Réaction #6519

ord-e7e3a364972640cab00e95d8a664a41d

Équation de réaction

NCCNC(=O)Cc1cccc(NC(=O)Cc2ccc(Nc3ncnc4c3ncn4[C@@H]3O[C@H](CO)[C@@H](O)[C@H]3O)cc2)c1
ADAC
O=C[C@H](O)[C@H](O)[C@H](O)CO
ribose
CC1(C)CC(N=C=S)CC(C)(C)N1[O]
4-isothiocyanato-TEMPO
O
water
NCCNC(=O)Cc1cccc(NC(=O)Cc2ccc(Nc3ncnc4c3ncn4[C@@H]3O[C@H](CO)[C@@H](O)[C@H]3O)cc2)c1
2
NCCNC(=O)Cc1cccc(NC(=O)Cc2ccc(Nc3ncnc4c3ncn4[C@@H]3O[C@H](CO)[C@@H](O)[C@H]3O)cc2)c1
ADAC
→
CC1(C)CCCC(C)(C)N1[O].NCCNC(=O)Cc1cccc(NC(=O)Cc2ccc(Nc3ncnc4c3ncn4[C@@H]3O[C@H](CO)[C@@H](O)[C@H]3O)cc2)c1
TEMPO ADAC

Réactifs

NCCNC(=O)Cc1cccc(NC(=O)Cc2ccc(Nc3ncnc4c3ncn4[C@@H]3O[C@H](CO)[C@@H](O)[C@H]3O)cc2)c1
ADAC
O=C[C@H](O)[C@H](O)[C@H](O)CO
ribose
CC1(C)CC(N=C=S)CC(C)(C)N1[O]
4-isothiocyanato-TEMPO
O
water
—
thiourea carbonyl
NCCNC(=O)Cc1cccc(NC(=O)Cc2ccc(Nc3ncnc4c3ncn4[C@@H]3O[C@H](CO)[C@@H](O)[C@H]3O)cc2)c1
2
NCCNC(=O)Cc1cccc(NC(=O)Cc2ccc(Nc3ncnc4c3ncn4[C@@H]3O[C@H](CO)[C@@H](O)[C@H]3O)cc2)c1
ADAC

Réactifs

Aucun

Solvants

CN(C)C=O
DMF

Conditions de réaction

Conditions détaillées
See reaction.notes.procedure_details.

Traitement

  1. 1
    Autrethe precipitate was collected
  2. 2
    Lavagewashed with a minimum of MeOH and ether
  3. 3
    Autrerecrystallized from DMF/ether/petroleum ether
  4. 4
    Autreto give a product which
  5. 5
    Autregave proton NMR and ESR spectra consistent with the structure

Mode opératoire

ADAC, 2 (11.8 mg, 20 umol), was suspended in 0.5 ml DMF and treated with 4-isothiocyanato-TEMPO (2,2,6,6,-tetramethyl-1-piperidinyloxy, free radical (7 mg, Aldrich). After 1 hour 1.5 ml water was added to the solution, and the precipitate was collected, washed with a minimum of MeOH and ether, and recrystallized from DMF/ether/petroleum ether, to give a product which was homogeneous by thin layer chromatography and gave proton NMR and ESR spectra consistent with the structure. Yield 8.3 mg (51%). Cf-MS peak at 758 (m+1-MeO) and 626 (m+1 -ribose). IR shows a peak at 1580 cm-1, characteristic of a thiourea carbonyl stretch.

Source

DOI: 10.6084/m9.figshare.5104873.v1Brevet: US05248770uspto-grants-1993_09