Ethanol → 1,1-Dimethylethyl 5-ethoxy-3,4-dihydro-2(1H)-isoquinolinecarboxylate

HRID 1416358Notes

Reaction equation

HRID 1416358 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:17][CH2:16][C:15]2[C:10](=[CH:11][CH:12]=[CH:13][C:14]=2[OH:18])[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[C:19]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C[CH:20]=1.C(O)C.CCOC(/N=N/C(OCC)=O)=O>O1CCCC1.ClCCl.CO>[C:1]([O:5][C:6]([N:8]1[CH2:17][CH2:16][C:15]2[C:10](=[CH:11][CH:12]=[CH:13][C:14]=2[O:18][CH2:19][CH3:20])[CH2:9]1)=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

8

Reactant 4

HCID 702EthanolHCID 11776TriphenylphosphineHCID 5462977Diethyl azodicarboxylateHCID 10538586tert-Butyl 5-hydroxy-3,4-dihydroisoquinoline-2(1H)-carboxylate

Product 1

HCID 154342991,1-Dimethylethyl 5-ethoxy-3,4-dihydro-2(1H)-isoquinolinecarboxylate

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

2.1 g (8.43 mmol) of 2-t-butoxycarbonyl-5-hydroxy-1,2,3,4-tetrahydroisoquinoline (Example 7), 2.77 g (10.5 mmol) triphenylphosphine and 0.75 mL (12.6 mmol) ethanol were dissolved in dry tetrahydrofuran and 1.63 mL (10.5 mmol) diethylazodicarboxylate was added dropwise. After completion of the reaction (tlc, 1% MeOH), the mixture was diluted with dichloromethane, washed with aqueous sodium bicarbonate and with aqueous sodium chloride, evaporated to dryness and purified by silicagel chromathography (System B). Yield 1.55 g, 66%. 1H NMR (CDCl3): 7.12 (1H, t, 8.1 Hz), 6.69 (2H, t, 8.1 Hz), 4.55 (2H, s), 4.02 (2H, q, 6.8 Hz), 3.63 (2H, t, 5.6 Hz), 2.76 (2H, t, 5.9 Hz), 1.48 (9H, s), 1.41 (3H, t, 7.1 Hz).

Workup

  1. washwashed with aqueous sodium bicarbonate and with aqueous sodium chloride
  2. customevaporated to dryness
  3. custompurified by silicagel chromathography (System B)

Sources & evidence

ORD record
ord-2fc3de0a7c144fcc85ca49ec2a5a511e
Source dataset
uspto-grants-1999_06
Patent number
US05912342

Reaction notes

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