Ammonium Chloride → [[(Propane-1,3-diyl)dioxy]bis[(2-nitro-5-methoxy-1,4-phenylene)carbonyl]]bis[2-(hydroxymethyl)-4-methylidenepyrrolidine]

HRID 915708Notes

Reaction equation

HRID 915708 reaction equation
CCCC[N+](CCCC)(CCCC)CCCC.[F-].[CH2:19]([O:51][C:52]1[CH:57]=[C:56]([O:58][CH3:59])[C:55]([C:60]([N:62]2[CH2:66][C:65](=[CH2:67])[CH2:64][CH:63]2[CH2:68][O:69][Si](C(C)(C)C)(C)C)=[O:61])=[CH:54][C:53]=1[N+:77]([O-:79])=[O:78])[CH2:20][CH2:21][O:22][C:23]1[CH:28]=[C:27]([O:29][CH3:30])[C:26]([C:31]([N:33]2[CH2:37][C:36](=[CH2:38])[CH2:35][CH:34]2[CH2:39][O:40][Si](C(C)(C)C)(C)C)=[O:32])=[CH:25][C:24]=1[N+:48]([O-:50])=[O:49].[NH4+].[Cl-]>C1COCC1>[CH2:21]([O:22][C:23]1[CH:28]=[C:27]([O:29][CH3:30])[C:26]([C:31]([N:33]2[CH2:37][C:36](=[CH2:38])[CH2:35][CH:34]2[CH2:39][OH:40])=[O:32])=[CH:25][C:24]=1[N+:48]([O-:50])=[O:49])[CH2:20][CH2:19][O:51][C:52]1[CH:57]=[C:56]([O:58][CH3:59])[C:55]([C:60]([N:62]2[CH2:66][C:65](=[CH2:67])[CH2:64][CH:63]2[CH2:68][OH:69])=[O:61])=[CH:54][C:53]=1[N+:77]([O-:79])=[O:78]

Participants

5

Reactant 3

HCID 25517Ammonium ChlorideHCID 2724141Tetrabutylammonium FluorideHCID 131726584[[(Propane-1,3-diyl)dioxy]bis[(2-nitro-5-methoxy-1,4-phenylene)carbonyl]]bis[2-(tert-butyldimethylsilyloxymethyl)-4-methylidenepyrrolidine]

Product 1

HCID 86606191[[(Propane-1,3-diyl)dioxy]bis[(2-nitro-5-methoxy-1,4-phenylene)carbonyl]]bis[2-(hydroxymethyl)-4-methylidenepyrrolidine]Yield 94%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of TBAF (3.98 mL of a 1M solution in THF, 3.98 mmol) was added to the bis-silyl ether 34 (1.41 g, 1.59 mmol) in THF (35 mL) at 0° C. (ice/acetone). The reaction mixture was allowed to warm to room temperature and after a further 30 minutes saturated NH4Cl (120 mL) was added. The aqueous solution was extracted with EtOAc (3×80 mL), washed with brine (80 mL), dried (MgSO4), filtered and evaporated in vacuo to give a dark orange oil which was purified by flash chromatography (97% CHCl3/MeOH) to provide the pure diol 35 as a light orange solid (0.98 g, 94%): [α]19D=−31.9° (c=0.09, CHCl3); 1H NMR (270 MHz, CDCl3) (Rotamers) δ 7.75 and 7.71 (s×2, 2Harom), 6.96 and 6.84 (s×2, 2Harom), 5.08, 5.02 and 4.88 (br s×3, 4H, NCH2C═CH2), 4.61-4.50 (m, 2H, NCHCH2OH), 4.35-4.33 (m, 4H, OCH2CH2CH2O), 4.02-3.65 (m, 14H, NCHCH2OH, NCH2C═CH2 and OCH3), 2.88-2.43 (m, 6H, NCH2C═CH2CH2 and OCH2CH2CH2O); 13C NMR (67.8 MHz, CDCl3) (Rotamers) δ 167.9 and 166.9 (NC═O), 154.9 and 154.3 (Cquat), 148.4 and 148.2 (Cquat), 143.3 and 142.6 (Cquat), 137.2 and 137.0 (Cquat), 127.6 and 127.3 (Cquat), 109.1 (C—Harom), 108.4 (NCH2C═CH2), 108.2 (C—Harom), 65.6 and 65.4 (OCH2CH2CH2O), 64.5 and 63.3 (NCHCH2OH), 60.5 and 60.0 (NCHCH2OH), 56.8 and 56.7 (OCH3), 52.9 (NCH2C═CH2), 35.0 and 34.3 (NCH2C═CH2CH2), 29.6 and 28.6 (OCH2CH2CH2O); MS (FAB) (Relative Intensity) 657 (M++1, 10), 639 (M-OH, 2), 612 (1), 544 (M-NCH2CCH2CH2CHCH2OH, 4), 539 (1), 449 (16), 433(9), 404 (8), 236 (32), 166 (65), 151 (81), 112 (82), 82 (100); IR (NUJOL7) 3600-3200 (br, OH), 2923, 2853, 2360, 1618, 1582, 1522 (NO2), 1459, 1408, 1375, 1335 (NO2), 1278, 1218, 1061, 908, 810, 757 cm−1.

Workup

  1. additionwas added
  2. extractionThe aqueous solution was extracted with EtOAc (3×80 mL)
  3. washwashed with brine (80 mL)
  4. dry with materialdried (MgSO4)
  5. filtrationfiltered
  6. customevaporated in vacuo
  7. customto give a dark orange oil which
  8. customwas purified by flash chromatography (97% CHCl3/MeOH)

Sources & evidence

ORD record
ord-4f4b1687d5274cec89570ee39402ff62
Source dataset
uspto-grants-2007_09
Patent number
US07265105B2

Reaction notes

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