Acetonates substituted, alkali metal

The alkali metal dicyano(phthalocyaninato)cobalt-(III) complexes M [PcM(CN)2] were characterized by infrared spectroscopy and in the case of peripherally substituted phthalocyanines also by UV-vis and H NMR spectroscopy. The H NMR spectra of the complexes recorded in acetone-c/ft show the expected number and intensities of signals that confirm the proposed structures. The fact that H NMR spectra are obtained supports the proposed oxidation state -1- 3 and the octahedral ligand field of the Co atom. Otherwise a paramagnetic substance would result. 

Alkali metal salts of 0-alkyl 1-(substituted phenoxyacetoxy)alkylphosphonic acids IIA-IIE could be easily synthesized by the reaction of (9,(9-dialkyl 1-(substituted phenoxyacetoxy)alkylphosphonates lA or IC with corresponding lithium bromide, sodium iodide, or potassium iodide in refluxing acetone. The synthetic route of IIA-IIE is shown in Scheme 3.5. For the synthesis of IIA-IIE, 1-hydrox-yalkylphosphonates M2, substituted phenoxyacetyl chloride MS, and 0,(9-dialkyl 1-(substituted phenoxyacetoxy)alkylphosphonates lA or IC could be prepared according to the known methods as stated in Chap. 2. 0,0-Dialkyl phosphonate Ml was used directly as obtained commercially or prepared by the reaction of phosphorus trichloride and methanol. Ml reacted with different aldehydes to give 0,0-diaUtyl 1-hydroxyalkylphosphonates M2. The substituted phenoxyacetic acids M4 were prepared in satisfactory yields by the reaction of corresponding substituted phenols with 2-chloroacetic acid or ethyl 2-bromoacetate followed by hydrolysis. The substituted phenoxyacetyl chlorides M5 could be easily obtained by the treatment of M4 with excess thionyl chloride. M2 reacted with MS to provide lA or IC (Scheme 3.5). 

Alkali metal O-alkyl 1-(substituted phenoxyacetoxy)alkylphosphonates IIA-IIE could be easily synthesized by the reaction of 0,0-dialkyl 1-(substituted phen-oxyacetoxy)alkylphosphonates lA or IC with lithium bromide, sodium iodide, and potassium iodide in refluxing acetone (Scheme 9.10). 

General procedure A solution of the appropriate 0,0-dialkyl 1-(substituted phenoxyacetoxy)alkylphosphonate (0.02 mol) and oven-dried lithium bromide, sodium iodide, or potassium iodide (0.02 mol) in dry acetone (molecular sieve 4 A, 40 mL) was refluxed with stirring under nitrogen for 2-22 h. The solution was evaporated under reduced pressure. The residual solid was reciystallized from dichloromethane to afibrd corresponding pure product as a white solid or ctystal. IIA-IIE could be obtained by this procedure in 43-88 % yields and these alkali metal salts were easily deliquescent in air [20-23]. 

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