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DOI: 10.1055/s-0030-1260327
Pyridine-Mediated Synthesis of 1,3-Diazetidin-2-ones (Aza-β-lactams): Novel Investigations on Isocyanate-Carbodiimde Reaction
Publication History
Publication Date:
22 September 2011 (online)
Abstract
The reported cycloaddition reaction of isocyanates and symmetric carbodiimides is reinvestigated in the presence of pyridine. The Huisgen zwitterion generated by the 1:1 addition of pyridine to arylsulfonyl isocyanate is trapped by dialkyl carbodiimide to obtain symmetrical 1,3-diazetidin-2-ones via a novel intramolecular rearrangement.
Key words
1,3-diazetidin-2-one - aza-β-lactam - carbodiimide - arylsulfonyl isocyanate - pyridine
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References and Notes
To a magnetically stirred solution
of pyridine (160 mg, 2 mmol) and p-toluenesulfonyl
isocyanate (400 mg, 2 mmol) in CH2Cl2 (5 mL)
was added dicyclohexyl carbodiimide (410 mg, 2 mmol) in CH2Cl2 (2mL).
The reaction mixture was stirred for 12 h in r.t. After completion
of the reaction, the solvent was removed under reduced pressure,
and the residue was purified by column chromatography over silica gel
(Merck 230-240 mesh) using a hexane-EtOAc (20:1) mixture
as eluent. The product was recrystallized from Et2O to
obtain product 11a as colorless crystals,
mp 110-112 ˚C, 0.17 g, yield 42%.
IR (KBr): νmax = 1866 (C=O),
1648 (C=N), 1532 and 1439 (Ar), 1317 and 1151 (SO2)
cm-¹. Anal. Calcd (%) for
C21H29N3O3S (403.53):
C, 62.51; H, 7.24; N, 10.41. Found: C, 62.55; H, 7.25; N, 10.42%.
MS (EI, 70 eV): m/z (%) = 322
(88), 279 (14), 248 (21), 220 (19), 197 (28), 155 (66), 123 (17),
91 (100), 69 (15), 55 (43), 41 (7). ¹H NMR (500.13 MHz, CDCl3): δ = 1.09-1.96
(20 H, m, 20 H of 2 Cy), 2.45 (Me), 3.68 (2 H, br, 2 NCH), 7.33
(2 H, d, ³
J
HH = 7.8
Hz, 2 CH of Ph), 7.85 (2 H, d, ³
J
HH = 7.8
Hz, 2 CH of Ph). ¹³C NMR (125 MHz,
CDCl3): δ = 21.55
(Me), 25.01 (2 CH2), 25.18 (4 CH2), 30.89
(4 CH2), 54.65 (2 NCH), 126.74 (2 CH of Ph), 129.49 (2
CH of Ph), 138.55 (C
ipso
-SO2),
143.65 (C
ipso
-Me), 154.88
(C=O), 157.05 (C=N).
Crystal
Data for 11a
C21H33N3O3S
(CCDC 824721): M
W = 407.57,
orthorhombic, space group 2ac, a = 21.8645
(18) Å, b = 9.7928
(9) Å, c = 10.0106
(9) Å, α = 90.00, β = 90.00, γ = 90.00, V = 2143.4
(3) ų, Z = 4, D
c = 1.263
mg/m³, F(000) = 880, crystal
dimension 0.26 ¥ 0.18 ¥ 0.07 mm, radiation, Mo
Kα (λ = 0.71073 Å),
1.86 ≤ 2θ ≤ 25.00,
intensity data were collected at 298 (2) K with a Bruker APEX area-detector diffractometer,
and employing ω/2θ scanning
technique,
in the range of -21 ≤ h ≤ 26, -11 ≤ k ≤ 11, -9 ≤ l ≤ 11;
the structure was solved by a direct method, all nonhydrogen atoms
were positioned and anisotropic thermal parameters refined from
2014 observed reflections with R (into) = 0.1497
by a full-matrix least-squares technique converged to R = 0.1334
and Raw = 0.3306 [I > 2 σ(I)].
Compound 11c
Colorless crystals,
mp 109-111 ˚C, 0.18 g, yield 46%.
IR
(KBr): νmax = 1874 (C=O),
1659 (C=N), 1532 and 1439 (Ar), 1363 and 1150 (SO2)
cm-¹. Anal. Calcd (%) for C20H27N3O3S
(389.51): C, 61.67; H, 6.99; N, 10.79. Found: C, 61.66; H, 6.71;
N, 10.82. MS (EI, 70 eV): m/z (%) = 389 (2) [M+],
368 (18), 313 (21), 292 (26), 240 (37), 197 (22), 155 (87), 111
(57), 91 (87), 57 (100), 43 (54). ¹H NMR (500.13 MHz, CDCl3): δ = 1.12-1.96
(20 H, m, 20 H of Cy), 3.68 (2 H, br, 2 NCH), 7.54 (2 H, t, ³
J
HH = 7.4
Hz, 2 CH of Ph), 7.61 (1 H, t, ³
J
HH = 7.1
Hz, CH of Ph), 7.97 (2 H, d, ³
J
HH = 8.6
Hz, 2 CH of Ph). ¹³C NMR (125 MHz,
CDCl3): δ = 25.01
(2 CH2), 25.17 (4 CH2), 30.90 (4 CH2),
54.70 (2 NCH), 126.68 (2 CH of Ph), 128.89 (2 CH of Ph), 132.80 (CH
of Ph), 141.42 (C
ipso
-SO2),
154.77 (C=O), 157.34 (C=N).