KPPh2 → HCID 11788120, compound

HRID 916890Notes

Reaction equation

HRID 916890 reaction equation
[CH:1]1[CH:6]=[CH:5][C:4]([P-:7][C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)=[CH:3][CH:2]=1.[K+].F[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=1[NH:22][C:23]1[C:28]([CH:29]([CH3:31])[CH3:30])=[CH:27][CH:26]=[CH:25][C:24]=1[CH:32]([CH3:34])[CH3:33]>O1CCOCC1>[C:8]1([P:7]([C:4]2[CH:3]=[CH:2][CH:1]=[CH:6][CH:5]=2)[C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=2[NH:22][C:23]2[C:28]([CH:29]([CH3:31])[CH3:30])=[CH:27][CH:26]=[CH:25][C:24]=2[CH:32]([CH3:34])[CH3:33])[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=1

Participants

4

Reactant 2

HCID 11042360KPPh2HCID 24895321HCID 24895321, compound

Product 1

HCID 11788120HCID 11788120, compound

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

A 250-mL Schlenk flask equipped with a condenser was flashed with nitrogen thoroughly. To this flask was added KPPh2 (73 mL, 0.5 M in THF solution, Aldrich, 36.9 mmol). THF was removed in vacuo and a solution of N-(2-fluorophenyl)-2,6-diisopropylaniline (10 g, 36.9 mmol) in 1,4-dioxane (40 mL) was added with a syringe. The transparent, ruby reaction solution was heated to reflux for 5 d, during which time the reaction condition was monitored by 31P {1H} NMR spectroscopy. All volatiles were removed from the resulting orange solution under reduced pressure and degassed deionized water (100 mL) was added. The product was extracted with deoxygenated dichloromethane (100 mL). The dichloromethane solution was separated from the aqueous layer, from which the product was further extracted with dichloromethane (20 mL×2). The combined organic solution was dried over MgSO4 and filtered. All volatiles were removed in vacuo to yield the product as pale yellow oil. The product was purified by washing it with boiling EtOH (10 mL×4) until it became white powder; yield 15.2 g (94%). 1H NMR (CDCl3, 200 MHz) δ 7.39 (m, 10, PC6H5), 7.0-7.22 (m, 4, Ar), 6.82 (m, 1, Ar), 6.65 (t, 1, Ar), 6.15 (m, 1, Ar), 5.95 (d, 1, JHP=8, NH), 2.90 (septet, 2, CHMe2), 1.06 (d, 6, CHMe2), 0.94 (d, 6, CHMe2). 1H NMR (C6D6, 200 MHz) δ 7.48 (m, 4, Ar), 6.60-7.15 (m, 10, Ar), 6.92 (m, 1, Ar), 6.59 (t, 1, Ar), 6.34 (m, 1, Ar), 6.26 (d, 1, JHP=8, NH), 3.13 (septet, 2, CHMe2), 1.09 (d, 6, CHMe2), 0.97 (d, 6, CHMe2). 31P{1H} NMR (C6D6, 202 MHz) δ−20.11. 31P{1H} NMR (Et2O, 121.5 MHz) δ−19.87. 31P{1H} NMR (CDCl3, 121.5 MHz) δ−20.17. 13C NMR (CDCl3, 75.3 MHz) δ 150.57 (J=17.1), 147.41, 135.35, 135.26, 135.24, 133.93 (JCP=19.6), 130.28, 128.92, 128.47 (JCP=7.5), 127.14, 123.70, 118.71, 117.63, 111.60, 28.18 (CHMe2), 24.40 (CHMe2), 23.03 (CHMe2). Anal. Calcd. for C30H32NP: C, 82.35; H, 7.37; N, 3.20. Found: C, 82.32; H, 7.36; N, 3.28.

Workup

  1. customA 250-mL Schlenk flask equipped with a condenser
  2. customTHF was removed in vacuo
  3. temperaturewas heated
  4. temperatureto reflux for 5 d, during which time the reaction condition
  5. customAll volatiles were removed from the resulting orange solution under reduced pressure
  6. customdegassed deionized water (100 mL)
  7. additionwas added
  8. extractionThe product was extracted with deoxygenated dichloromethane (100 mL)
  9. customThe dichloromethane solution was separated from the aqueous layer, from which the product
  10. extractionwas further extracted with dichloromethane (20 mL×2)
  11. dry with materialThe combined organic solution was dried over MgSO4
  12. filtrationfiltered
  13. customAll volatiles were removed in vacuo

Sources & evidence

ORD record
ord-c35a8c57ff7d43ceaa22d21c885b101d
Source dataset
uspto-grants-2007_09
Patent number
US07271276B2

Reaction notes

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