Phosphinic acid reactions

Phosphinic Acid Reactions. Reaction of n-butylstannoic acid with diphenylphosphate instead of a carboxylic acid also results in the formation of a drum composition [ n-BuSn(0) 02P (OPh)2] g (Chandrasekhar, V. Holmes, J. M. Day, R. 0. Holmes, R. R., unpublished work). However, when diphenylphosphinic acid is reacted with n-butylstannoic acid under reflux in toluene, a new structural form of tin is obtained (7 ). The reaction proceeds according to Equation 4 giving the stable oxide composition in 90% yield, mp 198-208°C dec. 

Hydroxy- and cpoxyalkyl-phosphonic and phosphinic acids, and related sulphur or selenium co/npou/jt/s-Conventional reactions between 1,2-propadienylphosphinic acid and substituted benzaldehydes yield [(a-hydroxybenzyl)( 1,2-propadienyl)]phosphinic acids. Reactions between (1-oxoalkyl)pho.sphonic esters and nitromethane in the pre.sence of a base (K2CO3) yield the esters (281). The compounds (282 n = 1 or 2), and (283) are obtainable conventionally from the cyclic ketone and dimethyl... 

The reaction proceeds quantitatively and the hydroiodic acid can be removed by repeated distillation at 5.3 kPa (40 mm Hg), leaving pure H2PO2 as the product. Phosphinic acid may also be prepared by the treatment of barium hypophosphite [14871-79-5] with a stoichiometric quantity of sulfuric acid to precipitate barium sulfate. 

Commercially, phosphinic acid and its salts are manufactured by treatment of white phosphoms with a boiling slurry of lime. The desired product, calcium phosphinite [7789-79-9], remains ia solution andiasoluble calcium phosphite [21056-98-4] is precipitated. Hydrogen and phosphine are also formed, the latter containing sufficient diphosphine to make it spontaneously flammable. The details of this compHcated reaction, however, are imperfectly understood. Under some conditions, equal amounts of phosphoms appear as phosphine and phosphite, and the volume of the hydrogen Hberated is nearly proportional to the hypophosphite that forms. 

The addition of P—H bonds across a carbonyl function leads to the formation of a-hydroxy-substituted phosphines. The reaction is acid-cataly2ed and appears to be quite general with complete reaction of each P—H bond if linear aUphatic aldehydes are used. Steric considerations may limit the product to primary or secondary phosphines. In the case of formaldehyde, the quaternary phosphonium salt [124-64-1] is obtained. 

Phosphonous acid diesters undergo the Arbusov reaction with a wide variety of organic halides, giving esters of secondary phosphinic acids, as is demonstrated in Eq. (88) ... 

Using other alkylated benzene hydrocarbons, e.g., amyl-, hexyl-, octyl-, or nonylbenzene, similar surface-active phosphinic acids are formed by reaction with PC13 in the presence of anhydrous aluminum trichloride. The resulting alkylarylphosphinic acids form stable salts with primary, secondary, or tertiary hydroxy amines or aromatic amines [166,171]. 

Another reaction for synthesizing phosphinic acid derivatives was described by Jungermann and coworkers [173-176], It is based on the reaction of olefins with phosphorus trichloride in the presence of a Friedel-Crafts catalyst, according to Eq. (106) ... 

Other cyclizations at phosphorus have been observed when certain phosphinates were used in the acid-catalyzed Mannich reaction. As observed previously with various phosphonous acid derivatives, reaction of aliphatic phosphinic acids with primary amines favored the formation of 2 1 adducts (73). Thus, glycine and other a-amino acids reacted under the typical conditions with excess formaldehyde and alkyl phosphonous acids to give the bis-phosphinylmethyl adducts 125. 

In a similar way to the aminolysis of the P-N bond mentioned above (Scheme 9), alcoholysis of phosphinous amides leads to the alkyl esters of the respective phosphinous acids [30, 121]. This reaction occurs with inversion of the absolute configuration of the phosphorus atom, and has been used in a synthetic sequence leading to optically active tertiary phosphanes 22 [122] (Scheme 23). 

B. Reactions.—(/) Nucleophilic Attack at Phosphorus. A reinvestigation of the reaction between phosphorus trichloride and t-butylbenzene in the presence of aluminium chloride has shown that the product after hydrolysis is the substituted phosphinic acid (11), and not the expected phosphonic acid (12). Bis(A-alkylamino)phosphines have been reported to attack chlorodiphenyl phosphine with nitrogen, in the presence of a base, to give bis-(A-alkyl-A-diphenylphosphinoamino)phenylphosphines (13). In (13), the terminal phosphorus atoms are more reactive than the central one towards sulphur and towards alkyl halides. 

B. By Hydrolysis Reactions.—Details have appeared of the synthesis of dibenzophosphorin oxides (15) from 5-alkyldibenzophospholes, by reaction with methyl propiolate in the presence of water, and of confirmatory syntheses from phosphinic acid chlorides, as shown below. Evidence for the suggested mechanism of the ring-expansion reaction is presented. The hydrolysis of enamine phosphine oxides is an efficient, although somewhat indirect, method for the preparation of j8-ketoalkylphosphine oxides (16) [see Section 3(iii), for the preparation of enamine oxides]. Reasonable yields (48—66%) of trialkylphosphine oxides (17) have been obtained by the alkaline hydrolysis of the products from the pyrolysis at 220 °C of red phosphorus with alkyl halides, in the presence of iodine. 

C. By Oxidation.—This year s literature has been notable for attempts to study the details of certain phosphine oxidation reactions. In one such investigation nitric acid was found to oxidize phosphines, or phosphine sulphides, to phosphine oxides with inversion of configuration at phosphorus, whereas dinitrogen tetroxide, in the absence of acid, was found to oxidize the same compounds with predominant retention. The partial racemization observed with the latter reagent was probably due to the racemization of the oxides, since methylphenyl-n-propylphosphine oxide... 

C. Reactions of Phosphoric and Phosphinic Acid Derivatives.—The optically active phosphinate ester (90) has been shown to react with benzyl Grignard reagents or lithium anilide with inversion of configuration. Oxidation of... 

The deoxygenation of peroxycarbonates (53) with phosphines and phosphites has been examined. Reaction with phosphites favours pyrocarbonate formation (Path A) whilst phosphines favour carbonate formation (Path B). Secondary phosphine oxides are oxidized to phosphinic acids by perbenzoic acid. The kinetics of the deoxygenation of hydroperoxides by triphenylphosphine have been examined and the reaction shown to be catalysed by strong acids. ... 

A differential vapour-pressure technique has been used to determine the molecular weights of phosphonic and phosphinic acids in 95% ethanol. Cryoscopic and n.m.r. studies have been made on solutions of phosphinic acids in sulphuric acid and oleum. Mass spectrometry has indicated the ready formation of phosphinylium ions after electron bombardment of phosphonic and phosphinic acids and their derivatives. However, the cryoscopic results in sulphuric acid indicated that reaction did not proceed beyond protonation, and the n.m.r. study on oleum solutions suggested that sulphonation occurred. 

The regioselectivity of these reactions was reversed (the Markovnikov product was now favored) simply by the addition of a catalytic amount of phosphinic acid (Scheme 5-23, Eq. (1) compare Scheme 5-21) [18]. 

Trimethylsilylacetylene is an exception, giving the anti-Markovnikov product. Internal alkynes also underwent the reaction, as observed without phosphinic acid (Scheme 5-23, Eq. 2). 

Scheme5-24 Eq. (1) Proposed mechanism for Eq. (2) Stoichiometric reactions relevant to the phosphinic acid-modified palladium-catalyzed proposed mechanism hydrophosphinylation of alkynes.

Reactions and Properties of Phosphonic and Phosphinic Acids and their Derivatives.-A free radical mechanism has been proposed to account for the cleavage of the phosphorus-carbon bond in the alkylphosphonic acids (155) by E coli to give a mixture of alkane (methane only, from methylphosphonic acid) and terminal alkene. 

A palladium catalyst with a less electron-rich ligand, 2,2-dipyridyl-methylamine-based palladium complexes (4.2), is effective for coupling of aryl iodides or bromides with terminal alkynes in the presence of pyrrolidine and tetrabutylammonium acetate (TBAB) at 100°C in water.37 However, the reactions were shown to be faster in NMP solvent than in water under the reaction conditions. Palladium-phosphinous acid (POPd) was also reported as an effective catalyst for the Sonogashira cross-coupling reaction of aryl alkynes with aryl iodides, bromides, or chlorides in water (Eq. 4.18).38... 

A reaction of the first type, in a broad sense, uses the mixture obtained from n-BuLi and the phosphinic acid (mes)2P(H)=0 (mes = 2,4,6-trimethylphenyl) in thf/hexane to which the Cd amide Cd[N(SiMe3)2]2 is added a mixed amide-phosphinite is obtained, namely [ MeSi)2N Cd (mes)2PO 2Li-2 thf]. The structure analysis (153 K) reveals that the two phosphinite ligands act as a double bridge between Cd and Li to give a six-membered, twisted ring with two independent Cd—P bonds (rav(Cd—P) 259.4 pm) the exocyclic Cd—N bond is rather short (213.6 pm).226... 

In contrast to the situation on flash pyrolysis, methyleneoxophosphoranes generated by thermolysis or photolysis in the presence of protic nucleophiles can be directly trapped to form corresponding derivatives of phosphinic acid (17- 19) however, the possibility of competing insertion of carbenes into the H/X bond of the additives is always present, giving phosphine oxides with X in the a-position (16- 18). Reaction branching at the carbene 16 was first observed on photolysis of 7 in water 13) and prompted detailed investigations on the phosphorylcarbene/ methyleneoxophosphorane rearrangement. 

The generated palladium chlorides possessing phosphinous acid ligands were found to be remarkably active and efficient catalysts in the presence of bases for a variety of cross-coupling reactions of aryl halides with aiylboronic... 

The reaction of dialkyl esters of 1,2-alkadienylphosphonic and phosphinic acids with methyl and phenylsulphenyl chloride, leads exclusively to 2,5-dihydro-l,2-oxaphosphole-2-oxide derivatives [113-115],... 

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