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Volume # 3(64), May - June 2009 — "Perfluoroalkylisonitriles"

Fluorine Notes, 2009, 64, 7-8

 

PERFLUOROALKYLISONITRILES
 

A.F.Gontar

 A.N.Nesmeyanov Institute of Organoelements Compounds RAS. 119991, Vavilova str.28, Moscow, Russia.
e-mail:
gontar@ineos.ac.ru

 

It has been found that the reaction of fluoroazaalkenes (RfN=CF2) with trialkylphosphites brings to synthesis of adducts- trialkylperfluoroalkylfluorophosphoranes that may be used without isolation in individual form for production of perfluoroalkylisonitriles (1-3) unavailable earlier.

 

Experimental

Trifluoromethylisonitrile CF3- N=C ( 1)

Trimethylphosphite (12.4 g, 0.1 mol) is placed in a four-neck flask fitted with a thermometer, stirrer, gas supply and gas outlet pipes connected with a cold trap cooled to -120oC. The flask is cooled to a temperature of -40oC with a mixture of acetone- solid carbon dioxide and perfluoro-2-azapropene (13.3g,0.1mol) let pass at stirring. Then cooling is stopped and after the reaction mass reaches room temperature the flask is heated on a boiling water bath to 85-90oC.

The entrapped products are fractionated in a low temperature still. There is produced 7.5g of trifluoromethylisonitrile, boiling temperature from -83 to -81oC. The yield is 79%.
Found,%: C, 24.93; N ,14.52; MWt 94.8
C2NF3 Calculated,%: ?, 25.26; N ,14.73;MWt 95.0


Pentafluoroethylisonitrile C2F5N=C (2)

Analogously to (1) from trimethylphosphite (12.4g, 0.1 mol) and perfluoro-2-azabut-1ene (18.3g, 0.1 mol) there is produced pentafluoroethylisonitrile (10.6g); BP -42oC. The yield is 73.2%.
Found, %: C, 25.13, N, 9.57; MW 143.8.
C3NF5 Calculated, %: C, 24.83; N, 9.66, MW 145.0.

Heptafluoropropylisonitrile C3F7N=C (3)

Similar to (1) from trimethylphosphite (12.4g, 0.1 mol) and perfluoroaza-2-pent-1-ene there is produced perfluoropropylisonitrile (15.9g); BP -25 oC.The yield is 70.9%.
Found, %: C, 24.13; N, 7.29; MW 196.3
C4NF7 Calculated, %: C, 24.62; N, 7.18; MW 195

References

1. Makarov S.P.‚ Englin M.A., ZhOKh, 1967, t. 37‚ s. 2781

2. Banks B.E., Hasseldine R.N., J. Chem. Soc. 1969, (C), p. 2119,

Fluorine Notes, 2009, 64, 7-8

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