1076 H. W. KOESKY,H . H . GIERE,A N D D. P.BABE
Inorgcmzc Chemistry CONTRIBUTION F l i O M THE ANORGANISCH-CHEMISCHES INS~ITUT DER UNIVERSITAT GOTTISGEN,GOTTINGEN, GERMANY
Preparation of Substituted Fluorosulfonyl Isocyanides. XXVIIl BY HERBERT W. ROESKY, HORST H . GIERE,
AND
DANIEL P. BABB
Receiced LJrocember 4 , 1969 FS02NHC(O)CFH2was prepared by the reaction of FS021\'C0 with rnonofluoroacetic acid with evolution of carbon dioxide. A study of the reactions of FS02XHC(0)CFH2and FSO,KHC(O)CF, with PClj has resulted in the preparation and characterization of the compounds
FSOzN=C
/
\
c1 FSOaS=C CFH2
ClSO,?;=C
\
CF8
\
CF3
The reaction of FS02S=CClCFa with ammonia and several amines led to compounds of the general formula FSOAN=CCFJ , S(C2H;)2. Partial hydrolysis of FSOIN=CClCF, gave FSO?XHC(0)CFa. The compounds where X = XH2, K( C H S ) ~and have been isolated and their structures Characterized by infrared, nmr, and mass spectrometry and elemental analyses.
Introduction Recently the preparation of the heterocyclic compound2 0
/I Ai\ x o s S
was reported as resulting from the reaction of CISOzN= Pc13 and trifluoroacetic acid. The purpose of this work was to examine some of the reactions of FSOzN=PC& and FSOlNCO with fluorinated acetic acids in an attempt to prepare linear or cyclic fluorosulfonyl-nitrogen compounds. The resulting compounds, FSOzNHC(O)R, were treated with phosphorus pentachloride to form additional members of the series FS02N=CC1R3-& by elimination of HCI and P0Cl3. Reaction of FS02NHC(O)CF3 with PCI, produced CISO&"CCICF,, in addition to the FSOZcompound. Compounds of the general formula FSO2N=CXCF3 where X = NH2, N(CH&, and N(CzH6)zresulted from the reaction of FS02N=CC1CF3 with NH3, (CHJ2NH, and (C2H5),NH. Hydrolysis of FSOaN=CCICFy produced FSOsN H C ( 0 ) CF3. Experimental Section Reagents.-CF8COOH, PCL, and the amines were obtained from Merck A.G. or Fluka A.G. These reagents were used without further purification. FSO2NCO was prepared by the fluorination of ClSO2NCO with antimony trifluoride.6 MonoHuoroacetic acid, CFHzCOOH, was prepared by the reaction of (FCH2COO)gBa with sulfuric acid.7 (1) Paper XXVI: H. W. Roesky and L). P. Babb, Iitoiu. Nucl. Chein., Lelters, in press. (2) H. W. Roesky, A n g e v . Chem., 81,493 (1969). (3) H. W. Roesky, ibid., 81, 119 (1969). (4) H. W. Roesky and H. H. Giere, C h r m . Ber., 102, 3707 (1969). ( 5 ) H. W. Roesky and S. Tutkunkardes, Z. A m i n . A l l g e m , Chem., in press. (6) H. W. Roesky and A. Hoff, C h e v t . B e y . , 101, 162 (1968). (7) M . Hudlicky, "Chemie der organischen FluorverbiIiduIigeri," \'El3 Verlag der Wissenschaften, Berlin, 1YG0, p 124.
General Methods.-All reactions were carried out in Pyrex flasks under an atmosphere of nitrogen. Prior t o use the nitrogen was dried over a column of P ~ O I O .Because the compounds could be extremely toxic, all operations were performed in a wellventilated hood. Infrared spectra (Table I ) were recorded using a Leitz infrared spectrophotometer. The spectra of liquids were obtained in the liquid phase as capillary films with potassium bromide windows and as gases in a gas cell of 10-cm length. Kuclear magnetic resonance spectra (Table 11) were recorded using a Varian A-56/60 spectrometer. Tetramethylsilane and trichlorofluoromethane were used as external standards. Elemental analyses (Table 111) were performed by Beller Microanalytical Laboratory, Gottingen, Germany. Boiling points of liquids are given in Table 111. Mass spectra were obtained using an Atlas UFCH 4 spectrometer and the spectrum of FS02hT=CClCI'3 is given in Tablc IV. Preparation of Monofluoroacetylfluorosulfonylimide, FSOANHCOCFH2.-The reaction was carried out in a one-neck 500-nil flask equipped with a magnetic stirrer, a reflux condenser, and a nitrogen T adapter. A 125.0-g sample (1.0 mol) of FS02NCO and 78.0 g (1.O mol) of FCHZCOOHwere heated to 80' and maintained a t that temperature for about 5 hr. After cooling to room temperature crystals of FSO?NHC(O)CHsF were formed. This compound was not characterized in detail. Preparation of N-FluorosulfonylfluoromethylcarbimideChloride, FS02N=CClCHrF.-In a two-neck flask equipped with a mechanical stirrer and a reflux condenser with a drying tube werc placed 600 ml of CCL, 159.0 g (1.0 mol) of FSOzKHC(O)CI-I2F, and 208.0 g (1.0 mol) of PCL. The mixture was heated for 1 h r a t 80". The resulting POC18 a n d CClr were removed by means of a mater pump vacuum a n d the residue was distilled under vacuum; yield, 91.0 g (51%) (0.51 mol). Preparation of Trifluoroacetylfluorosulfony1imide.-FSOZKHCOCF3 was first prepared by Heinze.* -4 sample of 234.5 g (1.0 mol) of FS02N=PC13 and 114.0 g 11.0 mol) of CF3COOH was heated for 60 h r a t 90-100' in a flask equipped with a rcflux condenser topped with a drying tube. The POC13 formed in the reaction was removed under water pump vacuum (10-12 inm) and the product purified by distillation under high vacuum (0.01 mm); yield, 156 g ( S O Y , ) (0.8 mol). Preparation of N-FluorosulfonyltrifluoromethylcarbimideChloride, FS02N=CClCF8.-The reaction was carried out in a 500-ml three-neck flask equipped with a distillation head, a dropping funnel, and a mechanical stirrer. To 206 g (1.0 mol) of PCl: was added 195 g (1.0 mol) of FSO&HC(O)CFs, and the mixture (8) 1'. I
