P-Toluenesulfonylhydrazide → HCID 10459179, compound

HRID 2376233Notes

Reaction equation

HRID 2376233 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([C:8](=[CH:12][C:13]2[CH:17]=[C:16]([C:18]3[CH:23]=[CH:22][C:21]([Cl:24])=[C:20]([Cl:25])[CH:19]=3)[N:15]([C:26]3[CH:31]=[CH:30][C:29]([O:32][CH2:33][CH3:34])=[CH:28][CH:27]=3)[N:14]=2)[C:9]([OH:11])=[O:10])[CH:5]=[CH:6][CH:7]=1.S(NN)(C1C=CC(C)=CC=1)(=O)=O.CC([O-])=O.[Na+]>CCO.O>[Cl:1][C:2]1[CH:3]=[C:4]([CH:8]([CH2:12][C:13]2[CH:17]=[C:16]([C:18]3[CH:23]=[CH:22][C:21]([Cl:24])=[C:20]([Cl:25])[CH:19]=3)[N:15]([C:26]3[CH:27]=[CH:28][C:29]([O:32][CH2:33][CH3:34])=[CH:30][CH:31]=3)[N:14]=2)[C:9]([OH:11])=[O:10])[CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 3

HCID 15303P-ToluenesulfonylhydrazideHCID 517045Sodium AcetateHCID 68873573HCID 68873573, compound

Product 1

HCID 10459179HCID 10459179, compoundYield 23.1%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 962WaterSolvent2×

Conditions

Temperature
100 °C

Procedure

To a solution of 2-(3-chloro-phenyl)-3-[5-(3,4-dichloro-phenyl)-1-(4-ethoxy-phenyl)-1H-pyrazol-3-yl]-acrylic acid (Example 108, Step B; 0.043 g, 0.084 mmol) in EtOH (5 mL) was added tosylhydrazine (0.22 g, 1.2 mmol). To the light yellow solution was added a mixture of NaOAc (0.098 g, 1.2 mmol) in H2O (1 mL). The resulting mixture was heated to 100° C. overnight, then cooled to rt, diluted with H2O (10 mL), and extracted with CH2Cl2 (3×10 mL). The combined organic layers were dried (MgSO4) and then concentrated to provide a yellow oil. The oil was purified by preparative reversed-phase HPLC (acetonitrile/water) to afford the pure alkane as a colorless oil (10 mg, 23%). TLC (silica gel, 9:1 CH2Cl2/MeOH): Rf=0.43. HPLC: Rt=10.7 (Method A). MS (ESI): mass calculated for C26H21Cl3N2O3, 514.06; m/z found, 513 [M−H]−. 1H NMR (400 mHz, CDCl3): 7.32-7.23 (m, 6H), 7.14-7.10 (m, 2H), 6.92-6.89 (m, 1H), 6.88-6.85 (m, 2H), 6.23 (s, 1H), 4.03 (q, J=6.9 Hz, 2H), 4.04-4.00 (m, 1H), 3.50 (dd, J=6.7, 14.7 Hz, 1H), 3.09 (dd, J=8.7, 14.7 Hz, 1H), (1.42 (t, J=7.0 Hz, 3H),

Workup

  1. additionTo the light yellow solution was added
  2. temperaturecooled to rt
  3. extractionextracted with CH2Cl2 (3×10 mL)
  4. dry with materialThe combined organic layers were dried (MgSO4)
  5. concentrationconcentrated
  6. customto provide a yellow oil
  7. customThe oil was purified by preparative reversed-phase HPLC (acetonitrile/water)

Sources & evidence

ORD record
ord-82f3543820d04665a931b8cf24ca0b12
Source dataset
uspto-grants-2008_12
Patent number
US07465808B2

Reaction notes

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