Potassium diethyl phosphite

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

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. 

Commercial iodobenzene is dried over molecular sieves. Use of ratios of potassium diethyl phosphite to iodobenzene smaller than 2 1 gives lower yields. Bromobenzene is much less reactive than iodobenzene and gives poor yields by this procedure. 

Potassium diethyl phosphite Phosphorous acid, diethyl ester, potassium salt (8,9) (54058-00-3)... 

Potassium cyanide, 56, 20 Potassium diethyl phosphite, 58, 135, 138 Potassium 1,1,1,3,3,3-hexafluoro-2-phenyl-2 propanolate, 57, 22 Potassium iodide, 55, 71 Potassium permanganate, 55,68,58,47, 52 Potassium p-toluenesulfinate, 57, 8 /-Proline, iV-benzyloxycarbonyl-3-hy-droxy-, 56, 89... 

A comparison of the suitability of solvents for use in Srn 1 reactions was made in benzenoid systems46 and in heteroaromatic systems.47 The marked dependence of solvent effect on the nature of the aromatic substrate, the nucleophile, its counterion and the temperature at which the reaction is carried out, however, often make comparisons difficult. Bunnett and coworkers46 chose to study the reaction of iodoben-zene with potassium diethyl phosphite, sodium benzenethiolate, the potassium enolate of acetone, and lithium r-butylamide. From extensive data based on the reactions with K+ (EtO)2PO (an extremely reactive nucleophile in Srn 1 reactions and a relatively weak base) the solvents of choice (based on yields of diethyl phenylphosphonate, given in parentheses) were found to be liquid ammonia (96%), acetonitrile (94%), r-butyl alcohol (74%), DMSO (68%), DMF (63%), DME (56%) and DMA (53%). The powerful dipolar aprotic solvents HMPA (4%), sulfolane (20%) and NMP (10%) were found not to be suitable. A similar but more discriminating trend was found in reactions of iodobenzene with the other nucleophilic salts listed above.46 Nearly comparable suitability of liquid ammonia and DMSO have been found with other substrate/nucleophile combinations. For example, the reaction of p-iodotoluene with Ph2P (equation (14) gives 89% and 78% isolated yields (of the corresponding phosphine oxide) in liquid ammonia and DMSO respectively.4 ... 

Acceleration by KI in the substitution reaction of aryl halides with potassium diethyl phosphite or with the 2-naphthoxide ion has also been explained on the basis of an ET through the exciplex of the charge-transfer complex formed between the aryl halide and the iodide ions34a. It has also been reported that iodide ions catalysed the photostimulated reaction of bromoarenes with diethyl phosphite ion34b. 

Fig. 30 Experimental and simulated cyclic voltammograms of the electrochemical inducement of the substitution of chloride in 4-chlorobenzonitrile by potassium diethyl phosphite (0.663 M) in liquid NH at — 40°C. (Saveant, 1980)...

Ethyl 2-iodobenzoate reacts with potassium diethyl phosphite in liquid ammonia under irradiation in a Bunnett-type reaction to produce the coupling product in 64% yield (Scheme 8.41). ° ... 

Two examples serve to show the relative usefulness of the Michaelis-Becker and Michaelis-Arbuzov procedures. In the first, 540 (Z = Br) suffers debromination when heated with triethyl phosphite, and 541 was prepared only from 540 (Z = Cl) and sodium or potassium diethyl phosphite . In the second example, the formation, from 542, of the enol phosphate 543 in the Michaelis-Arbuzov case, is obviated by the use of sodium diethyl phosphite when the desired phosphonate 544 was obtained l... 

Potassium dialkyl phosphite ions react rapidly with aryl iodides in liquid ammonia under irradiation to form diethyl esters of arylphosphonic acid in almost quantitative yields238. The photostimulated reaction of (EtO)2PO ions with 5-chloro-7-iodo-8-isopropoxyquinoline gave 70% of the substitution product with retention of the 5-chloro substituent239. The same nucleophile was formed in THF, and in a mixture of solvents (1 4 THF MeCN) reacts under irradiation with ArX (o-, ra-,/ -iodoanilines, 2-iodo, 3-iodo, 2-bromo and 3-bromopyridines and 3-bromoquinoline) rendering the substitution product in high yields (70-98%) (equation 130)240. 

Texier-BouUet, F., and Foucaud, A., Reactions in heterogenous liquid-solid medium. Wittig-Homer reactions and diethyl phosphite addition on the carbonyl compounds in the presence of potassium fluoride dihydrate. Tetrahedron Lett., 21, 2161, 1980. 

Platonov, A.Y., Sivakov, A. A., Chistokletov, V.N., and Maiorova, E.D., Transformations of electrophilic reagents in a diethyl phosphite-potassium carbonate-ethanol system, Izv. Akad. Nauk, Ser. Khim., 369, 1999 Russ. Chem. Bull. (Engl. Transl.), 367, 1999. 

Villemin, D., and Racha, R., Anionic activation of diethyl phosphite by potassium fluoride. Tetrahedron Lett., 27, 1789, 1986. 

Anthrylphosphonic add 167 Anthracene (53.6 g, 0.3 mole), diethyl phosphite (170 ml, 1.33 moles), and di-/er/-butyl peroxide (30.1 ml, 0.168 mole) are heated for 4 h at 150°, whereafter much (120 ml) of the diethyl phosphite is recovered by distillation in a vacuum. The residue is treated with water (200 ml), collected, washed with water, and, for hydrolysis, heated under reflux for 72 h with a mixture of ethanol (500 ml) and concentrated hydrochloric acid (150 ml). The resulting solution is evaporated and the solid residue is heated with 5% aqueous potassium hydroxide (500 ml). Filtration and acidification then precipitate a yellow crude product (38.6 g), m.p. 279-282°, which is washed with water. For purification this product (6.5 g) is stirred with charcoal in a solution of sodium acetate (10 g) in water (100 ml) for 0.5 h at 70°. Filtration and acidification precipitate the white acid which, after drying at 120° in a vacuum, has m.p. 282-283° (dec.) (6.2 g). 

HAZARD RISK Closed containers may explode when exposed to heat or flame finely dispersed particles form explosive mixtures in air forms explosive mixtures with diethyl phosphite and potassium hydroxide exothermic decomposition emits toxic fumes of carbon monoxide, carbon dioxide and nitrogen oxides NFPA Code H 3 F 1 R 0. 

Head-to-tail dimerization of nitrile imine 60, formed in the reaction of A -(4-nitrophenyl)furan-2-carbohydrazonoyl chloride 59 with triethylamine <2001JCCS693> or with diethyl phosphite in the presence of potassium carbonate <2006PS683>, afforded tetrazine 61 (Scheme 14). 

Alkylation of Phosphorus Derivatives. The formation of diethyl phosphite anions has been achieved successfully with KHMDS and LiHMDS. The following reaction with acid chlorides is strongly influenced by the counter-ion, as only the rearrangement product was observed with the lithium base, whereas the desired hydroxybisphosphate was the major product when using the potassium base (eq 48). 

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 ... 

Khachatryan. R.A., Ovsepyan, S.A., and Indz.hikyan, M.G., Synthesis of 2-propenyl- and 2-propynyl-phosphonates from diethyl hydrogen phosphite and potassium carbonate, Zh. Obshch. Khim., 57, 1709, 1987 . 1. Gen. Chem. USSR (Engl. Transl.), 57, 1524, 1987. 

Amino-l-nitro-l,2,4-triazole (581), obtained by nitration of 5-amino-triazole with acetyl nitrate, rearranges, on heating, to the nitramino-triazole (582). ° The combined action of sodium hydroxide, potassium iodide, tri-ethylamine, and sodium dihydrogen phosphite on the chloro-nitro-triazole (583) results in a mixture of the rearranged triazole (584), 3-chloro-l,2,4-triazole, and the coupled product (585). The stable betaine (586) has been prepared by treatment of 4-phenyl-1,2,4-triazole with phenacyl bromide, followed by tri-ethylamine. The meso-ionic triazolium thiolate (537 X = S) reacts with chlorine to form the dichloride (587 X = SCU), which has been converted into the betaine (588) by the action of diethyl bromomalonate in the presence of triethylamine. ... 

C9-11 pareth-8 Diethyl sulfate Dilauryl phosphite Dimethylaminoethyl acrylate Dimethylaminopropylmethacrylamide 2,6-Dimethylmorpholine Dimethylolpropionic acid Formaldehyde Formic acid Isobutylene/isoprene copolymer Phosphorus trichloride Polyaluminum chloride Potassium oxalate Rapeseed (Brassica campestris) oil Ricinoleic acid Silicone elastomer Sodium oleth-7 phosphate Sodium oxalate Sodium PCA Synthetic wax Tallowaminopropylamine Tallow propylene diamine Triethylenemelamine ,Urea-formaldehyde resin Vinyl acetate finishing agent, textiles permanent-press fabrics Glyoxal... 

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