Triphenylphosphine → 1-(4-Chloro-phenyl)-3-((Z)-3-tributylstannanyl-but-2-enyloxy)-1H-pyrazole
Reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH2:20]([Sn:24]([CH2:34][CH2:35][CH2:36][CH3:37])([CH2:30][CH2:31][CH2:32][CH3:33])/[C:25](/[CH3:29])=[CH:26]\[CH2:27][OH:28])[CH2:21][CH2:22][CH3:23].[Cl:38][C:39]1[CH:44]=[CH:43][C:42]([N:45]2[CH:49]=[CH:48][C:47](O)=[N:46]2)=[CH:41][CH:40]=1>C1COCC1>[Cl:38][C:39]1[CH:40]=[CH:41][C:42]([N:45]2[CH:49]=[CH:48][C:47]([O:28][CH2:27]/[CH:26]=[C:25](\[Sn:24]([CH2:20][CH2:21][CH2:22][CH3:23])([CH2:30][CH2:31][CH2:32][CH3:33])[CH2:34][CH2:35][CH2:36][CH3:37])/[CH3:29])=[N:46]2)=[CH:43][CH:44]=1Participants
Conditions
- Temperature
- -75 °C
Procedure
To 8.09 g (30.8 mmol) triphenylphosphine in 200 ml THF have been added with stirring at −75° C. 6.23 g (30.8 mmol) azodicarbonic acid diisopropyl ester. The mixture has been stirred at this temperature for 5 min. Then 10.39 g (28.8 mmol) (Z)-3-tributylstannanyl-but-2-en-1-ol have been added dropwise and stirred for 5 min at −75° C. After addition of 4.00 g (20.6 mmol) 1-(4-chlorophenyl)-3-hydroxypyrazole at −75° C. a red suspension was formed. The mixture was allowed to warm up to ambient temperature and stirred for 3 d. After removal of the solvents in vacuo 29 g oil have been collected and purified by chromatography on 120 g silica with MTBE/heptane. Yield 8.3 g (75%) oil. δ=0.85 (m); 0.95 (m); 1.30 (m); 1.50 m); 2.00 (s); 4.65 (d); 5.90 (d); 6.43 (t); 7.35 (d); 7.52 (d); 7.68 (d).
Workup
- stirringThe mixture has been stirred at this temperature for 5 min
- stirringstirred for 5 min at −75° C
- customwas formed
- temperatureto warm up to ambient temperature
- stirringstirred for 3 d
- customAfter removal of the solvents in vacuo 29 g oil
- customhave been collected
- custompurified by chromatography on 120 g silica with MTBE/heptane
Sources & evidence
- ORD record
- ord-f2857fa6d92942769975b8f6ba467ad6
- Source dataset
- uspto-grants-2016_03
- Patent number
- US09271501B2
Reaction notes
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