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Dimethylformamide → (2-Chloro-7-cyano-naphthalen-1-yl)-acetic acid ethyl ester

HRID 1992628
Notes
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Reaction equation

HRID 1992628 reaction equation
[CH2:1]([O:3][C:4](=[O:25])[CH2:5][C:6]1[C:15]2[C:10](=[CH:11][CH:12]=[C:13](OS(C(F)(F)F)(=O)=O)[CH:14]=2)[CH:9]=[CH:8][C:7]=1[Cl:24])[CH3:2].[CH3:26][N:27](C=O)C>C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd].[C-]#N.[Zn+2].[C-]#N>[CH2:1]([O:3][C:4](=[O:25])[CH2:5][C:6]1[C:15]2[C:10](=[CH:11][CH:12]=[C:13]([C:26]#[N:27])[CH:14]=2)[CH:9]=[CH:8][C:7]=1[Cl:24])[CH3:2]
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

5

Reactant 2

HCID 6228DimethylformamideHCID 86623472(2-Chloro-7-trifluoromethanesulfonyloxy-naphthalen-1-yl)-acetic acid ethyl ester

Product 1

HCID 66869743(2-Chloro-7-cyano-naphthalen-1-yl)-acetic acid ethyl ester

Reagents, catalysts & solvents 2

HCID 11186Zinc cyanide (Zn(CN)2)Catalyst
HCID 11979704
Tetrakis(triphenylphosphine)palladium
Catalyst

Conditions

Temperature
125 °C

Procedure

(2-Chloro-7-trifluoromethanesulfonyloxy-naphthalen-1-yl)-acetic acid ethyl ester (9.30 g, 23.43 mmol) is dissolved in DMF (80 ml) under an atmosphere of argon. Palladium(0) tetrakis(triphenylphosphane) (1.08 g, 0.9375 mmol) and zinc(II) cyanide (5.50 g, 46.87 mmol) are added. The reaction mixture is heated to 125° C. After 1 h, TLC analysis indicates complete consumption of starting material. The suspension is cooled to RT and poured onto water. After stirring for 15 minutes, filtration and concentration affords the crude reaction product. Purification by FCC (hexane/EtOAc 4:1) affords the title compound. 1H NMR (CDCl3, 400 MHz): δ 1.26 (t, J=8.8 Hz, 3H), 4.19 (q, J=8.8 Hz, 2H), 4.28 (s, 2H), 7.62-7.66 (m, 2H), 7.79 (d, J=9.9 Hz, 1H), 7.92 (d, J=9.9 Hz, 1H), 8.32 (s, 1H). ES+−MS; 274.2 [M+H]+.

Workup

  1. customconsumption of starting material
  2. temperatureThe suspension is cooled to RT
  3. additionpoured onto water
  4. filtrationfiltration and concentration
  5. customaffords the crude
  6. customreaction product
  7. customPurification by FCC (hexane/EtOAc 4:1)

Sources & evidence

ORD record
ord-9f5ed786440c4f19ad76588bd9c8e4eb
Source dataset
uspto-grants-2010_01
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US07648989B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes