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Gazieva et al.
synthesized by the reaction of the corresponding ureas with glyꢀ
oxal.9,21—23 Sulfamides were synthesized according to known
procedures.24—26
Highꢀpressure experiments were carried out on a piston—
cylinderꢀtype apparatus in 1.6ꢀmL Teflon tubes.
This study was financially supported by the Russian
Academy of Sciences (Program of the Division of Chemꢀ
istry and Materials Science of the Russian Academy of
Sciences No. OKhꢀ10).
5(3H)ꢀOxotetrahydroꢀ1Hꢀimidazo[4,5ꢀc][1,2,5]thiadiazole
2,2ꢀdioxides (2e—g) and 4ꢀ(propylaminosulfonylimino)ꢀ
1,3ꢀdiethylimidazolidinꢀ2ꢀone (4b) (general procedure). Comꢀ
pound 1a (or 1b,c) (0.01 mol) and sulfamide 5a (or 5b)
(0.01 mol) were dissolved in water (5 mL) at pH 6. The reaction
mixture was heated at 60 °C for 1 h. After cooling to room
temperature, compound 2e (or 2f) precipitated within a few
days. In the synthesis of compounds 2g and 4b, water was
distilled off in vacuo at temperature no higher than 40 °C until
an oily precipitate of compounds 2g (Rf = 0.34) and 4b
(Rf = 0.75) was obtained. The compounds were separated by
silica gel column chromatography (40×100) using a 1 : 3
acetone—chloroform mixture. The yields and physicochemical
characteristics of compounds 2e—g are given in Tables 3 and 4.
The characteristics of compound 4b are consistent with those
reported earlier.12
4,6ꢀDiethylꢀ1,3ꢀdimethylꢀ5(3H)ꢀoxoꢀ and 3,4,6ꢀtriethylꢀ1ꢀ
methylꢀ5(3H)ꢀoxotetrahydroꢀ1Hꢀimidazo[4,5ꢀc][1,2,5]thiaꢀ
diazole 2,2ꢀdioxides (2b,i). 4,5ꢀDihydroxyꢀ1,3ꢀdiethylimidazolꢀ
idinꢀ2ꢀone (1c) (0.17 g, 1 mmol) and 1,3ꢀdialkylsulfamide 5e or
5f (1 mmol) were dissolved in acetone (1.0 mL) in a Teflon tube.
Then one drop of concentrated HCl was added, and acetone was
added until the tube was filled. The tube was placed in a highꢀ
pressure apparatus and kept at 1000 MPa and 12 °C for 16 h.
Then the pressure was relieved, the solvent was distilled off, and
the oily residue was triturated with ethyl acetate until a white
precipitate formed. The physicochemical characteristics of comꢀ
pound 2i are given in Tables 3 and 4. The characteristics of
compound 2b have been reported earlier.8
Nꢀ(1,3ꢀDiethylꢀ5ꢀhydroxyꢀ2ꢀoxoimidazolidinꢀ4ꢀyl)ꢀN,N´ꢀ
dialkylsulfamides 7a,b. A solution of 1,3ꢀdiethylꢀ4,5ꢀdihydroxyꢀ
imidazolidinꢀ2ꢀone 1c (0.17 g, 1 mmol), 1,3ꢀdialkylsulfamide
5e or 5f (1 mmol), and AcOH (2 drops) in acetone (1.6 mL) was
placed in a Teflon tube. The tube was placed in a highꢀpressure
apparatus and kept at 1000 MPa and room temperature for
5 min. Then the pressure was relieved and again produced
after 5 min. This cycle was repeated nine times (10 min per
cycle). Then the reaction mixture was kept at 1000 MPa for
3 h, the solvent was distilled off, and the oily residue was trituꢀ
rated with ethyl acetate until a white precipitate formed.
The precipitate was recrystallized from acetone. The yields and
physicochemical characteristics of compounds 7a,b are given in
Tables 3 and 4.
Xꢀray diffraction study. Principal crystallographic paramꢀ
eters and the Xꢀray data collection and refinement statistics for
compounds 2a,d,f are given in Table 5. The structures were
solved by direct methods. The hydrogen atoms of the NH groups
were located in difference electron density maps. All other
hydrogen atoms were positioned geometrically. An analysis of
difference Fourier maps showed that the propyl substituent in
one of the independent molecules in the structure of 2f is disorꢀ
dered over two positions with occupancies of 0.75 and 0.25.
The structures were refined based on F2 with anisotropic disꢀ
placement parameters for nonhydrogen haktloms. The positions of
the hydrogen atoms were refined isotropically using a riding
model. All calculations were carried out with the use of the
SHELXTL PLUS 5 program package.27
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