Sodium Bicarbonate → HCID 57336962, compound

HRID 2403650Notes

Reaction equation

HRID 2403650 reaction equation
Cl.[C:2]([NH:6]/[N:7]=[C:8]1/[CH:9]=[CH:10][C:11]2([CH2:27][CH2:28]/1)[CH2:16][CH2:15][N:14]([C:17]([O:19][CH2:20][C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)=[O:18])[CH2:13][CH2:12]2)([CH3:5])([CH3:4])[CH3:3].C(=O)(O)[O-].[Na+]>ClCCl>[C:2]([NH:6]/[N:7]=[C:8]1/[CH:9]=[CH:10][C:11]2([CH2:27][CH2:28]/1)[CH2:12][CH2:13][N:14]([C:17]([O:19][CH2:20][C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)=[O:18])[CH2:15][CH2:16]2)([CH3:5])([CH3:3])[CH3:4]

Participants

4

Reactant 2

HCID 516892Sodium BicarbonateHCID 57337174HCID 57337174, compound

Product 1

HCID 57336962HCID 57336962, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

(E)-benzyl 9-(2-tert-butylhydrazono)-3-azaspiro[5.5]undec-7-ene-3-carboxylate hydrochloride salt (8.00 g, 19.7 mmol) was dissolved in dichloromethane (100 mL) and treated with sodium bicarbonate (1.70 g, 19.7 mmol). The solution was stirred for 30 minutes and was then filtered and concentrated under reduced pressure to yield (E)-benzyl 9-(2-tert-butylhydrazono)-3-azaspiro[5.5]undec-7-ene-3-carboxylate. A 250 mL round bottom flask was charged with dimethylformamide (80 mL) and cooled to 0° C. Phosphorous oxychloride (5.51 mL, 59.1 mmol) was added dropwise over 2 minutes, and the solution was stirred for 30 minutes at 0° C. To this solution was added the (E)-benzyl 9-(2-tert-butylhydrazono)-3-azaspiro[5.5]undec-7-ene-3-carboxylate in dimethylformamide (15 mL) and the reaction was heated at 80° C. for 18 hours. The reaction was cooled to room temperature and concentrated under reduced pressure. The resultant oil was dissolved in ethyl acetate (500 mL) and washed with brine (2×150 mL). The aqueous layer was extracted with an additional 100 mL ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and concentrated. The resultant oil was purified by flash column chromatography (10-80% ethyl acetate/heptane) to yield 4.89 g (65%) of the title compound as a pale yellow oil. +ESI (M+H) 380.0; 1H NMR (400 MHz, CDCl3, δ): 7.25-7.36 (m, 5 H), 7.18 (s, 1 H), 6.57 (d, J=10.0 Hz, 1 H), 5.86 (d, J=10.0 Hz, 1 H), 5.12 (s, 2 H), 3.51-3.69 (m, 2 H), 3.36-3.53 (m, 2 H), 2.58 (s, 2 H), 1.59-1.74 (m, 2 H), 1.52-1.58 (m, 9 H), 1.41-1.53 (m, 2 H).

Workup

  1. filtrationwas then filtered
  2. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-296a0a6ba94748c5b070bbd907a88035
Source dataset
uspto-grants-2014_08
Patent number
US08802688B2

Reaction notes

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