Phosphorus nitrile chloride

As another inorganic analogue of benzene reference may be made to the constitution of the polymeric phosphorus nitrile chlorides, in which the PN bonds in the ring also appear to be... 

Phosphorus nitrile chloride forms adduct (10) with DMF in the ratio 1 4, which is useful for the preparation of formamidines and azavinylogous formamidinium salts. It is supposed that the dehydration of primary amides to nitriles with (PNChls as well as the formation of 2-alkylbenzothiazoles from 2-(methylthio)anilides and (PNChls in the presence of triethylamine proceed via similar adducts." ... 

EMmethyl polysiloxane + predpitated silica + phosphorus nitrile chloride + polyethylene glycol stearate... 

Poly(phosphorus nitrile chloride) Bzn, carbon tetrachloride, chloroform, Aliphatic hydrocarbons 611... 

Less-expensive preparations, in terms of materials, have involved reactions between phosphorus(III) chloride and lithium cyanate, in benzene,3 or sodium and potassium cyanates in polar solvents such as nitriles, ketones, nitroparaffins, and esters.4 Liquid sulfur dioxide has also been found useful as a solvent for reaction between phosphorus(III) chloride and sodium cyanate.6... 

On the other hand, Evans and Lockhart126 reported that treating 105 (R -R6 = H R7 = OMe R8 = R9 = H) with PPA gave 18 (R1 = H R2 = OMe) as the major product and only some l-benzazepin-2-one. The use of sulfuric acid resulted in tarry products. The 2-tetralone oxime (118, R1 = R2 = R3 = Me R4 = R5 = H) was reported126 to give 24% yield of 86 (R -R4 = Me Rs = R6 = H). Since then, Conley and Lange127 have studied 2-tetralone oximes and shown another mechanism by which the products of Beckmann rearrangement were formed. When the oxime 118 (R1 = Me R2-R6 = H) was treated with phosphorus penta-chloride, a 93-96% yield of the nitrile 119 was obtained. The nitrile could... 

It should be no surprise that reactions which involve phosphorus(III) chlorides and propenamides may yield nitriles as the principal products (Scheme 46), the nitrile being potentially derivable from two possible intermediates. Amongst the phosphorus(III) dichlorides used here have been MePCl2 , EtPCl2, PhPCl2 and p-... 

The phosphorylation of nitriles sometimes yields imidoyl chlorides 186,25evidenced by the isolation of the heterocyclic phosphorus compounds XLVII from the reaction of malonitrile and phosphorus penta-chloride... 

At present, heat shield materials consist of poly(tetrafluorethylene), Si02-filled reinforced phenolic resins, or Si02-filled epoxide/polyamide combinations. Development-stage materials are polyimides, silicones, phosphor nitrilic chlorides, and polyboron phosphorus compounds. 

Phosphorus oxide chloride Nitriles from carboxylic acid amides s. 17,463... 

Phosphorus oxide chloride/pyridine Protection of carbamyl groups as nitriles... 

Phosphorus pentachloridelhydrogen chloride a,a-Dichlorocarboxylic adds from nitriles... 

X Principal elements, phosphorus, nitrogen and halogen Polyphosphoric nitrile chloride... 

In the presence of Triethylamine, PI3 or P2l4 effects the conversion of aldehyde oximes or primary nitro compounds to nitriles. For example, treatment of the aldoxime derived from phenylac-etaldehyde with 1 equiv of PI3 (CH2Cl2-Et3N, 25 °C, 15 min) affords benzyl cyanide in 83% yield (eq 10). Similarly, treatment of 1-nitrodecane with 2 equiv of PI3 (CH2Cl2-Et3N, 25 °C, 15 min) affords 1-cyanononane (82%) (eq 11). Other reagents for the direct conversion of primary nitro compounds to nitriles include Sn(SPh)4/Ph3P/DEAD, TMSI, Sulfur Dioxide and Phosphorus(III) Chloride. ... 

Place 45 g. of benzamide (Section IV, 188) and 80 g. of phosphorus pentoxide in a 250 ml. Claisen flask (for exact experimeutal details on the handling and weighing out of phosphoric oxide, see under Acetamide, Section 111,111). Mix well. Arrange for distillation (Fig.//, 29, 1 or Fig. II, 20, 1) under reduced pressure use a water pump with an air leak in the system so that a pressure of about 100 mm. is attained. Heat the flask with a free flame until no more liquid distils the nitrile will pass over at 126-130°/100 mm. Wash the distillate with a little sodium carbonate solution, then with water, and dry over anhydrous calcium chloride or magnesium sulphate. Distil under normal pressure (Fig. II, 13, 2 or II, 13, 6) from a 50 ml. flask the benzonitrile passes over as a colourless liquid at 188-189° (compare Section IV,66). The yield is 28 g. 

Thiazole carboxamides are readily dehydrated to nitriles in good yields by heating with phosphorus oxychloride (91), phosphorus pentoxide (87, 71), or phosphoryl chloride (16) (Scheme 19). 

Pyridazinecarboxamides are prepared from the corresponding esters or acid chlorides with ammonia or amines or by partial hydrolysis of cyanopyridazines. Pyridazinecarboxamides with a variety of substituents are easily dehydrated to nitriles with phosphorus oxychloride and are converted into the corresponding acids by acid or alkaline hydrolysis. They undergo Hofmann degradation to give the corresponding amines, while in the case of two ortho carboxamide groups pyrimidopyridazines are formed. 

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%,... 

A thioamide of isonicotinic acid has also shown tuberculostatic activity in the clinic. The additional substitution on the pyridine ring precludes its preparation from simple starting materials. Reaction of ethyl methyl ketone with ethyl oxalate leads to the ester-diketone, 12 (shown as its enol). Condensation of this with cyanoacetamide gives the substituted pyridone, 13, which contains both the ethyl and carboxyl groups in the desired position. The nitrile group is then excised by means of decarboxylative hydrolysis. Treatment of the pyridone (14) with phosphorus oxychloride converts that compound (after exposure to ethanol to take the acid chloride to the ester) to the chloro-pyridine, 15. The halogen is then removed by catalytic reduction (16). The ester at the 4 position is converted to the desired functionality by successive conversion to the amide (17), dehydration to the nitrile (18), and finally addition of hydrogen sulfide. There is thus obtained ethionamide (19)... 

Other synthetic routes to phosphazenes, using phosphorus(v) compounds as substrates, are more limited. An example of the reaction of a nitrile with a phos-phorus(v) chloride is provided by Scheme 4.48 In benzene solution, or in the absence... 

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