2-Sulfonyliminohexahydro-1,3,5-triazines
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 3, March, 2001
483
MeCN, and dried in air. Compounds 3g,h,n,o were obtained
after crystallization from the corresponding solvent (see Table 1).
Procedure C. A mixture or arylsulfonylguanidine 1a,b,d
(10 mmol), (CH2O)n (12 mmol), and TsOHH2O (0.1 g) or
ZnCl2 (0.1 g) was thoroughly ground in a mortar and trans-
ferred into a wide tube. Then a solution of trihexahydro-1,3,5-
triazine (4a,b) (3.3 mmol) in Et2O (12 mL) was added to the
reaction mixture. After removal of Et2O on a warm water bath,
the tube was transferred into a boiling water bath. Subsequent
operations were carried out as described in procedure A.
Compounds 3a,e,i,p were obtained.
The physicochemical and spectral characteristics of the
corresponding hexahydrotriazines 3 prepared according to dif-
ferent procedures are identical.
5-Methyl-2-p-tosyliminohexahydro-1,3,5-triazine (3a).
1H NMR, δ: 2.28 (s, 3 H, MeN); 2.34 (s, 3 H, MeAr); 4.03 (s,
4 H, NCH2N); 7.28 and 7.67 (both d, 2 H each, Ar, J = 8.0 Hz);
7.55 (br.s, 2 H, NH).
2-(4-Acetamidophenylsulfonyl)imino-5-cyclohexylhexahydro-
1,3,5-triazine (3l). 1H NMR, δ: 0.871.17 and 1.411.81
(both m, 10 H, CH2 of cyclohexane); 2.07 (s, 3 H, Me);
2.152.27 (m, 1 H, CH of cyclohexane); 4.19 (s, 4 H, NCH2N);
7.51 (br.s, 2 H, NH of the ring); 7.69 (s, 4 H, Ar); 10.20 (s,
1 H, CONH).
2-(4-Acetamidophenylsulfonyl)imino-5-(1-benzylpiperidin-4-
yl)hexahydro-1,3,5-triazine (3m). 1H NMR, δ: 1.191.40 and
1.581.85 (both m, 6 H, CH2 of piperidine); 2.07 (s, 3 H, Me);
2.102.30 (m, 1 H, CH of piperidine); 2.642.84 (m, 2 H,
CH2 of piperidine); 3.38 (s, 2 H, CH2Ph); 4.18 (s, 4 H,
NCH2N); 7.157.35 (m, 5 H, Ph); 7.50 (br.s, 2 H, NH of the
ring); 7.65 (s, 4 H, C6H4SO2); 10.10 (s, 1 H, CONH).
2-(4-Acetamidophenylsulfonyl)imino-5-(4-chlorophenyl)he-
1
xahydro-1,3,5-triazine (3n). H NMR, δ: 2.09 (s, 3 H, Me);
4.71 (s, 4 H, NCH2N); 7.03 and 7.22 (both d, 2 H each,
C6H4Cl, J = 8.7 Hz); 7.63 (s, 4 H, C6H4SO2); 7.80 (br.s, 2 H,
NH of the ring); 10.18 (s, 1 H, CONH).
5-Allyl-2-p-tosyliminohexahydro-1,3,5-triazine (3b).
1H NMR, δ: 2.34 (s, 3 H, Me); 3.03 (d, 2 H, CH2CH=CH2,
J = 4.8 Hz); 4.08 (s, 4 H, NCH2N); 5.005.18 (m, 2 H,
CH=CH2); 5.655.88 (m, 1 H, CH); 7.28 and 7.69 (both d,
2 H each, Ar, J = 8.1 Hz); 7.57 (br.s, 2 H, NH).
2-(4-Acetamidophenylsulfonyl)imino-5-(4-nitrophenyl)he-
1
xahydro-1,3,5-triazine (3î). H NMR, δ: 2.08 (s, 3 H, Me);
4.89 (s, 4 H, NCH2N); 7.20 and 8.08 (both d, 2 H each,
C6H4NO2, J = 9.1 Hz); 7.59 (s, 4 H, C6H4SO2); 7.89 (br.s,
2 H, NH of the ring); 10.03 (s, 1 H, CONH).
5-(2-Hydroxyethyl)-2-p-tosyliminohexahydro-1,3,5-triazine
(3c). 1H NMR, δ: 2.34 (s, 3 H, Me); 2.53 (t, 2 H, NCH2CH2,
J = 4.7 Hz); 3.48 (br.t, 2 H, CH2CH2O, J = 4.7 Hz); 4.12 (s,
4 H, NCH2N); 4.55 (br.s, 1 H, OH); 7.28 and 7.67 (both d,
2 H each, Ar, J = 8.0 Hz); 7.58 (br.s, 2 H, NH).
Sodium (2-p-tosyliminohexahydro-1,3,5-triazin-5-yl)acetate
(3d). 1H NMR, δ: 2.34 (s, 3 H, Me); 3.00 (s, 2 H, CH2CO);
4.07 (s, 4 H, NCH2N); 7.28 and 7.67 (both d, 2 H each, Ar,
J = 8.0 Hz); 7.75 (br.s, 2 H, NH).
5-Benzyl-2-p-tosyliminohexahydro-1,3,5-triazine (3e).
1H NMR, δ: 2.36 (s, 3 H, Me); 3.56 (s, 2 H, CH2Ph); 4.08 (s,
4 H, NCH2N), 7.347.48 (m, 5 H, Ph); 7.28 and 7.71 (both d,
2 H each, C6H4Me, J = 8.2 Hz); 7.63 (br.s, 2 H, NH).
5-[1-Benzylpiperidin-1-yl]-2-p-tosyliminohexahydro-1,3,5-
triazine (3f). 1H NMR, δ: 1.201.42, 1.591.84, and 2.152.30
(all m, 7 H, 3 CH2, CH of piperidine); 2.37 (s, 3 H, Me);
2.672.81 (m, 2 H, CH2 of piperidine); 3.39 (s, 2 H, CH2Ph);
4.18 (s, 4 H, NCH2N); 7.21 and 7.65 (both d, 2 H each,
C6H4Me, J = 8.1 Hz); 7.227.32 (m, 5 H, Ph); 7.58
(br.s, 2 H, NH).
5-(4-Chlorophenyl)-2-p-tosyliminohexahydro-1,3,5-triazine
(3g). 1H NMR, δ: 2.36 (s, 3 H, Me); 4.72 (s, 4 H, CH2N); 7.07
and 7.25 (both d, 2 H each, C6H4Cl, J = 8.9 Hz); 7.20 and 7.55
(both d, 2 H each, C6H4Me, J = 8.1 Hz); 7.86 (br.s, 2 H, NH).
5-(3-Nitrophenyl)-2-p-tosyliminohexahydro-1,3,5-triazine
(3h). 1H NMR, δ: 2.30 (s, 3 H, Me); 4.87 (s, 4 H, NCH2N);
7.12 (d, 2 H, C6H4Me, J = 8.1 Hz); 7.477.61 and 7.747.91
(both m, 6 H, H arom.); 7.96 (br.s, 2 H, NH).
5-Methyl-2-(4-nitorphenylsulfonyl)iminohexahydro-1,3,5-
1
triazine (3ð). H NMR, δ: 2.38 (s, 3 H, Me); 4.05 (s, 4 H,
NCH2N); 7.75 (br.s, 2 H, NH); 8.05 and 8.35 (both d, 2 H each,
Ar, J = 8.8 Hz).
2-Butylsulfonylimino-5-[(2-furyl)methyl]hexahydro-1,3,5-
1
triazine (3q). H NMR, δ: 0.88 (t, 3 H, Me; J = 7.0 Hz);
1.301.73 (m, 4 H, CH2 of the chain); 2.85 (t, 2 H, CH2 of the
chain, J = 7.7 Hz); 3.77 (s, 2 H, CH2Het); 4.13 (s, 4 H,
NCH2N); 6.34 (d, 1 H, Het, J = 8.6 Hz); 6.406.46 (m, 1 H,
Het); 7.49 (br.s, 2 H, NH); 7.61 (s, 1 H, Het).
5-(1-Benzylpiperidin-4-yl)-2-butylsulfonyliminohexahydro-
1,3,5-triazine (3r). 1H NMR, δ: 0.92 (t, 3 H, Me, J = 7.2 Hz);
1.302.06 (m, 10 H, 2 CH2 of the chain, 3 CH2 of piperidine);
2.552.92 (m, 5 H, CH2 of the chain, CH2, CH of piperidine);
3.43 (s, 2 H, CH2Ph); 4.23 (s, 4 H, NCH2N); 7.157.35 (m,
5 H, Ph); 7.42 (br.s, 2 H, NH).
2-Butylsulfonylimino-5-(4-chlorophenyl)hexahydro-1,3,5-
triazine (3s). 1H NMR, δ: 0.8 (t, 3 H, Me, J = 7.0 Hz);
1.141.60 (m, 4 H, CH2 of the chain); 2.75 (t, 2 H, CH2 of the
chain, J = 7.6 Hz); 4.77 (s, 4 H, NCH2N); 7.18 and 7.35
(both d, 2 H each, Ar, J = 8.5 Hz); 7.65 (br.s, 2 H, NH).
Nitration of compound 3a. Compound 3a (0.54 g, 2 mmol)
was added portionwise to a mixture of concentrated H2SO4
(2.5 mL) and HNO3 (d 1.47; 5 mL) cooled in an ice bath. The
reaction mixture was stirred at 5 °C for 1 h and then poured
onto crushed ice (20 g). The precipitate that formed was filtered
off, washed several times with ice water, and dried in air. After
crystallization from 50% EtOH, compound 3i was obtained in a
yield of 0.46 g (73.6%), m.p. 211213 °C.
5-Methyl-2-(4-methyl-3-nitrophenylsulfonyl)iminohexa-
1
hydro-1,3,5-triazine (3i). H NMR, δ: 2.29 (s, 3 H, MeN);
References
2.57 (s, 3 H, Me); 4.05 (s, 4 H, NCH2N); 7.65 (d, 1 H, Ar,
J = 8.3 Hz); 7.69 (br.s, 2 H, NH); 7.98 (d, 1 H, Ar, J = 8.3 Hz);
8.30 (s, 1 H, Ar).
1. Eur. Pat EP 428.941; Chem. Abstrs., 1991, 115, 183374; Jpn.
Pat. JP 10.45.755[98.145.755]; Chem. Abstrs., 1998, 128,
154104; Jpn. Pat. JP 08.245.322[96.245.322]; Chem. Abstrs.,
1997, 126, 15863.
2. Jpn. Pat. 3573('61); Chem. Abstrs., 1963, 58, 10126.
3. P. R. Carter, D. H. Hey, and D. S. Morris, J. Chem. Soc.,
1932, 1353.
4. L. Kahovec, J. Am. Chem. Soc., 1939, 33, 8118.
5. J. Gramore, J. Chem. Soc., 1932, 1353.
6. US Pat. 2.359.363; Chem. Abstrs., 1945, 39, 713.
5-(4-Chlorophenyl)-2-(4-methyl-3-nitrophenylsulfonyl)imino-
1
hexahydro-1,3,5-triazine (3j). H NMR, δ: 2.58 (s, 3 H, Me);
4.75 (s, 4 H, NCH2N); 7.01 and 7.19 (both d, 2 H each, C6H4Cl,
J = 8.5 Hz); 7.54 (d, 1 H, C6H3Me, J = 8.3 Hz); 7.84 (d, 1 H,
C6H3Me, J = 8.3 Hz); 7.97 (s, 2 H, NH); 8.24 (s, 1 H, C6H3Me).
2-(4-Acetamidophenylsulfonyl)-5-allyliminohexahydro-1,3,5-
1
triazine (3k). H NMR, δ: 2.07 (s, 3 H, Me); 3.03 (d, 2 H,
CH2CH=CH2, J = 4.8 Hz); 4.09 (s, 4 H, NCH2N); 5.025.20
(m, 2 H, CH=CH2); 5.655.88 (m, 1 H, CH=CH2); 7.57 (br.s,
2 H, NH of the ring); 7.69 (s, 4 H, Ar); 10.21 (s, 1 H, CONH).
Received November 2, 2000