Acetoacetic Acid → HCID 16096754, compound

HRID 1244785Notes

Reaction equation

HRID 1244785 reaction equation
[CH3:1][C:2](CC(O)=O)=[O:3].[CH3:8][O:9][C:10]1[CH:15]=[CH:14][C:13]([C:16]2[C:28]3[C:29]4[C:34]([O:35][C:36](=[O:37])[C:27]=3[N:26]3[C:17]=2[C:18]2[C:23]([CH2:24][CH2:25]3)=[C:22]([O:41][CH3:42])[C:21]([O:43][CH3:44])=[C:20]([O:45][CH3:46])[CH:19]=2)=[CH:33][C:32]([OH:38])=[C:31]([O:39][CH3:40])[CH:30]=4)=[CH:12][C:11]=1[OH:47].[C:48](OC(=O)C)(=[O:50])[CH3:49]>N1C=CC=CC=1.CN(C1C=CN=CC=1)C.C(OCC)(=O)C>[CH3:1][C:2]([O:47][C:11]1[CH:12]=[C:13]([C:16]2[C:28]3[C:29]4[C:34]([O:35][C:36](=[O:37])[C:27]=3[N:26]3[C:17]=2[C:18]2[C:23]([CH2:24][CH2:25]3)=[C:22]([O:41][CH3:42])[C:21]([O:43][CH3:44])=[C:20]([O:45][CH3:46])[CH:19]=2)=[CH:33][C:32]([O:38][C:48]([CH3:49])=[O:50])=[C:31]([O:39][CH3:40])[CH:30]=4)[CH:14]=[CH:15][C:10]=1[O:9][CH3:8])=[O:3]

Participants

7

Reactant 3

HCID 96Acetoacetic AcidHCID 7918Acetic AnhydrideHCID 5481589Lamellarin T

Product 1

HCID 16096754HCID 16096754, compoundYield 83%

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 1049PyridineSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
18 °C

Procedure

Lamellain T diacetate: Lamellarin T (48 mg, 0.088 mmol) was dissolved in a solution of acetic anhydride (1.0 mL) and pyridine (1.0 mL) containing DMAP (several crystals) and the solution stirred at 18° C. for 26 h. The solution was then diluted with ethyl acetate (15 mL) and washed with NaHCO3 (a saturated solution in H2O, 20 mL) and citric acid (10% in H2O, 20 mL) dried over (MgSO4) and concentrated under reduced pressure. The residue was subjected to flash chromatography on silica gel (sequential elution with 2:1, 1:1 hexane/ethyl acetate) the relevant fractions (Rf 0.42 1:1 hexane/ethyl acetate) were concentrated giving the title compound (47 mg, 83%) as a white solid mp 251–2° C. IR (KBr disc, cm−1) 2937, 2840, 1769, 1718, 1603, 1545, 1507, 1475, 1456, 1414, 1295, 1266, 1201, 1141, 1117, 1036. 1H NMR (300 MHz, CDCl3) δ 7.31 (dd, J=2.1, 8.4 Hz, 1H), 7.22 (d, J=2.1 Hz, 1H), 7.14 (d, J=8.7 Hz, 1H), 7.07 (s, 1H), 4.90 (m, 1H), 4.60 (m, 1H), 3.90 (s, 3H), 3.89 (s, 3H), 3.86 (s, 3H), 3.45 (s, 3H), 3.39 (s, 3H), 3.13 (m, 2H), 2.30 (s, 6H). 13C NMR+APT (75.5 MHz CDCl3) δ 168.7 (C), 168.4 (C), 155.0 (C), 151.9 (C), 147.5 (C), 144.8 (C), 142.2 (C), 140.6 (C), 138.7 (C), 135.6 (C), 129.5 (CH), 127.6 (C), 127.2 (C), 125.4 (CH), 122.6 (C), 119.8 (C), 116.1 (C), 114.8 (C), 114.4(C), 112.9 (CH), 111.7 (CH), 105.4 (CH), 105.0 (CH), 60.9 (CH3), 60.8 (CH3), 56.2 (CH3), 55.5 (CH3), 55.2 (CH3), 42.1 (CH2), 21.7 (CH2), 20.4 (CH3). MS (70 eV) m/z (%): 629 (53, M+•), 587 (100, M+•-CH2CO); HRMS calcd for C34H31NO11 629.1897. Found 629.1907.

Workup

  1. washwashed with NaHCO3 (a saturated solution in H2O
  2. dry with material20 mL) and citric acid (10% in H2O, 20 mL) dried over (MgSO4)
  3. concentrationconcentrated under reduced pressure
  4. concentrationwere concentrated

Sources & evidence

ORD record
ord-333e007ec8fe464dbd0d31c65b1243f4
Source dataset
uspto-grants-2006_10
Patent number
US07122673B2

Reaction notes

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