N,N-di-n-butylformamide dimethyl acetal → HCID 86590003, compound

HRID 1293514Notes

Reaction equation

HRID 1293514 reaction equation
[CH2:1]([N:5]([CH:10]=[N:11][C:12]1[N:17]=[C:16]([N:18]=[CH:19][N:20]([CH2:25][CH2:26][CH2:27][CH3:28])[CH2:21][CH2:22][CH2:23][CH3:24])[N:15]=[C:14]2[N:29]([C@@H:32]3[O:37][C@H:36]([CH2:38][OH:39])[C@@H:34]([OH:35])[CH2:33]3)[N:30]=[CH:31][C:13]=12)[CH2:6][CH2:7][CH2:8][CH3:9])[CH2:2][CH2:3][CH3:4].[Br:40]C1C2C(=NC(N)=NC=2N)N([C@@H]2O[C@H](CO)[C@@H](O)C2)N=1.COC(OC)N(CCCC)CCCC>CO>[CH2:1]([N:5]([CH:10]=[N:11][C:12]1[N:17]=[C:16]([N:18]=[CH:19][N:20]([CH2:25][CH2:26][CH2:27][CH3:28])[CH2:21][CH2:22][CH2:23][CH3:24])[N:15]=[C:14]2[N:29]([C@@H:32]3[O:37][C@H:36]([CH2:38][OH:39])[C@@H:34]([OH:35])[CH2:33]3)[N:30]=[C:31]([Br:40])[C:13]=12)[CH2:6][CH2:7][CH2:8][CH3:9])[CH2:2][CH2:3][CH3:4]

Participants

5

Reactant 3

HCID 11275722N,N-di-n-butylformamide dimethyl acetalHCID 15539888356038-31-8HCID 66893755HCID 66893755, compound

Product 1

HCID 86590003HCID 86590003, compoundYield 50%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

As described for 8a, with 2b (350 mg, 1 mmol) and N,N-di-n-butylformamide dimethyl acetal (720 μl, 3.1 mmol) in MeOH (7 ml) for 2 h at 40°. After FC (eluant: A→B) two main products were isolated. The faster migrating zone gave 8b as a foam (310 mg, 50%). TLC(B): Rf0.3. UV (MeOH): 235 (22500), 275 (14500), 320 (22100). 1H-NMR ((D6)DMSO): 0.94-0.99 (m, CH2CH3); 1.32-1.44 (m, CH2CH3); 1.59-1.73 (m, CH2CH2); 2.21 (m, H—C(2′)); 2.91 (m, H—C(2′)); 3.32-3.78 (2m, H2—C(5′), NCH2); 3.89 (m, H—C(4′)); 4.40 (m, H—C(3′)); 4.78 (t, J=5.8, HO—C(5′)); 5.19 (d, J=4.4, HO—C(3′)); 6.81 (‘t’, J=6.5, H—C(1′)); 8.69 (s, N═CH); 8.94 (s, N═CH). Anal. calc. for C28H47BrN8O3 (623.6): C, 53.93; H, 7.60; N, 17.97; Found: C, 54.01; H, 7.52; N, 18.05. The slower zone furnished 3-bromo-1-[2-deoxy-β-D-erythro-pentofuranosyl]-N6-((di-n-butylamino)methylene)-1H-pyrazolo [3,4-d]-pyrimidin-4,6-diamine (9b) (75 mg, 16%). TLC(B): Rf0.3. UV (MeOH): 236 (21600), 276 (14000), 320 (21900). 1H-NMR ((D6)DMSO): 0.90-0.96 (m, CH2CH3); 1.30-1.39 (m, CH2CH3); 1.59-1.73 (m, CH2CH2); 2.23 (m, H—C(2′)); 2.89 (m, H—C(2′)); 3.35-3.78 (2m, H2—C(5′), NCH2); 3.84 (m, H—C(4′)); 4.43 (m, H—C(3′)); 4.80 (t, J=5.7, HO—C(5′)); 5.23 (d, J=4.6, HO—C(3′)); 6.40 (s, NH2); 6.81 (‘t’, J=6.4, H—C(1′)); 8.65 (s, N═CH). Anal. calc. for C19H30BrN7O3 (484.4): C, 47.11; H, 6.24; N 20.24; Found: C, 47.23; H, 6.52; N, 20.35.

Workup

  1. customAfter FC (eluant: A→B) two main products were isolated

Sources & evidence

ORD record
ord-5dc522daac7649bcb94b2a648c005d56
Source dataset
uspto-grants-2007_07
Patent number
US07238795B2

Reaction notes

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