Phosphorus trichloride preparation

Preparation of 4-cyanophenylzinc bromide by transmetallation and its reaction with phosphorus trichloride preparation of tris (4-cyanophenyl)phosphine-borane complex8... 

Pure phosphine can be prepared by the reduction of a solution of phosphorus trichloride in dry ether with lithium aluminium hydride ... 

Phosphonic acid, H3PO3, often called just phosphorous acid , is prepared by the hydrolysis of phosphorus trichloride a stream of air containing phosphorus trichloride vapour is passed into ice-cold water, and crystals of the solid acid separate ... 

Phosphorus pentachloride is prepared by the action of chlorine on phosphorus trichloride. To push the equilibrium over to the right, the temperature must be kept low and excess chlorine must be present. Hence the liquid phosphorus trichloride is run dropwise into a flask cooled in ice through which a steady stream of dry chlorine is passed the solid pentachloride deposits at the bottom of the flask. 

The following preparation of triethyl phosphite illustrates the interaction of phosphorus trichloride and ethanol in the presence of dimethylaniline the preparation of di-isopropyl hydrogen phosphite illustrates that of phosphorus trichloride and isopropanol in the absence of a tertiary amine. 

Organophosphorus Derivatives. Neopentyl glycol treated with pyridine and phosphorus trichloride in anhydrous dioxane yields the cycHc hydrogen phosphite, 5,5-dimethyl-l,3-dioxaphosphorinane 2-oxide (2) (32,33). Compounds of this type maybe useful as flameproofing plasticizers, stabilizers, synthetic lubricants, oil additives, pesticides, or intermediates for the preparation of other organophosphoms compounds (see Flame retardants Phosphorus compounds). 

Amino-pyridazines and -pyridazinones react with monomethyl- or iV,A-dimethyl-formamide and other aliphatic amides in the presence of phosphorus trichloride, thionyl chloride, phosgene or benzenesuUonyl chloride to give mono- or di-alkylaminomethyl-eneamino derivatives. The same compounds can be prepared conveniently with A,iV-dimethylformamide dimethyl acetal in high yield (Scheme 50). 

Salicyl-u-toluide has been prepared only by the action of phosphorus oxychloride upon a mixture of salicylic acid and o-toluidine. The useful methods of preparation of salicylanilide are by the interaction of salicylic acid and aniline in the presence of phosphorus trichloride, by heating phenyl salicylate and aniline, and from o-hydroxybenzamide and bromobenzene in the presence of small amounts of sodium acetate and metallic copper. A number of these and other anilides have been described. ... 

Bischloromethyl ether has been prepared by saturation of formalin with dry hydrogen chloride by the reaction of paraformaldehyde with phosphorus trichloride or phosphorus oxychloride, by solution of paraformaldehyde in concentrated sulfuric acid and treatment with ammonium chloride or dry hydrogen chloride, and by suspension of paraformaldehyde in seventy or eighty percent sulfuric acid and treatment with chlorosulfonic acid. It is formed together with the asymmetrical isomer when methyl ether is chlorinated and when paraformaldehyde is treated with chlorosulfonic acid. The present method has been published. ... 

These formulae explain the scission products of the two alkaloids and the conversion of evodiamine into rutaecarpine, and were accepted by Asahina. A partial synthesis of rutaecarpine was effected by Asahina, Irie and Ohta, who prepared the o-nitrobenzoyl derivative of 3-)3-amino-ethylindole-2-carboxylic acid, and reduced this to the corresponding amine (partial formula I), which on warming with phosphorus oxychloride in carbon tetrachloride solution furnished rutaecarpine. This synthesis was completed in 1928 by the same authors by the preparation of 3-)S-amino-ethylindole-2-carboxylic acid by the action of alcoholic potassium hydroxide on 2-keto-2 3 4 5-tetrahydro-3-carboline. An equally simple synthesis was effected almost simultaneously by Asahina, Manske and Robinson, who condensed methyl anthranilate with 2-keto-2 3 4 5-tetrahydro-3-carboline (for notation, see p. 492) by the use of phosphorus trichloride (see partial formulae II). Ohta has also synthesised rutaecarpine by heating a mixture of 2-keto-2 3 4 5-tetrahydrocarboline with isatoic anhydride at 195° for 20 minutes. 

The difficulties encountered in the synthesis of 2-alkyl- and 2-aryl-substituted selenazoles lie principally in the preparation of the corresponding selenoamides. In this respect, a method is worthy of note in which the use of selenoamides is dispensed with. For this, a nitrile, a hydrogen selenide, and an a-halogenoketone are reacted together in the presence of a condensation catalyst. Phosphorus oxychloride, alone or mixed with zinc chloride or phosphorus trichloride, is specially suitable. The yields of the corresponding 2-alkylseIenazoles are up to a maximum of 25%,... 

Preparation of Intermediate Compound 2-Methyl-3-o-Tolyl-6-Sulfamyl-7-Chloro-4(3H)-Quinazoiinone Set up a 5-liter 3-necked flask fitted with a stirrer, condenser and a drying tube. To a stirred mixture of 100 g (0.342 mol) of powdered 4-chloro-5-sulfamyl-N-acetylanthranilic acid, 40.2 g (0.376 mol) of o-toluidine and 2.0 liters of dry toluene was added dropwise, over a period of 15 minutes, 21.7 ml (34.1 g) (0.248 mol) of phosphorus trichloride. The mixture was then refluxed for 10 hours. The solid turned somewhat gummy towards the latter part of the first hour. The mixture then became more free flowing as heating was continued. Let stand overnight. The yellow solid was filtered, washed with toluene and dried. The toluene filtrate was discarded. The dried solid was triturated with 1.5 liters of 10% sodium bicarbonate, filtered and the cake washed with water. The filtrate on acidification yielded 11.5 g of the starting acid. The damp product was dissolved in 4,5 liters of 95% ethanol and the solution treated with charcoal and filtered. On cooling filtrate yielded 69.5 g (55.5%) of the title compound, MP 271.5° to 274°C. 

There are many methods for the preparation of ethane-1-hydroxy-1,1-diphosphonic acid including reacting phosphorus trichloride and acetic acid in the presence of tributylamine [106], phosphorus with acetic acid and oxygen [108], acetic anhydride with phosphorous acid and acetyl chloride [80,84-86,109,110], and acetic anhydride with phosphoric acid and acetic acid [111]. By another method ketene and phosphorous acid can be used [112], as shown in Eq. (68) ... 

Phosphorus trichloride, PCI, and phosphorus pentachloride, PC15, are the two most important halides of phosphorus. The former is prepared by direct chlorination... 

A comprehensive review of the preparation, reactions, and n.m.r. spectra of phosphorus-fluorine compounds has appeared. This year s literature has been notable for the first detailed applications of ab initio SCF-MO calculations to the problems of bonding in halogenophosphines and their derivatives. - Comparison of the results of such theoretical calculations with experimental data obtained from photoelectron spectra shows a good correlation in the case of phosphorus trichloride and phosphoryl chloride, and of phosphorus trifluoride and its borane complex. ... 

Equations 2, 3, and 4 summarize the method proposed by the Germans for preparing parathion (compound E-605). Schrader 13) has reported that thiophosphoryl chloride was synthesized from phosphorus trichloride and sulfur by heating at 130° in a lead-lined autoclave. Woodstock and Adler 14) carried out a similar reaction at 150° to 160° C. 

Chatt, J. et al., J. Chem. Soc., Dalton Trans., 1985, 1131-1136 A modified method of preparation from ethylene, phosphorus trichloride and phosphorus in a stainless autoclave gives a highly pyrophoric reaction residue. 

Banks, R. E. et al., J. Chem. Soc., Perkin Trans. 1, 1974, 2535-2536 During an increased-scale preparation of the dioxyl by permanganate oxidation of the hydrolysate of a nitrosotrifluoromethane-tetrafluoroethylene-phosphorus trichloride adduct, an impurity in the dioxyl, trapped out at — 96°C ( — 196°C) and <2.5 mbar, caused a violent explosion to occur when the trap content was allowed to warm up. A procedure to eliminate the hazard is detailed. 

Moller, T. et al., Inorg. Synth, 1954, 4, 72 During the preparation from phosphorus trichloride and sulfur, the quantity and quality of the aluminium chloride catalyst is critical to prevent the exothermic reaction going out of control. 

In the preparation of triphenylphosphine from chlorobenzene, phosphorus trichloride and sodium dispersed in toluene or xylene, the possibility of explosion is avoided by adding about 1 mol% of a lower alcohol, based on sodium usage. 

Both yellow and red phosphorus ignite on contact with fluorine and chlorine red ignites in liquid bromine or in a heptane solution of chlorine at 0°C. Yellow phosphorus explodes in liquid bromine or chlorine, and ignites in contact with bromine vapour or solid iodine [1]. Interaction of bromine and white phosphorus in carbon disulfide gives a slimy by-product which explodes violently on heating [2], Interaction of phosphorus and iodine in carbon disulfide is rather rapid [3], A less hazardous preparation of diphosphorus tetraiodide from phosphorus trichloride and potassium iodide in ether is recommended [4],... 

Heterocyclic phosphines 32 were prepared from base-induced condensation of a secondary 1,8-diamino-naphthalene with phosphorus trichloride (the corresponding As- and Sb-analogues were obtained analogously) and converted into cyclic phosphenium cations 33 by Lewis acid promoted halide abstraction using GaCl3 or trimethylsilyl triflate as reagents (Scheme 18) [15, 92],... 

Chloro-1,3,2-oxazaphospholanc (chlorophosphoramidite) 43 derived from (IR, 25)-(-)-cphedrine 42 was prepared for the first time as early as 1977 by its reaction with phosphorus trichloride (Scheme 15) [32, 33], Later, similar procedures were reported for its isolation as a single epimer which, on the basis of spectroscopic and derivatisation studies, has been assigned configuration [34-36],... 

A series of 2-chloro-l,3,2-oxazaphospholidine derivatives 131a-f were prepared by reaction of six enantio-pure alcohols 129a-f with phosphorus trichloride carried out in the presence of an organic base as HC1 scavenger (Scheme 38) [69], The 31P and II-NMR spectra of crude 131a, d, e containing a small amount of the HC1 salt produced during the synthesis of 131, as well as the distilled samples, indicated that the formed chloro derivatives were ca. 1 1 mixtures of the cis and trans isomers. 

A number of P-chirogenic diaminophosphine oxides (DIAPHOXs) 275 derived from aspartic acid were prepared via hydrolysis of triaminophosphine intermediate 274, generated in a fully diastereoselective reaction of triamines 273 with phosphorus trichloride (Scheme 65) [102, 103],... 

Another alternate synthetic method for the manufacturing of niclosamide is reported [1], Phosphorus trichloride (PC13) is slowly introduced into a boiling xylene solution containing 5-chlorosalicylic acid and 2-chloro-4-nitroaniline in equimolar ratio and the heating continued for 3 h. Crystals of niclosamide separate on cooling and are recrystallized from ethanol [7,8], van Tonder et al. [9] prepared and characterized three crystal forms of niclosamide namely the anhydrate and the two monohydrates. 

Oleoyl chloride has been prepared by treatment of oleic acid with thionyl chloride,3 phosphorus trichloride or pentachloride, and oxalyl chloride.4 The highest yield (86%) reported was secured by use of oxalyl chloride in carbon tetrachloride, but the more economical phosphorus trichloride gave a yield of 60%. The standard procedures for obtaining aliphatic acid chlorides have been described many times without inclusion of details other than physical properties. Only references to the procedures useful in the laboratory are given. 

Preparation of vinyldichlorophosphine — Reaction of phosphorus trichloride with an organomercury compound... 

Preparation of 6-amino-l-hydroxyhexylidenediphosphonic acid — Reaction of a carboxylic acid with phosphorous acid and phosphorus trichloride... 

Van Hooijdonk, M.C.J.M., Gerritsen, G., and Brandsma, L., Preparation of primary and secondary alkyl phosphines from elemental phosphorus or phosphorus trichloride in organic solvents, Phosph., Sulf, Silic. Relat. Elem., 162, 39, 2000. 

These materials, generally prepared from the corresponding Grignard reagents by the addition of cadmium chloride, provide a milder reagent system than the Grignard that allows selectivity in reaction with phosphorus trichloride (Equation 4.21).34-43-63... 

Acetals have been used in the presence of Lewis acids, particularly zinc chloride and ferric chloride, for the addition of phosphorus-halogen species to prepare 1-alkoxyphosphonic dichlorides and dialkyl 1-alkoxyphosphonates (from phosphorus trichloride and dialkyl phosphinous chlorides, respectively).143-145 It should be noted that good yields of these types of products have also been reported in the absence of catalysts.146 147 Other types of substrates have also been used in these types of processes. These include acylals,148 amidals,149 orthoformates,150 and orthoacetates.151... 

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