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2,8,9-Triisobutyl-2,5,8,9-tetraaza-1-phosphabicyclo(3.3.3)undecane → 4-(4-Methyl-2-(2-propylthiazolo[5,4-b]pyridin-7-ylamino)phenylthio)phenol

HRID 607148
Notes
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Reaction equation

HRID 607148 reaction equation
C(N1CCN2CCN(CC(C)C)P1N(CC(C)C)CC2)C(C)C.CC(C)([O-])C.[Na+].Cl[C:31]1[CH:36]=[CH:35][N:34]=[C:33]2[S:37][C:38]([CH2:40][CH2:41][CH3:42])=[N:39][C:32]=12.[NH2:43][C:44]1[CH:49]=[C:48]([CH3:50])[CH:47]=[CH:46][C:45]=1[S:51][C:52]1[CH:57]=[CH:56][C:55]([OH:58])=[CH:54][CH:53]=1>C1(C)C=CC=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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH3:50][C:48]1[CH:47]=[CH:46][C:45]([S:51][C:52]2[CH:57]=[CH:56][C:55]([OH:58])=[CH:54][CH:53]=2)=[C:44]([NH:43][C:31]2[CH:36]=[CH:35][N:34]=[C:33]3[S:37][C:38]([CH2:40][CH2:41][CH3:42])=[N:39][C:32]=23)[CH:49]=1
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

7

Reactant 4

HCID 45712432,8,9-Triisobutyl-2,5,8,9-tetraaza-1-phosphabicyclo(3.3.3)undecane2×HCID 23676156Sodium t-butoxideHCID 668081234-(2-Amino-4-methyl-phenylsulfanyl)-phenolHCID 668084877-Chloro-2-propyl-thiazolo[5,4-b]pyridine

Product 1

HCID 250106684-(4-Methyl-2-(2-propylthiazolo[5,4-b]pyridin-7-ylamino)phenylthio)phenol
Yield 8.3%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst2×HCID 1140TolueneSolvent

Procedure

A dry nitrogen-purged flask was charged with 2,8,9-triisobutyl-2,5,8,9-tetraaza-1-phospha-bicyclo[3.3.3]undecane (40.4 mg, 0.118 mmol), tris(dibenzylideneacetone)-dipalladium (27 mg, 0.0295 mmol), and sodium tert-butoxide (87.7 mg, 0.885 mmol). A solution of the product of Example 5G (125.5 mg, 0.590 mmol) in anhydrous toluene (5 mL) was added via syringe, followed by the product from Example 6c (136 mg, 0.590 mmol). The reaction was heated at reflux in a preheated 110° oil bath for 14 hours, cooled to room temperature, treated with additional 2,8,9-triisobutyl-2,5,8,9-tetraaza-1-phospha-bicyclo[3.3.3]undecane (40.4 mg) and tris(dibenzylideneacetone)dipalladium (27 mg), and heated at reflux for an additional 7 hours. The reaction was cooled to room temperature and the solvent removed by rotary evaporation in vacuo. Purification by silica gel flash chromatography with a gradient of 15% to 30% ethyl acetate/methylene chloride gave impure material. Purification by silica gel flash chromatography with a gradient of 1% to 2% methanol/methylene chloride afforded the desired title compound as a light yellow solid (20 mg, 0.049 mmol, 8%). 1H NMR (300 MHz, DMSO-D6) δ ppm: 1.03 (t, J=7.35 Hz, 3H) 1.76-1.94 (m, 2H) 2.31 (s, 3H) 3.10 (t, J=7.35 Hz, 2H) 5.76 (s, 1H) 6.67-6.73 (m, 2H) 6.96-7.04 (m, 1H) 7.08-7.14 (m, 1H) 7.20 (d, J=8.46 Hz, 2H) 7.29 (s, 1H) 8.14 (d, J=5.52 Hz, 1H) 8.55 (s, 1H) 9.73 (s, 1H); MS (DCI/NH3) m/z 408 (M+H)+.

Workup

  1. customA dry nitrogen-purged flask
  2. temperatureThe reaction was heated
  3. temperatureat reflux in a preheated 110° oil bath for 14 hours
  4. temperatureheated
  5. temperatureat reflux for an additional 7 hours
  6. temperatureThe reaction was cooled to room temperature
  7. customthe solvent removed by rotary evaporation in vacuo
  8. customPurification by silica gel flash chromatography with a gradient of 15% to 30% ethyl acetate/methylene chloride
  9. customgave impure material
  10. customPurification by silica gel flash chromatography with a gradient of 1% to 2% methanol/methylene chloride

Sources & evidence

ORD record
ord-6751c4f4919640af8d19829422dd6ad5
Source dataset
uspto-grants-2011_03
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US07915411B2

Reaction notes

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