REPLACEMENT OF IMINE FRAGMENT
893
1, 3, 2, 4, 5-dioxadithiazine-2,2,4,4-tetroxide (V).
Found, %: C 23.67; F 27.01; N 3.94; S 18.21.
C7F5NO6S2. Calculated, %: C 23.80; F 26.9; N
3.97; S 18.15. By hydrolysis of 0.1 g of tetroxide V
with water at 50 C we obtained 0.06 g (97%) of
pentafluorobenzamide, mp 150 C (publ. 150 C [11]).
Table 1. Then the solvent was removed, the residue
was treated with hexane to obtain dioxides IIa i. The
reaction time, yields, melting points, IR spectra of
dioxides IIa i are given in Table 1, H NMR spectra
of dioxides IIc e, h and elemental composition of
dioxides IIc, e h are presented in Table 2.
1
To a solution of 0.75 g (2.12 mmol) of tetroxide
(V) in 10 ml of CH2Cl2 at 80 C was added at
vigorous stirring a mixture of 0.16 g (4.24 mmol) of
acetonitrile and 0.15 g (2,12 mmol) of pyridine in
10 ml of CH2Cl2, The mixture was kept for 1 h at
80 C and 2 h at 16 C. The precipitate of PySO3 was
filtered off. After evaporation of solvent from the
filtrate we obtained 0.66 g (99%) of dioxide Ie, mp
2-Trichloromethyl-6-(4-chlorophenyl)-1,4,3,5-
oxathiadiazine-4,4-dioxide (IIa) was obtained by
reaction of dioxide (Ia) and 4-chlorobenzonitrile;
2-trichloromethyl-6-phenyl-1,4,3,5-oxathiadiazine-
4,4-dioxide (IIb) from dioxide Ia and benzonitrile;
2-isopropyl-6-trichloromethyl-1,4,3,5-oxathiadi-
azine-4,4-dioxide (IIc) from dioxide Ib and iso-
propyl thiocyanate; 2-piperidino-6-trichloromethyl-
1,4,3,5-oxathiadiazine-4,4-dioxide (IId) from di-
oxide Ib and N-cyanopiperidine; 2-piperidino-6-tri-
bromomethyl-1,4,3,5-oxathiadiazine-4,4-dioxide
(IIe) from dioxides Ic and Id and N-cyanopiperidine;
2-morpholino-6-tribromomethyl-1,4,3,5-oxathiadi-
azine-4,4-dioxide (IIf) from dioxide Id and N-cyano-
1
105 C. IR spectrum (CH2Cl2, , cm ): 1730, 166z0
(C=N), 1380, 1200 (SO2). Found, %: C 34.51; H
1.01; F 30.15; N 8.99; S 10.25. C9H3F5N2O3S.
Calculated, %: C 34.41; H 0.96; F 30.23; N 8.92;
S 10.20.
The hydrolysis of 0.15 g of dioxide Ie at 20 C
afforded 0.15 g (97%) of N-acetyl-N -pentafluoro-
benzoylsulfamide (IVa), mp 89 C. IR spectrum (oily
morpholine;
2-diethylamino-6-tribromomethyl-
1,4,3,5-oxathiadiazine-4,4-dioxide (IIg) from di-
oxide (Id) and N,N-diethylcyanamide; 2-pentafluoro-
phenyl-6-piperidino-1,4,3,5-oxathiadiazine-4,4-di-
oxide (IIh) from dioxide (Ie) and N-cyanopiperidine;
2,6-bis(trichloromethyl)-1,4,3,5-oxathiadiazine-
4,4-dioxide (IIi) from dioxide Ib and trichloroaceto-
nitrile.
1
compound, , cm ): 3300, 3240 (N H); 1735, 1670
(C=O); 1370, 1160 (SO2). Found, %: C 32.49; H
1.48; F 28.50; N 8.47; S 9.61. Neutralization equiv
165.60. C9H5F5N2O4S. Calculated, %: C 32.54; H
1.52; F 28.59; N 8.43; S 9.65. Neutralization equiv
166.10.
General procedure for hydrolysis of dioxides
IIe h. With 30% solution of NaOH was treated
0.25 mmol of dioxide IIe h for 5 min, and the mix-
ture was cooled to 0 C. To the mixture was added
0.2 ml of H2SO4. The separated precipitate was
washed with water and dried. We obtained the cor-
responding N-amidosulfonylureas (IVc f) (97 99%):
N-tribromoacetamido-N , N -pentamethylene-
sulfonylurea (IVc), N-tribromoacetamido-N ,N -
2,6-Bis(pentafluorophenyl)-1,4,3,5-oxathiadi-
azine-4,4-dioxide (If).
A
mixture of 1.26
g
(6.53 mmol) of pentafluorobenzonitrile and 0.25 g
(3.27 mmol) of SO3 was heated for 12 h to 65 C.
Then the product was washed with hexane. We ob-
tained 1.44 g (99%) of dioxide If, mp (decomp.)
149 C (from dichloromethane hexane). IR spectrum
1
(CH2Cl2, , cm ): 1650 (C=N), 1345, 1205 (SO2).
By hydrolysis of dioxide If with 30% solution of
NaOH followed by treating with H2SO4 at 0 C we
obtained 98% of N,N -bis(pentafluorobenzoyl)sulf-
amide (IVb), mp (decomp.) 127 C (from ethanol).
bis(dimethylene)oxysulfonylurea
(IVd),
N-tri-
bromoacetamido-N ,N -diethylsulfonylurea (IVe),
N,N-pentamethylene-N -pentafluorobenzamido-
sulfonylurea (IVf). The precipitates were crystal-
1
IR spectrum (oily substance, , cm ): 3340 (N H),
lized from
a
mixture dichloromethane hexane
1705 (C=O), 1345, 1165 (SO2). Found, %: C 34.69;
H 0.45; F 39.19; N 5.83; S 6.57. Neutralization
equiv 240.12. C14H2F10N2O4S. Calculated, %: C
34.73; H 0.42; F 39.23; N 5.79; S 6.62. Neutraliz-
ation equiv 242.11.
(2: 1). Yields, melting points, and IR spectra of
sulfonylureas IVc f are given in Table 3, elemental
composition and neutralization equivalents in Table 4.
Pentafluorobenzamido-4-pentafluorophenyl-6-
piperidino-1,2,3,5-oxathiadiazine-2-oxide (III). A
solution of 0.21 g (1.93 mmol) of N-cyanopiperidine
and 0.3 g (0.64 mmol) of dioxide If in 20
ml of benzene was heated to 70 C for 15 h. The
solvent was distilled off, the residue was treated in
succession with hexane and ether. We obtained 0.33 g
Transimination of dioxides Ia e into dioxides
IIa i. To a solution of 0.6 mmol of dioxide Ia
in 10 ml of benzene was added 0.7 mmol of an
appropriate cyanide R3CN in 4 ml of benzene at 80 C
under atmosphere of dry nitrogen. The mixture was
kept at this temperature for the time specified in
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 6 2002