and Vail, S.L., Enhancement of Polarographic Reduction Current of Formaldehyde by Ammonium Catalysis on the Dehydration Reaction , Anal. Lett., in preparation.
3.
Constant, L. A., unpuhlished data.
4.
Crowe, G.A., Jr. and Lynch, C.C., Polarographic Acetamide-Formaldehyde and Benzamide- Formaldehyde Kinetic Studies , J. Am. Chem. Soc.72, 3622-3623 (1950 ).
5.
Drews, M.J., Yeh, K., and Barker, R.H., RecentFindings in Flame Retardant Finishing, Textilveredlung8, 180-186 (1973).
6.
Frank, A.W., Gonzales, E.J., Margavio, M.F., Vail, S.L., and Reeves, W.A., "New or Unusual Approache to Flameproofing," Presented at the 13th Cotton Utilization Research Conference, New Orleans, La., May 14-16, 1973,
7.
Gonzales, E. J., unpublished results.
8.
Gonzales, E.J. and Vail, S.L., Dimethyl and Diethyl Phosphoramidates as Flame Retardants for Cotton, JFF/Fire Retardant Chem.1, 142-151 (1974).
9.
Grove, G.A., Jr. and Lynch, C.C., Polarographic UreaFormaldehyde Kinetic Studies, J. Am. Chem. Soc.71, 3731-3733 (1949).
10.
Hendrix, J.E. , Drake, G.L., Jr., and Barker , R. II., Pyrolysis and Combustion of Cellulose. II. Thermal Analysis of Mixtures of Methyl α-D-Glycopyranoside and Levoglucosan with Model Phosphate Flame Retardants, J. Appl. Polym. Sci.16, 41-59 (1972).
11.
Hendrix, J.E. and Drake, G.L., Jr.. Pyrolysis and Combustion of Cellulose. III. Mechanistic Basis for the Synergism Involving Organic Phosphates and Nitrogenous Bases, J. Appl. Polym. Sci.16, 257-274 (1972).
12.
Malowan, J.E., "Inorganic Synthesis," Vol. 4, Bailar, J. C., Jr., Editor-in chief, McGraw-Hill, New York, 1953, pp. 77-78.
13.
Margavio, M.F. , Pepperman, A.B., Jr., Constant , L.A., Gonzales, E.J., and Vail, S.L., A Chlorine Bleach Resistant Durable Flame Retardant Finish for Cotton Based on Chloromethyl Phosphonie Diamide, JFF/Fire Retardant Chem.4, 192-206 (1977).
14.
Pepperman, A.B., Jr., Margavio , M.F., and Vail, S.L., Efficiency of Phosphorus Compounds Containing P-N Bonds as Flame Retardants for Cotton Cellulose , JFF/Fire Retardant Chem.3, 276-286 (1976).
15.
Smythe, L.E. , Urea Formaldehyde Kinetic Studies. III. Polarographic Studies in Dilute Solution, J. Am. Chem. Soc.75, 574-576 (1953).
16.
Soignet, D.M. , Berni, R.J., Wadsworth , J.I., and Benerito , R.R., Kinetic Studies of Addition of Formaldehyde to Carbamates, Anal. Lett.7, 379-397 (1974).
17.
Vogt, W., Synthese der β-Hydroxyathanphosphonsaure, Tetrahedron Lett.1281-1284 (1970).
18.
Walker, J.F. , "Formaldehyde", Van Nostrand-Reinhold , New York, 1964, pp. 486-488.
19.
Winkel, A. and Proske, G., Uber die Elektrolytische Reduktion Organischer Verbindungen an der Quicksilber-Tropfelektrode , Chem. Ber.69, 693-706 (1936).
