Hydrochloric Acid → (Z)-methyl 4-hydroxy-2-oxo-4-(phenanthren-3-yl)but-3-enoate

HRID 1749145Notes

Reaction equation

HRID 1749145 reaction equation
NCC(NC1C=CC(N2C(C3C=CC4C=CC5C(C=4C=3)=CC=CC=5)=CC(C(NC(C)C)=O)=N2)=CC=1)=O.[CH:37]1[C:50]2[CH:49]=[CH:48][C:47]3[C:42](=[CH:43][CH:44]=[CH:45][CH:46]=3)[C:41]=2[CH:40]=[C:39]([C:51](=[O:53])[CH3:52])[CH:38]=1.[C:54](OCC)(=[O:60])[C:55]([O:57][CH2:58]C)=[O:56].[H-].[Na+].Cl>CO>[OH:53]/[C:51](/[C:39]1[CH:38]=[CH:37][C:50]2[CH:49]=[CH:48][C:47]3[C:42]([C:41]=2[CH:40]=1)=[CH:43][CH:44]=[CH:45][CH:46]=3)=[CH:52]\[C:54](=[O:60])[C:55]([O:57][CH3:58])=[O:56]

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 7268Diethyl OxalateHCID 24758Sodium hydrideHCID 748673-AcetylphenanthreneHCID 862712391-(4-(2-Aminoacetamido) phenyl)-N-isopropyl-5-(phenanthren-3-yl)-1H-pyrazole-3-carboxamide

Product 1

HCID 117667451(Z)-methyl 4-hydroxy-2-oxo-4-(phenanthren-3-yl)but-3-enoateYield 80%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

1-(4-(2-Aminoacetamido) phenyl)-N-isopropyl-5-(phenanthren-3-yl)-1H-pyrazole-3-carboxamide (15)Step a. To the mixture of 1-(phenanthren-3-yl)ethanone (1; 6.6 g, 30 mmol) and diethyl oxalate (2 ml) in MeOH (100 mL) was added sodium hydride (2.9 g, 120 mmol) portion-wise within 10 min. The reaction mixture was stirred at room temperature for 4 h, cooled down to 0° C. and acidified with 2N HCl. The precipitate was collected, washed with cold ethanol and dried to yield (Z)-methyl 4-hydroxy-2-oxo-4-(phenanthren-3-yl)but-3-enoate (1) as yellow crystal (7.3 g, 80%). It was used for the next step without further purification. 1H-NMR (300 MHz, DMSO-d6) δ 9.47 (s, 1H), 9.09 (d, J=7.8 Hz, 1H), 8.26 (d, J=9.0 Hz, 1H), 8.15 (d, J=9.0 Hz, 1H), 8.06-8.01 (m, 2H), 7.94 (d, J=7.8 Hz, 1H), 7.80-7.69 (m, 2H), 7.51 (s, 1H), 3.90 (s, 3H).

Workup

  1. temperaturecooled down to 0° C.
  2. customThe precipitate was collected
  3. washwashed with cold ethanol
  4. customdried

Sources & evidence

ORD record
ord-cd23b86f04ef4782a54fe74473ab997c
Source dataset
uspto-grants-2015_10
Patent number
US09156790B2

Reaction notes

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