(2-Chloro-6-cyano-naphthalen-1-yl)-acetic acid ethyl ester → (2-Chloro-6-formyl-naphthalen-1-yl)-acetic acid ethyl ester

HRID 639199Notes

Reaction equation

[CH2:1]([O:3][C:4](=[O:19])[CH2:5][C:6]1[C:15]2[C:10](=[CH:11][C:12]([C:16]#N)=[CH:13][CH:14]=2)[CH:9]=[CH:8][C:7]=1[Cl:18])[CH3:2].[PH2]([O-])=[O:21].[Na+]>O.N1C=CC=CC=1.C(O)(=O)C.[Ni]>[CH2:1]([O:3][C:4](=[O:19])[CH2:5][C:6]1[C:15]2[C:10](=[CH:11][C:12]([CH:16]=[O:21])=[CH:13][CH:14]=2)[CH:9]=[CH:8][C:7]=1[Cl:18])[CH3:2]

Participants

Conditions

Temperature: 100 °C

Procedure

(2-Chloro-6-cyano-naphthalen-1-yl)-acetic acid ethyl ester (1.39 g, 5.07 mmol) is dissolved in a mixture of water (17 ml), pyridine (33 ml) and glacial acetic acid (17 ml). Sodium hypophosphite (4.30 g, 40.62 mmol) and Raney nickel (3.2 g) are then added at RT. The reaction mixture is heated to 100° C. for 1 h. TLC analysis indicates complete consumption of starting material. The reaction mixture is cooled to RT and filtered through Celite. After addition of silica gel, the solvents are removed on a rotary evaporator. Purification by FCC (hexane/EtOAc 5:1) yields the title compound. 1H NMR (CDCl3, 400 MHz): δ 1.17 (t, J=8 Hz, 3H), 4.10 (q, J=8 Hz, 2H), 4.24 (s, 2H), 7.52 (d, J=10 Hz, 1H), 7.82 (d, J=10 Hz; 1H), 7.94-7.98 (m, 2H); 8.26 (s, 1H), 10.09 (s, 1H). ES−-MS: 275.2, 277.3 [M−H]−.

Workup

customconsumption of starting material
temperatureThe reaction mixture is cooled to RT
filtrationfiltered through Celite
additionAfter addition of silica gel
customthe solvents are removed on a rotary evaporator
customPurification by FCC (hexane/EtOAc 5:1)

Sources & evidence

ORD record: ord-f0de6e7233494d6f95a4e1d6d9cdf2f4
Source dataset: uspto-grants-2010_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07691861B2

Reaction notes

Loading…