Diphenylmethylidenehydrazine → HCID 57635766, compound

HRID 2109921Notes

Reaction equation

HRID 2109921 reaction equation
I[C:2]1[CH:3]=[C:4]([CH3:10])[CH:5]=[CH:6][C:7]=1[O:8][CH3:9].[C:11](=[N:24][NH2:25])([C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.CC([O-])(C)C.[Na+]>C1(C)C=CC=CC=1.CCOC(C)=O.O.CC([O-])=O.CC([O-])=O.[Pd+2].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2>[CH3:9][O:8][C:7]1[CH:6]=[CH:5][C:4]([CH3:10])=[CH:3][C:2]=1[NH:25][N:24]=[C:11]([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1

Participants

9

Reactant 3

HCID 79304DiphenylmethylidenehydrazineHCID 1427263-Iodo-4-methoxytolueneHCID 23676156Sodium t-butoxide

Product 1

HCID 57635766HCID 57635766, compoundYield 95.4%

Reagents, catalysts & solvents 5

HCID 167845palladium(II) acetateCatalystHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)CatalystHCID 962WaterSolventHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
85 °C

Procedure

To a stirred, degassed suspension of 3-iodo-4-methoxytoluene (19.84 g, 80 mmol, 1 equiv), benzophenone hydrazone (17.99 g, 88 mmol, 1.1 equiv), Xantphos (93 mg, 0.16 mmol, 0.2 mol %), and Pd(OAc)2 (36 mg, 0.16 mmol, 0.2 mol %) in anhydrous toluene (96 mL) was added NaOtBu (11.09 g, 112 mmol, 1.4 equiv) in one portion at rt. The mixture was heated to 85° C. and stirred for 12 h. The reaction mixture was cooled, diluted with 200 mL EtOAc and 100 mL water, then the layers separated. The insoluble Pd residues were separated as the aqueous layer was removed. The organic phase was washed 2×100 mL water, then brine, and dried over Na2SO4. The solution was concentrated under reduced pressure, giving an orange-yellow solid. The solid was triturated in 50 mL MeOH, collected via filtration, and washed with 50 mL MeOH. Drying under suction gave the title compound as a yellow solid (24.16 g, 95% yield). 1H NMR (400 MHz, DMSO-d6) δ 2.25 (s, 3H), 3.56 (s, 3H), 6.53 (dd, 1H), 6.72 (d, 1H), 7.30 (m, 6H), 7.46 (d, 2H), 7.56 (m, 1H), 7.62 (m, 2H), 7.79 (s, 1H). ES-MS m/z 317.1 (MH+); HPLC RT (min) 4.26.

Workup

  1. customTo a stirred, degassed
  2. temperatureThe reaction mixture was cooled
  3. customthe layers separated
  4. customThe insoluble Pd residues were separated as the aqueous layer
  5. customwas removed
  6. washThe organic phase was washed 2×100 mL water
  7. dry with materialbrine, and dried over Na2SO4
  8. concentrationThe solution was concentrated under reduced pressure
  9. customgiving an orange-yellow solid
  10. customThe solid was triturated in 50 mL MeOH
  11. filtrationcollected via filtration
  12. washwashed with 50 mL MeOH
  13. customDrying under suction

Sources & evidence

ORD record
ord-7a6d5602b77c4a5893d8a76a188eeb0d
Source dataset
uspto-grants-2009_04
Patent number
US07517878B2

Reaction notes

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