Organic fluoronitrogens. XII. Amino addition compounds of fluorimines

J. Org. Chem., Vol. $8,No. 6,1873 1075

ORGANICFLUORONITROOENS. XI1

Organic Fluoronitrogens. XII.' Amino Addition Compounds of Fluorimines. Tetrakis(difluoramino)methane C. D. WRIGHTAND J. L. ZOLLINGER* Contribution No. 671 from the Central Research Laboratories, SM Company, St. Paul, Minnesota 66153 Received September .97, 197.9 The addition of amino compounds to N-fluotimines to yield saturated and unsaturated products is described. Pentafluoroguanidine (1) and ammonia react at 110' to form the adduct HzNC(NFz)zNFH (2). On warming to 25O, 2 loses HNFz to yield H,NC(NFz)=NF (3). Fluorination of 2 a t low temperature affords the completely fluorinated derivative, C(NF2)d (4), an explosive, oxidizing liquid.

-

A previous paper' described the addition of hydroxy compounds to N-fluorimines and the chemistry of the products. I n this paper, NH adducts of fluorimines, especially pentafluoroguanidine (1), 2 will be considered. Many of the NF compounds discussed in this paper are explosive and all work was conducted on a small scale with appropriate shielding. The principal reactions which occur when amino compounds are treated with 1are shown below. N Fz

RiItzNH

I -HNFz + (FzN)zC=NF +RiRzNCNFH

__f

I

1

NFz A

T F Z

If 2 is allowed to warm to room temperature, HNFz is eliminated and 1,1,2-trifluoroguanidine(3) is formed in high yield. NFz 25'

I

a"

+ (FzN)zC=NF 1

- 1100

NFz

I

NFz LI

L

Tetrakis(difluoramino)methane.-Fluorination of 2 with a large excess of dilute Fz a t about -30" (neat) gave a mixture of products shown in the equation below, which were separated by glpc (peak area per cents observed were 20, 16, 14,