Phenyl Phosphonous Dichloride

Phosphonium, (carboxymelhyl)triphenyl-, bromide, ethyl ester, 70, 246 Phosphonous dichloride, phenyl- (644-97-3), 70, 273 Phthalimide, N-(3-bromopropyl)-, 70. 195 Piperidine, 2-methyl- (109-05-7), 70, 265 Pirkle Type 1-A column, 70, 64... 

Chemical Designations - Synonyms Phenyl Phosphonous Dichloride, Phenylphosphine Dichloride, Dichlorophenylphosphine Chemical Formula CjHjPClj. 

It is interesting to note that [(E)-2-phenylethenyl]-[018]phosphonic dichloride (116) upon treatment with (-)-ephedrine (42) in the presence of triethylamine afforded an equimolar mixture of (2S,4S,5R)- and (2/ ,4S, 5/ )-2,3-dimethyl-5-phenyl-2-[(E)-2-phenylethenyl]-l,3,2-oxazaphospholidin-2-[180]one 117a and 117b. The two diastereomers were completely separated by flash chromatography and the diastereomer 117b was hydrolyzed with water H20-170 to the corresponding monoester 118 which was finally converted to dihydro-(l,2-dibromo-2-phenyl- 1-ethyl) (R)-160,170,180 phosphonic acid 119 (Scheme 33) [66],... 

The reaction of 2-deoxy-3,4,6-tri-0-methyl-2-methylamino-D-glucopyranose 149 with methyl(phenyl)phosphonic dichlorides (106a-b) or methylthiophosphonic dichloride in benzene in the presence of triethylamine afforded mixtures of four isomers of the corresponding 1,3,2 oxazaphospholidine-2-ones 150, 151 and... 

Preparation of Phosphorus Containing Terpolymers. Prepared by substitution of a portion of the acid chloride mixture by a calculated amount of phenyl phosphonic dichloride. The compositions of these polymers are summarized in Table 1. 

Phenylhydrazine Hydrochloride Phenylhydrazinium Chloride Phenyl Hydroxide Phenylmethanol Phenylmethyl Alcohol Phenylmethyl Amine Phenylphosphine Dichloride Phenylphosphine Thiodichloride Phenylphosphonothioic Dichloride Phenyl Phosphonous Dichloride Phenylpropylene 1 -Phenyltetradecane 1-Phenylundecane Phosgene Phosphoric Acid Phosphoric Sulfide... 

Phosphonic acid, phenyl-, diethyl ester [1754-49-0], 58,134, 137 Phosphonic dichloride, piperidino- [ 1498-56-2], 58, 137,138... 

The reaction of chloromethylphosphonic dichloride with tetra-phosphorus decasulfide or with thiophosphoryl chloride are the only methods of preparation for this compound reported. The method is applicable more generally, and the syntheses of methyl-, trichloromethyl-, ethyl-, propyl-, cyclohexyl-, phenyl-, and -chlorophenylphosphonothioic dichloride from the corresponding phosphonic dichlorides have been reported. Phos-phinic chlorides of varying structures could also be converted to the corresponding thiono compounds by comparable procedures. The present method is preferable to the thiophosphoryl chloride procedure in that it does not require working under pressure. 

Phosphorus oxychloride, which forms stable and often insoluble complexes with Friedel-Crafts catalysts, appears not yet to have been used with success in reactions of this type. The analogous reaction of thiophosphoryl chloride has been studied in detail, but only recently 158 its use has made phenyl(thio-phosphonic) dichloride, diphenyl(thiophosphinic) chloride, and triphenyl-phosphine sulfide conveniently accessible. The dichloride is obtained in about 45% yield, together with about 33% of the monochloride, when a mixture in the molar proportions PSC13 A1C13 C6H6 = 1 2 1 is heated at 80° for 15 min the ratios 1 2 4 are most favorable for preparation of the mono-... 

In fact, the Grignard reagent of 2-bromopyridine converted phenyl-phosphonous dichloride to bis(2-pyridyl)phenylphosphine (2) (140). An important step in the synthesis of 9-phenyl-9-phosphafluorene 9-oxide (4, R = H) involved reaction of the Grignard compound of 3 with phenylphosphonous dichloride (28,30). It was possible to effect... 

The procedure involves reaction in acetic anhydride, or in another solvent, followed by the addition of acetic anhydride to decompose the intermediate complex. The procedure has been extensively examined in relation to the 5-methyl- and 4,5-dimethyl-substituted compounds derived from ethenyl methyl and methyl isopropenyl ketones and with mesityl oxide which gives the 3,3,5-trimethyl-substituted compounds. Amongest the phosphorus reactants, the trichloride itself and methyl- " , ethyl- " " and phenyl- phosphonous dichlorides have been employed, as have ethyl and phenyP dichlorophosphites, ROPCI2. The use of 2-thienylphosphonous dichloride to give 137 is recorded as is that of the unsaturated ketone 138 to give 139. A more novel conversion is that of 140 into 141 in 25% yield with a similar conversion (15%) being observed for cholest-4-en-3-one. ... 

Few synthetic reactions are available for the direct formation of derivatives of phosphonic and phosphinic acids which possess a P—C(sp) bond. The phosphonylation of an alk-1-yne by PCI5 does not provide the alk-l-ynephosphonic derivative directly but, in analogy to the procedure for alkenes, the product retains chlorine. Thus phenylethyne with PCI5 affords a complex which, when decomposed by SO2, gives a high yield of (2-chloro-2-phenylethenyl)phosphonic dichloride The conversion of this into (2-phenyl-ethynyl)phosphonic dichloride represents a modification synthesis of a type to be discussed later in this chapter (Section VI.D). 

To a stirred solution of 105 g (0.396 mole) of [phenyl(tri-methylsilyl)methyl]phosphonous dichloride in 2-2.5 L of diethyl ether in a 4-L flask, 178 g (1.584 moles) of l,4-diazabicyclo[2.2.2]octane (DBO) is added. The mixture is stirred overnight at ambient temperature and then filtered. The solid is washed three times with 100-mL portions of pentane. The collected filtrates are concentrated to 1.5 L at ambient temperature under reduced pressure, and the base and its hydrochloride are separated by filtration. The solid is washed three times with 50-mL portions of pentane. This procedure (concentration and... 

A 1,4-dilithio system was used in the synthesis of the first phosphindole <67JA5732>. n-Butyllithium added to diphenylethyne to give the dilithium derivative (235), which was then treated with phenyl-phosphonous dichloride to form crystalline 3-n-butyl-l,2-diphenylphosphindole (236) in 40% yield (Scheme 63). This method remains of value, and has been employed by later workers to prepare the phosphindole as a model in other studies <7UA6205,76JHC65). 

When aluminium trichloride is dissolved in water, the complete replacement of chloride by water molecules with additional coordination of water molecules takes place and polynuclear hydrated is finally found in its solution. Intermediate species, such as [AlClJfoiv., can be detected in phosphorus oxychloride or in phenyl phosphonic dichloride jn the presence of antimony(V) chloride or ferric chloride . Other chloronium ions are formed in solvents of moderate donor number in the presence of a suitable acceptor . 

Such reactions have been followed in phosphorus oxychloride and phenyl-phosphonic dichloride in the presence of chloride ion acceptors such as ferric chloride or antimony(V) chloride. Only the tetrahedral PCU+dons are non-solvated, but all other chloronium ions seem to be solvated by at least one solvent molecule 62... 

Benzene Phosphorous Dichloride — (i) Chemical Designations — Synonyms Phenyl Phosphonous Dichloride, Phenylphosphine Dichloride, Dichlorophenyl-phosphine Chemical Formula CsHjPClj (ii) Observable Characteristics — Physical State (as normally shipped) Liquid Color Colorless Odor Acrid and pungent (iii) Physical and Chemical Properties — Physical State at 15 C and I atm. Liquid Molecular Weight 179.0 Boiling Point at I atm. 430, 221, 494 Freezing Point -60, -51, 222 Critical Temperature Not pertinent Critical Pressure Not pertinent Specific Gravity 1.140 at 25 °C... 

Figure 1. Infrared spectra of the condensation product of phenyl-phosphonic dichloride and ditriethylamine terephthalate.

Recently, phase transfer catalysis has been effectively exploited in the field of synthetic organic chemistry.However, there are scant reports on the syntheses of condensation polymers by phase transfer methods. Five years ago, we started a broad investigation into the use of phase transfer catalysis (PTC) to effect polycondensation. Since then, we have successfully synthesized various types of condensation polymers with high molecular weights. For example, aromatic polysulfonate ni from aromatic disulfonyl chloride I and bisphenol II [Eq.(l)], / aromatic polyphosphonate V from phenyl-phosphonic dichloride IV and II [Eq.(2)], and aromatic polyether VII from activated aromatic dichloride VI and II [Eq.(3)]. ... 

Preparation of poly(m-phenylene)phenyl phosphonate. These polymers were prepared by the method of Toy using resorcinol and phenylphosphoric dichloride (11). 

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