R. Colorado-Peralta et al. / Journal of Molecular Structure 981 (2010) 21–33
23
3H7b), 1.09 (br s, 9H, H9). 13C: [66.2, 66.0, 65.9, 1:2:1 ratio, C8],
59.9, 59.6 (C4 or C6), 58.0, 57.7 (C6 or C4), [56.1, 56.0, 55.8, 1:2:1
ratio, C7], 33.4 (C2), 20.1, 20.0 (C9). 11B: +9.1. MS, (20 eV) m/z
(%): 545(21), 420(38), 275(30), 241(36), 183(49), 134(29),
2.9. Tris-{2-(1,3,5-dithiazinan-5-yl)-1-methyl-ethanyl}-phosphite
[8( )]
Compound 8( ) was prepared following the procedure for 7,
from 5( ) (500 mg, 2.79 mmol), NEt3 (0.4 mL, 2.8 mmol) and PCl3
(0.08 mL, 0.9 mmol). Compound 8( ) is a pale yellow liquid
(500 mg, 95%). NMR (d ppm, CDCl3, 25 °C), 1H: 4.35 (br s, 12H,
H4, H6), 4.22 (ddd, 3H, 3J 3.1, 7.4, 6.3 Hz, H8), 4.05 (br s, 6H, H2),
3.07 (dd, 3H, 2J 13.0, 3J 3.1 Hz, H7a), 2.93 (dd, 3H, 2J 13.0, 3J
7.4 Hz, H7b), 1.21 (d, 9H, 3J 6.3 Hz, H9). 13C: [67.4 (d, 2J(13C–31P)
11.5 Hz), 67.3 (d, 2J(13C–31P) 11.2 Hz), 67.2 (d, 2J(13C–31P)
11.2 Hz), 67.1 (d, 2J(13C–31P) 11.7 Hz), 1:1:1:1 ratio, C8], 59.1 (C4,
C6), 55.6 (C7), 33.5 (C2), 20.5 (C9). 31P: +142.1 and +142.0, 3:1 ratio
3J(31P–1H) 7.4 Hz. Anal. Calcd. for C18H36N3O3PS6: C, 38.21; H, 6.41;
N, 7.43. Found: C, 38.25; H, 6.39; N, 7.58.
100(100), 58(82), 42(60). Anal. Calcd. for
C18H36BN3O3S6: C,
39.62; H, 6.65; N, 7.70. Found: C, 40.03; H, 6.96; N, 7.22.
2.6. Tris[(R)-(À)-2-(1,3,5-dithiazinan-5-yl)-1-methyl-ethanyl]-boric
ester [5(À)]
Compound 5(À) was prepared following the same procedure as
for compound 4, from 2(À) (500 mg, 2.8 mmol), NEt3 (0.4 mL,
2.8 mmol) and BCl3 in hexane (1 M, 0.93 mL, 0.93 mmol). Com-
pound 5(À) is a pale yellow liquid (510 mg, 98%). NMR (d ppm,
CDCl3, 25 °C), 1H: 4.38 (br s, 12H, H4, H6), 4.18 (qdd, 3H, 3J = 4.7,
7.4, 6.1 Hz, H8), 4.06 (br s, 6H, H2), 2.99 (dd, 3H, 2J 13.7, 3J
4.7 Hz, H7a), 2.84 (dd, 3H, 2J 13.7, 3J 7.4 Hz, H7b), 1.09 (d, 9H, 3J
6.1 Hz, H9). 13C: 66.5 (C8), 59.5 (C4, C6), 56.2 (C7), 34.0 (C2),
20.4 (C9). 11B: +17.2. 15N: À351.0. NMR (tol-d8, À50 °C), 1H: 4.52
(d, 3H, 2J 13.3, H4ax or H6ax), 4.45 (d, 3H, 2J 3.3, H6ax or H4ax),
4.26 (qdd, 3H, 3J 4.7, 7.7, 6.1, H8), 4.14 (d, 3H, 2J 13.3, H2ax), 3.79
(br d, 6H, 2J 13.3, H4eq, H6eq), 3.14 (br d, 3H, H2eq), 3.06 (dd,
3H, 2J 13.3, 3J 4.7, H7a), 2.76 (dd, 3H, 2J 13.3, 3J 7.7, H7b), 1.07 (d,
9H, 3J 6.1, H9). 13C: 65.8 (C8), 59.7 (C4 or C6), 58.0 (C6 or C4),
56.0 (C7), 33.5 (C2), 20.6 (C9). 11B: +9.1.3. MS, (20 eV) m/z (%):
545(21), 420(38), 275(30), 241(36), 183(49), 134(29), 100(100),
58(82), 42(60).
2.10. Tris-{(R)-(À)-2-(1,3,5-dithiazinan-5-yl)-1-methyl-ethanyl}-
phosphite [8(À)]
Compound 8(À) was prepared following the procedure for 7,
from 5(À) (500 mg, 2.8 mmol) NEt3 (0.4 mL, 2.8 mmol) and PCl3
(0.1 mL, 0.9 mmol). Compound 8(À) is
a pale yellow liquid
(510 mg, 97%). NMR (d ppm, CDCl3, 25 °C), 1H: 4.34 (br s, 12H,
H4, H6), 4.20 (qdd, 3H 3J 6.2, 3.3, 7.6 Hz, H8), 4.02 (br s, 6H, H2),
3.06 (dd, 3H, 2J 13.2, 3J 3.3 Hz, H7a), 2.92 (dd, 3H, 2J 13.2, 3J
7.6 Hz, H7b), 1.19 (d, 9H, 3J 6.2 Hz, H9). 13C: 67.1 (d, 2J(13C–31P)
10.7 Hz, C8), 59.0 (C4, C6), 55.5 (C7), 33.4 (C2), 20.4 (C9). 31P:
+142.0, 3J(31P–1H) 7.4 Hz.
2.7. Tris[2-(1,3,5-dithiazinan-5-yl)-1-phenyl-ethanyl]-boric ester
[6( )]
2.11. Tris-{2-(1,3,5-dithiazinan-5-yl)-ethanyl}-phosphate (9)
Compound 6( ) was prepared following the procedure for com-
pound 4, from 3( ) (500 mg, 2.1 mmol), NEt3 (0.3 mL, 2.1 mmol)
and BCl3 in hexane (1 M, 0.7 mL, 0.7 mmol). Compound 6( ) is a
pale yellow liquid (500 mg, 98%). NMR (d ppm, CDCl3, 25 °C), 1H:
7.40–7.10 (m, 15H, Ph), 5.10 (br dd, 3J 7.5, 4.2 Hz, 3H, H8), 4.28
(br s, 12H, H4, H6), 4.12 (br s, 6H, H2), 3.95 (br dd, 2J 13.5, 3J
4.2 Hz, 3H, H7a), 3.11 (br dd, 2J 13.5, 3J 7.5 Hz, 3H, H7b). 13C:
141.9 (Ci), 128.3 (Co), 127.6 (Cp), 126.1 (Cm), [73.7, 73.6, 73.5,
1:2:1 ratio, C8], 59.6 (br, C4, C6), [57.0, 56.9, 56.8, 1:2:1 ratio,
C7], 33.7 (C2). 11B: +17.8 (s). 15N: À350.4. VT NMR (tol-d8,
À60 °C) 1H 7.40–7.00 (m, 15H, H–Ph), 4.89 (d, 3H, 2J 13.0, H4a or
H6a), 4.83 (d, 3H, 2J 13.0, H6a or H4a), 4.70 (m, 2H, H8), 4.60 (d,
3H, 2J 13.3, H2a), 4.16 (d, 3H, 2J 13.0, H4e or H6e), 4.07 (d, 3H, 2J
13.0, H6e or H4e), 3.60 (d, 3H, 2J 13.3, H2e), 3.22 (m, 3H, H7a),
2.91 (m, 3H, H7b). 13C: 141.9, 141.8 (Ci), 128.1, 127.9 (Cm),
127.0, 126.9 (Cp), 126.0, 125.9 (Co), 73.8, 73.6(br) (C8), 59.8 (br,
C6 or C4), 57.6 (br, C4 or C6), 56.8(br), 56.6 (C7), 33.0 (C2). 11B:
+8.9. Anal. Calcd. for C33H42BN3O3S6Á1/2H2O: C, 53.50; H, 5.85; N,
5.67. Found: C, 53.33; H, 5.55; N, 5.51.
General procedure: To a solution of H2O2 (30%, 80 mL,
1.0 mmol) a solution of compound 7 (500 mg, 1.0 mmol) in CH2Cl2
(30 mL) was added. The mixture was stirred 2 h at rt, and the sol-
vent evaporated. Compound 9 is a colorless viscous liquid (430 mg,
83%). NMR (d ppm, CDCl3, 25 °C), 1H: 4.35 (br s, 12H, H4, H6), 4.12
(br t, 6H, 3J 5.5 Hz, H8), 4.02 (br s, 6H, H2), 3.29 (t, 6H, 3J 5.5 Hz,
H7). 13C: 63.1 (d, 2J(13C–31P) 6.2 Hz, C8), 58.5 (C4, C6), 49.5 (d,
3J(13C–31P) 4.6 Hz, C7), 33.8 (C2). 31P: +9.4.
2.12. Tris-{2-(1,3,5-dithiazinan-5-yl)-1-methyl-ethanyl}-phosphate
[10( )]
Compound 10( ) was prepared following the procedure for 9,
from 8( ) (500 mg, 0.9 mmol) and a solution of H2O2 (30%,
70 mL, 0.9 mmol). Compound 10( ) is a colorless viscous liquid
(500 mg, 97%). NMR (d ppm, CDCl3, 25 °C), 1H: 4.32 (qdd, 3H, 3J
5.9, 3.3, 7.3 Hz, H8), 4.27 (br s, 12H, H4, H6), 4.11 (br s, 6H, H2),
3.04 (dd, 3H, 2J 14.2, 3J 3.3 Hz, H7a), 2.81 (dd, 3H, 2J 14.2, 3J
7.3 Hz, H7b), 1.15 (d, 3J 5.9 Hz, H9). 13C: [73.4 (d, 2J(13C–31P)
6.1 Hz), 73.3 (d, 2J(13C–31P) 5.4 Hz), 1:1 ratio, C8], 59.3 (C4, C6),
[55.1 (d, 3J(13C–31P) 6.1 Hz), 55.0 (d, 3J(13C–31P) 5.4 Hz), C7], 33.7
(C2), [19.8 (d, 3J(13C–31P) 2.3 Hz), 19.7 (d, 3J(13C–31P) 2.3 Hz), C9].
31P: À1.60 (3J(31P–1H) 7.45 Hz), À1.65 (3J(31P–1H) 7.45 Hz), 1:3 ra-
tio. Anal. Calcd. for C18H36N3O4PS6Á1/6C7H8: C, 38.55; H, 6.30; N,
7.04. Found: C, 38.25; H, 6.39; N, 6.58.
2.8. Tris-{2-(1,3,5-dithiazinan-5-yl)-ethanyl}-phosphite (7)
General procedure : To a solution of compound 1 (500 mg,
3.0 mmol) in toluene (50 mL) NEt3 (0.43 mL, 3.0 mmol) was added
at À5 °C. The mixture was stirred 30 min at rt, then cooled to
À78 °C and PCl3 (137 mg, 1.0 mmol) dissolved in hexane (10 mL)
was added. The mixture was stirred for 2 h, at À78 °C, then the
reaction was left to warm to room temperature and filtered under
N2 atmosphere and the solvent evaporated. Compound 7 is a yel-
low liquid (500 mg, 95%). NMR (d ppm, CDCl3, 25 °C), 1H: 4.33 (br
s, 12H, H4, H6), 3.99 (br s, 6H, H2), 3.78 (dt, 6H, 3J 5.6 Hz, H8),
3.12 (t, 6H, 3J 5.6 Hz, H7). 13C: 60.1 (d, 2J(31P–13C) 9.9 Hz, C8),
58.8 (C4, C6), 50.0 (d, 3J(13C–31P) 4.6 Hz, C7), 33.9 (C2). 31P:
+140.6, 3J(31P–1H) 7.4 Hz. Anal. Calcd. for C15H30N3O3S6PÁCHCl3:
C, 32.16; H, 5.58; N, 7.50. Found: C, 32.34; H, 5.96; N, 7.85.
2.13. Tris-{(R)-(À)-2-(1,3,5-dithiazinan-5-yl)-1-methyl-ethanyl}-
phosphate [10(À)]
Compound 10(À) was prepared following the procedure for 9,
from 8(À) (500 mg, 0.9 mmol) and a solution of H2O2 (30%,
70 mL, 0.9 mmol). Compound 10(À) is colorless viscous liquid
(490 mg, 95%). NMR (d ppm, CDCl3, 25 °C), 1H: 4.38 (qdd, 3H, 3J
4.2, 3.7, 7.3 Hz, H8), 4.30 (br s, 12H, H4, H6), 4.16 (br s, 6H, H2),
3.12 (dd, 3H, 2J 10.2, 3J 3.7 Hz, H7a), 2.89 (dd, 3H, 2J 10.2, 3J