Aniline → HCID 57640776, compound

HRID 2111952Notes

Reaction equation

HRID 2111952 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH2:12][CH:11]([CH2:13][NH:14][C:15]([C:17]3[S:18][C:19]([Cl:22])=[CH:20][CH:21]=3)=[O:16])[O:10][N:9]=2)=[CH:4][CH:3]=1.[NH2:23][C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1.C([O-])([O-])=O.[Cs+].[Cs+].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>C1COCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[C:24]1([NH:23][C:2]2[CH:7]=[CH:6][C:5]([C:8]3[CH2:12][CH:11]([CH2:13][NH:14][C:15]([C:17]4[S:18][C:19]([Cl:22])=[CH:20][CH:21]=4)=[O:16])[O:10][N:9]=3)=[CH:4][CH:3]=2)[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1

Participants

7

Reactant 4

HCID 6115AnilineHCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 11582095HCID 11582095, compound

Product 1

HCID 57640776HCID 57640776, compound

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 8028TetrahydrofuranSolvent

Procedure

Aryl Bromide (Example 1, 100 mg, 0.25 mmol), aniline (27 uL, 0.30 mmol), Cs2CO3 (163 mg, 0.50 mmol) and Xantphos (43 mg, 0.075 mmol) were diluted with 4 mL of degassed THF. The resulting suspension was degassed for an additional 3 min then Pd2 (dba)3 (23 mg, 0.25 mmol) was added giving a dark violet suspension which became dark yellow-orange within a few minutes. The mixture was then refluxed overnight, changing to cloudy orange as the aryl bromide was consumed. The next day the mixture was partitioned with water and ethyl acetate, separated, and the organic layer extracted twice with ethyl acetate. The combined organic layers were dried over MgSO4, filtered, concentrated and purified by preparative HPLC affording the desired product as a white powder. MS found for C21H18ClN3O2S as (M+H)+ 412.0, 414.0.

Workup

  1. customThe resulting suspension was degassed for an additional 3 min
  2. customgiving a dark violet suspension which
  3. waitbecame dark yellow-orange within a few minutes
  4. temperatureThe mixture was then refluxed overnight
  5. customwas consumed
  6. customThe next day the mixture was partitioned with water and ethyl acetate
  7. customseparated
  8. extractionthe organic layer extracted twice with ethyl acetate
  9. dry with materialThe combined organic layers were dried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated
  12. custompurified by preparative HPLC

Sources & evidence

ORD record
ord-9a8a54c315eb40969e10f5618bb91554
Source dataset
uspto-grants-2009_04
Patent number
US07521470B2

Reaction notes

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