Potassium phosphites

H ] 10 9 grm. per litre at 20°. H. Stamm found that the salt is precipitated by ammonia from its cone. aq. soln. P. L. Dulong, H. Rose, and C. A. Wurtz prepared potassium phosphite, K2(HPOs), by neutralizing phosphorous acid with potassium hydroxide. 

H. Rose found the syrupy liquid crystallized when kept in vacuo. C. A. Wurtz said the salt can be dried at 280° without decomposition. P. L. Dulong said that the salt is deliquescent in air, and insoluble in alcohol. According to A. Gutmann, a cold or boiling soln. of sodium thiosulphate does not act on sodium or potassium phosphite—vide the arsenites. N. N. Mittra and N. R. Dhar found that the reaction with mercuric chloride and sodium phosphite as primary reactions is hastened by the simultaneous reaction of mercuric chloride with sodium arsenite or arsenious acid. 

The proposed mechanism for this catalytic asymmetric hydrophosphonylation is shown in Figure 35. The first step of this reaction is the deprotonation of dimethyl phosphite by LPB to generate potassium dimethyl phosphite. This potassium phosphite immediately coordinates to a lanthanoid to give I due to the strong oxophilicity of lanthanoid metals. The complex I then reacts (in the stereochemistry-determining step) with an imine to give the potassium salt of the a-aminophosphonate. A proton-exchange reaction affords the product... 

Potassium phosphites and hypophosphates.—Monopotassium and dipotassium hydrogen phosphite, potassium pyrophosphite, and potassium hypophosphaie are obtained by methods analogous to those employed for the corresponding sodium salts. 

PCI3 + 3 H2O HP0(0H)2 + 3 HCl Potassium phosphite is also a convenient precursor to phosphorous acid ... 

In practice aqueous potassium phosphite is treated with excess hydrochloric acid. By concentrating the solution and precipitations with alcohols, the pure acid can be separated from the salt. 

In addition to alcohols, some other nucleophiles such as amines and carbon nucleophiles can be used to trap the acylpalladium intermediates. The o-viny-lidene-/j-lactam 30 is prepared by the carbonylation of the 4-benzylamino-2-alkynyl methyl carbonate derivative 29[16]. The reaction proceeds using TMPP, a cyclic phosphite, as a ligand. When the amino group is protected as the p-toluenesulfonamide, the reaction proceeds in the presence of potassium carbonate, and the f>-alkynyl-/J-lactam 31 is obtained by the isomerization of the allenyl (vinylidene) group to the less strained alkyne. 

The reduction of benzofuroxans can lead to a variety of products, depending upon the conditions. Deoxygenation to benzofurazans (40) can be effected either directly, using trialkyl phosphites, -tributyl or triphenyl - phosphine, or indirectly, via o-quinone dioximes (41), using methanol and potassium hydroxide, or hydroxyl-amine and alkali. - - The dioximes may be isolated, but... 

C9H21BO3 5419-55-6) see Losartan potassium Rofecoxib triisopropyl phosphite... 

Potassium cyanide, 56, 20 Potassium diethyl phosphite, 58, 135, 138 Potassium 1,1,1,3,3,3-hexafluoro-2-phenyl-... 

To a solution of triphenyl phosphite (6.2 g, 0.02 mol) and thiomethoxy-acetaldehyde (2.25 g, 0.025 mol) in glacial acetic acid (18 ml), powdered N-phenylthiourea was added in a single portion. The reaction mixture was stirred at room temperature for 30 min and then for 30 min at 80°C. After the mixture was cooled to room temperature, water (5 ml) was added and the solution was maintained at room temperature for 10 h. The precipitate was removed by suction filtration, washed with 1 1 acetic acidtwater (2 x 10 ml), dried over potassium hydroxide in an evacuated dessicator, and recrystallized from chloroform/ methanol. In this manner there was isolated pure 0,0-diphe-nyl 2-methylthio-l-(iV-phenylthioureido)ethylphosphonate (8.61 g, 94%) of mp 136 to 138°C, which exhibited spectra and analytical data in accord with the proposed structure. 

As previously stated (p. 53) di-(2-chloroethyl) phosphoro-fluoridate can be prepared by the action of phosphorus oxydi-chlorofluoride on ethylene chlorohydrin. The compound can also be prepared by the fluorination of di (2-chloroethyl) phos-phorochloridate, prepared from di-(2-chloroethyl) hydrogen phosphite (XVIII), obtained by the action of phosphorus trichloride on ethylene chlorohydrin. This partial fluorination was effected by means of sodium fluoride, although the yield was not high. The chlorine atoms of the 2-chloroethyl groups were not affected by this procedure, a fact which falls into line with the observations of Saunders and Stacey (p. 12) that ethylene chlorohydrin is not readily fluorinated by sodium fluoride, but only by potassium fluoride under pressure in a rotating autoclave.1... 

We obtained diethyl phosphorocyanidate (V) in only small yield by the action of potassium cyanide on the corresponding phosphorochloridate. We were able to prepare it,6 however, by the action of cyanogen iodide on the phosphite. This is apparently a modified Arbusov reaction ... 

PECH did not react with potassium cyanate but reacted with equimolar potassium thiocyanate in DMF (90°Ci.16 h) to give the thiocyanated polymer (2g, IR, 2180 cm 1) in 53% of DS. Comparing the IR spectrum with those of model compounds, Me2CHCH2SCljl (2180 cm-1) and Me2CHCH2NCS (2200., 2125 cm-1), the isothiocyanate moieties are scarcely existed in the polymer 0. Since the -SCN is a protecting form of thiol likewise the -SCI, the polymer 20 are insolubilized with aqueous alkali presumably due to the S-S crosslinking (23.). Further, absorption at 2180 cm in 20 was completely disappeared treating it with two equivalents of triethyl phosphite at 90°C for 16 h in DMF probably due to the formation of phosphonate structure ( ,). ... 

A cation arriving with a nncleophilic anion is another important factor. The nucleophile can attack the substrate in the form of a free ion or an ionic pair. As a rule, lithium salts are less reactive than sodium and potassium salts. Russell and Mndryk (1982) reported several examples of this. The sodium salt of ethyl acetylacetate reacts with 2-nitro-2-chloropropane in DMF yielding ethyl 2-(wo-propylidene) acetylacetate. Under the same conditions, the lithium salt does not react at all. Potassium diethyl phosphite interacts with l-methyl-l-nitro-l-(4-toluylsulfonyl)propane in THF and gives diethyl 1-methyl-l-nitro-l-phosphite. The lithinm salt of the same reactant does not react with the same substrate in the same solvent. 

Methylcyclohexene, from 2-methyl-cyclohexanone tosylhydrazone and methyllithium, 51,69 Methylenecyclopropanes, 50,30 Methyl iodide, with triphenyl phosphite and cyclohexanol, 51,45 with triphenyl phosphite and neopentyl alcohol, 51,44 METHYL ftrans-2-IODO-l-TETRA-LIN)CARBAMATE, 51,112 Methyl (frans-2-iodo-l-tetralin)carba-mate, with potassium hydroxide to give 1,2,3,4-tetrahydronaph-thalene(l,2)imine, 51,53 Methyllithium, with camphor tosylhydrazone to give 2-bomene, 51, 66... 

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