Phosphorus trichloride chloride

Here again the simple formulation [Sb ] is used to represent all the cationic species present.) The hydrolysis is reversible and the precipitate dissolves in hydrochloric acid and the trichloride is reformed. This reaction is in sharp contrast to the reactions of phosphorus(III) chloride. 

Phosphorus trichloride reacts readily with three equivalents of an alcohol e.g, ethanol, in the presence of a tertiary amine such as pyridine, dimethyl-aniline, or diethylaniline, to form triethyl phosphite and hydrogen chloride, the latter being immediately neutralised by the tertiary amine. 

Place 38 ml. of isopropanol in a two-necked 500 ml. round-bottomed flask fitted with (a) a reflux water-condenser having a calcium chloride tube at the top, and (b) a dropping-funnel. Cool the flask in ice-water and then run 13 5 ml. of phosphorus trichloride in from the dropping-funnel during 15 minutes. Then allow the reaction-mixture to attain room temperature. Now replace the condenser and the... 

Method 1. Use the apparatus depicted iu Fig. Ill, 56, 1, but omit the thermometer also attach a cotton wool (or calcium chloride) tube to the side arm of the filter fiask receiver in order to prevent the entrance of moisture into the apparatus. Mount the reaction fiask in a water bath e.g., a large beaker or other convenient vessel). It is important that all the apparatus be perfectly dry, since both phosphorus trichloride and acetyl chloride are decomposed by water. The set-up should be assembled in the fume eupboard. 

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). 

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. ... 

Jsomerides of Morphine and Codeine. When morphine is treated with thionyl chloride, phosphorus trichloride or tribromide, the alcoholic hydroxyl group is replaced by the halogen, forming a-chloromorphide and bromomorphide respectively. The former on treatment with concentrated hydrochloric acid is converted into /3-chloromorphide. Schopf and Hirsch have provided evidence that the two are structural isomerides. With the same reagents codeine yields a parallel set of compounds, viz., a- and -chlorocodides, and bromocodide. The chief characteristics of these products may be summarised thus —... 

Compare geometries, atomic charges and electrostatic potential maps of thionyl chloride and phosphorus trichloride. How are they similar How are they different Can you redraw the Lewis structure of SOCI2 so that it gives abetter description of the electrostatic potential map ... 

Alcohol attack generates an unstable intermediate that undergoes nucleophilic attack by CL at carbon. Compare electrostatic potential maps of methanol, thionyl chloride intermediate, and phosphorus trichloride intermediate. What features of these maps are consistent with an electrophilic reactive intermediate ... 

The A -oxide reactions in quinazoline 3-oxide are, however, modified to a certain extent by the aforementioned properties. Thus, whereas it can be reduced to quinazoline with phosphorus trichloride or iron and ferrous sulfate in ethanol, reactions with alkali, acetic anhydride, and benzoyl chloride in the presence of cyanide result in ring fission (Scheme 4). 

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%,... 

Phosphor-athcr, m. phosphoric ether (ester of phosphoric acid, specif, ethyl phosphate), -basis, phosphorus base, -bestimmung, /. determination of phosphorus, -blei, n. lead phosphide Min.) pyromorphite. -bombe, f. phosphorus bomb. -brandgranate, /. phosphorus incendiary shell, -brei, m. phosphorus paste, -bromid, n. phosphorus bromide, specif, phosphorus pentabromide, phos-phorus(V) bromide, -bromijr, n. phosphorus tribromide, phosphorus(III) bromide, -bronze, /. phosphor bronze, -calcium, n. calcium phosphide, -chlorid, n. phosphorus chloride, specif, phosphorus pcntachloride, phosphorus(V) chloride, -chloriir, n. phosphorous chloride (phosphorus trichloride, phosphorus(III) chloride), -dampf, tn. phosphorus vapor or fume, -eisen, n. ferrophos-phorus iron phosphide, -eisensinter, m. diadochite. 

Amino-5-chlorobenzophenone- -oxime Chloroacetyl chloride Phosphorus trichloride... 

A mixture of 3 grams (0.01 mol) of 7-chloro-1-methyl-5-phenyl-3H-1,4-benzodiazepin-2(1 H)-one 4-oxide, 30 ml of chloroform and 1 ml of phosphorus trichloride was refluxed for one hour. The reaction mixture was then poured on ice and stirred with an excess of 40% sodium hydroxide solution. The chloroform was then separated, dried with sodium sulfate, filtered and concentrated in vacuo. The residue was dissolved in methylene chloride and crystallized by the addition of petroleum ether. The product, 7-chloro-Tmethyl-5-phenyl-3H-1,4-benzodiazepin-2(1 H)-one, was recrystallized from a mixture of acetone and petroleum ether forming colorless plates melting at 125°-126°C. 

Phosphorus Trichloride (Phosphorous chloride). PCI3, mw 270.73 colorl, clear fuming liq, mp —111.8°, bp 76°, d 1.547g/cc. Decomps rapidly in moist air. -Dissolves in w or ale with decompn and liberation of much heat. Sol in benz, chlf, eth and C disulfide. Prepd by passing a current of dry chlorine over gently heated P, which ignites. The trichloride, admixed with some pentachioride, distills over. A small amt of Pis added and the whole distilled (Refs 9 10)... 

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) ... 

CjHjoNOjPS 3147-20-4) see Ecothiopate iodide phosphorus trichloride (C1-,P 7719-12-2) see Isoflurophate phosphoryl chloride... 

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. ... 

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. 

O / O Miscellaneous Reactions. A study of the reactions of halogeno-olefins with phosphorus trichloride and oxygen has shown that phosphates [e.g. rra/i5-l,2-dichloroethylene gives 1,2,2-trichloroethyl phosphorodi-chloridate, (29)] are the major products. The minor product was identified as the analogous phosphonate (30), which had previously been reported... 

With phosphorus trichloride, a rather complex reaction results partly in the formation of [PhaP N uPPha PPhCl]+ Cl. The reactivity of the phosphorus(iii) atom is also demonstrated by its ability to desulphurize thiophosphoryl chloride, and its ready reactions with Group VI elements, diborane, and carbon disulphide ... 

B. Studies of Equilibria and Reactions.—N.m.r. spectroscopy is being increasingly employed to study the mode and course of reactions. Thus n.m.r. has been used to unravel the mechanism of the reaction of phosphorus trichloride and ammonium chloride to give phosphazenes, and to follow the kinetics of alcoholysis of phosphoramidites. Its use in the study of the interaction of nucleotides and enzymes has obtained valuable information on binding sites and conformations and work on the line-widths of the P resonance has enabled the calculation of dissociation rate-constants and activation energies to be performed. 

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