tert-Butanol → HCID 90731614, compound

HRID 1800434Notes

Reaction equation

HRID 1800434 reaction equation
[CH:1]1([C:4]([NH:6][C:7]2[S:8][C:9]3[C:14]([N:15]=2)=[CH:13][CH:12]=[C:11]([O:16][C:17]2[CH:18]=[C:19]([CH:23]=[CH:24][C:25]=2[O:26][CH3:27])C(O)=O)[N:10]=3)=[O:5])[CH2:3][CH2:2]1.[CH3:28][C:29]([OH:32])([CH3:31])[CH3:30].C([N:35]([CH2:38]C)CC)C.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:47])C=CC=CC=1>CN(C)C=O.O>[C:29]([O:32][C:38](=[O:47])[NH:35][C:19]1[CH:23]=[CH:24][C:25]([O:26][CH3:27])=[C:17]([O:16][C:11]2[N:10]=[C:9]3[S:8][C:7]([NH:6][C:4]([CH:1]4[CH2:2][CH2:3]4)=[O:5])=[N:15][C:14]3=[CH:13][CH:12]=2)[CH:18]=1)([CH3:31])([CH3:30])[CH3:28]

Participants

7

Reactant 4

HCID 6386tert-ButanolHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 86645992HCID 86645992, compound

Product 1

HCID 90731614HCID 90731614, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
120 °C

Procedure

To a solution of 3-({2-[(cyclopropylcarbonyl)amino][1,3]thiazolo[5,4-b]pyridin-5-yl}oxy)-4-methoxybenzoic acid (1.92 g, 4.98 mmol) produced in Example C4(v) in N,N-dimethylformamide (50 mL) and 2-methylpropan-2-ol (50 mL) were added triethylamine (5 mL, 35.9 mmol) and diphenylphosphoryl azide (3 mL, 13.9 mmol), and the mixture was stirred at 120° C. for 2 hr. After cooling the reaction solution to room temperature, the reaction solution was diluted with water (200 mL). The yielded solid was collected by filtration to give tert-butyl[3-({2-[(cyclopropylcarbonyl)amino][1,3]thiazolo[5,4-b]pyridin-5-yl}oxy)-4-methoxyphenyl]carbamate (primary product, 1.16 g). The filtrate was extracted with ethyl acetate-hexane (1:1, 150 mL×3), and the combined organic layer was washed with saturated brine (150 mL), and dried over anhydrous magnesium sulfate. The insoluble material was filtered off, the filtrate was concentrated under reduced pressure, and the residue was subjected to silica gel column chromatography (ethyl acetate/hexane=2/98→80/20) to give tert-butyl[3-({2-[(cyclopropylcarbonyl)amino][1,3]thiazolo[5,4-b]pyridin-5-yl}oxy)-4-methoxyphenyl]carbamate (secondary product, 994 mg). These products contained structurally unknown impurities but used for the next reaction without further purification.

Workup

  1. temperatureAfter cooling the reaction solution to room temperature
  2. filtrationThe yielded solid was collected by filtration

Sources & evidence

ORD record
ord-42c037047a9d41efaf7731ec544cc6e4
Source dataset
uspto-grants-2013_01
Patent number
US08344135B2

Reaction notes

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