Esterification Of Phosphinic Acids Research Articles

Novel One-pot Syntheses for Oligo-phosphonic and Phosphinic-Acid Esters

Abstract Sodium salts of phosphorous acid dialkyl esters or alkane phosphonous acid monoalkylesters react with chlorinated olefines and acetylenes to form tris- and tetrakis-phosphonic or phosphinic acid esters in good yields. Corresponding acids are obtained from esters by cleavage with HCl. Reaction mechanisms and molecular structures are investigated by 1D and 2D NMR studies.

PHOSPHORORGANISCHE VERBINDUNGEN 981CYANOPHOSPHINOYLIERUNG VON CARBONYLGRUPPEN—EIN ANALOGON ZU CYANOSILYLIERUNG

Abstract The carbonyl groups of saturated and unsaturated aliphatic and aromatic aldehydes and ketones add diphenylphosphinic acid nitrile and dimethylphosphinic acid nitrile according to (1) and (2) forming O-(phosphinoyl) cyanohydrins. O-(diphenylphosphinoyl) acrolein cyanohydrin isomerizes according to (3) to (2-diphenylphosphinoyloxy)-but-2-en-nitrile following a shift of the double bond (a) at 200°C or (b) on interaction with KOBut. Aminonitriles are formed according to (4) by a modified Strecker reaction on reacting O-(diphenylphosphinoyl) aldehyde (ketone) cyanohydrins with secondary amines. The anionic form of O-(diphenylphosphinoyl) aldehyde cyanohydrins reacts (a) with alkyl halides forming O-(diphenylphosphinoyl) ketone cyanohydrins (5) and (b) with aldehydes (6) to yield O-(diphenylphosphinoyl) acyloins after a transacylation. Phosphinic acid esters are cleaved quantitatively by fluorolysis using tetrabutylammonium fluoride at room temperature (7). Diphenylphosphinsaurecyanid und Dimethylphosp...

(O-n-butyl-p-phenyl-phosphonito-p)-mercury complexes

Phosphonito-mercury compounds C 6H 5(n- C 4H 9O)PHgX, (X = C 6H 5(n-C 4H 9O)P(O), Cl, Br, I, CN, C 6H 5, OAc, O 3SCF 3, SCN, SC 6H 5, SC 2H 5 and 2,5-pyrrolidindionato-N) were prepared from the corresponding phosphinic acid ester with HgO or with HgO and HgX 2. The new compounds are characterized by a HgP bond and decompose easily with fission of this bond. δ( 31P), δ( 199Hg) and 1J( 31P- 199Hg) data are reported.

Rhodium phosphine complexes as homogeneous catalysts. 7. Effect of phosphine structure on catalytic activity in acetone hydrogenation

The activity of catalysts for acetone hydrogenation formed in situ from [Rh(norbornadiene)Cl]2 and phosphines or phosphinic acid esters is determined by the electronic and steric effects of the ligand. The electronic parameter used was the infrared νco value of Rh(PR3)2(CO)Cl complexes containing the same P(III)-ligands. Catalytic activity increases with decreasing νco (i.e., increasing basicity of the ligand) and reaches its highest level with PEt3. Phosphines with larger, or branched, alkyl groups show still lower νco values but yield catalysts of lower, or even zero, activity because of the steric effects of the bulky ligands.

Spontaneous Alternating Copolymerization via Zwitterion Intermediates

AbstractThis article describes a new concept of copolymerization which occurs spontaneously without any added catalyst. A nucleophilic monomer (MN) combines with an electrophilic one (ME) to generate a zwitterion [+]MN—M, which is responsible for the initiation and propagation of copolymerization. Twenty‐three novel copolymerizations have been explored on the basis of the new concept. MN monomers which have been investigated are five‐ and six‐membered cyclic imino ethers, dihydro‐2(3H)‐furanimine, an azetidine, a cyclic phosphinic acid ester and a Schiff base; the ME monomers include β‐propiolactone, a cyclic dicarboxylic acid anhydride, a sultone, acrylic acid, acrylamide, a β‐hydroxyalkyl acrylate and ethylenesulfonamide. In most combinations, alternating 1 : 1 copolymers were produced. In addition to the above‐mentioned combinations, the alternating 1 : 1 copolymerization of cyclic phosphite with α‐keto acid was discovered.

Organische Phosphorverbindungen 44 Darstellung und Eigenschaften von Bis‐(ß‐chloräthyl)‐phosphinsäure‐Derivaten [1

AbstractReaction of ClCH2CH2PCl2 with ethylene oxide gives the phosphonous acid ester ClCH2CH2P (OCH2CH2Cl)2 which on heating to 120° rearranges to the phosphinic acid ester (ClCH2CH2)2P(O)OCH2CH2Cl (3). Chlorination of 3 with PCl5 in CCl4‐solution yields the phosphinic chloride (ClCH2CH2)P(O)Cl (4), which on treatment with P2S5 at 170° produces the thioderivative, (ClCH2CH2)2P(S)Cl, (5). Treatment of 4 and 5 with alcohols, mercaptanes, or amines in the presence of an acid binding agent leads to the corresponding phosphinic and thiophosphinic acid derivatives, (ClCH2CH2) P (X)Y, (X = O, S; Y = OR, SR, NR2) (6). Reaction of 6 with excess base yields the corresponding divinylphosphinic and divinylthiophosphinic acid derivatives (CH2 = CH)2P (X) Y (X = O, S; Y = OR, SR, NR2) (7).Bis‐(ß‐chloroethyl)‐phosphinates, e. g. (ClCH2CH2)2P (O) OEt, undergo a Michaelis‐Arbuzov reaction when heated with phosphites to 160–170° to give bis‐(phosphonylethyl)‐phosphinates, e.g. (EtO) (O)P[CH2CH2CH2P(O)(OEt)2]2 (8), which on hydrolysis with conc. HCl under reflux yield the corresponding acid HO2P(CH2CH2PO3H2)2.

Configuration of 1-oxo-1-ethoxy-1-phosphacyclopent-3-ene

1. By studying the IR spectra of 1-oxo-1-alkoxy-1-phosphacyclopent-3-enes, it was shown that they lack the isomeric equilibrium characteristic of acyclic phosphinic acid esters. 2. By comparing the experimental dipole moments of 1-oxo-1-ethoxy-1-phosphacyclopent-3-ene with the moments of possible configurations which were calculated from a vector diagram, a choice was made in favor of the cis arrangement of the alkoxy group with respect to the phosphoryl.

Alkylierung von merkaptanen mit alkylestern von säuren des phosphors

Mercaptans and alkyl esters of acids of phosphorus react at elevated temperatures to give alkyl aryl sulfides and the corresponding acids of phosphorus. Differences in reactivity within a series of five mercaptans and thirteen phosphoric, thiol- and thionphosphoric, phosphonic, and phosphinic acid esters have been investigated, side reactions are discussed.

Synthesis of ?-ketophosphine oxides

The preparation of some 3-ketophosphine oxides by the reaction of a phosphinic acid ester withα-halosubstituted ketones was described.

New method for synthesis of phosphinic and thiophosphinic acid esters Part II. Addition of dialkylphosphorus acids to the amide and esters of methacrylic acid

1. Dialkylphosphorous acids add on to methacrylamide, to give dialkylphosphoneisobutyramides. 2. The products of addition of higher dialkylphosphorous acids to methyl methacrylate, and of diethylphosphorous acid to alkyl methacrylates are described.