Sodium Carbonate → HCID 117602575, compound

HRID 1755504Notes

Reaction equation

HRID 1755504 reaction equation
Br[C:2]1[S:3][CH:4]=[CH:5][C:6]=1[C:7]1[CH:12]=[CH:11][C:10]([CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH3:20])=[CH:9][CH:8]=1.C([C:25]1(C)[C:30](O)=[C:29]([C:32]([CH3:35])(C)C)[CH:28]=[CH:27][CH2:26]1)(C)(C)C.C(=O)([O-])[O-].[Na+].[Na+].C(Cl)Cl.O.[CH3:47][C:48]([N:50]([CH3:52])C)=O>CC1C(P(C2C([CH2-])=CC=CC=2)C2C(C)=CC=CC=2)=CC=CC=1.CC1C(P(C2C([CH2-])=CC=CC=2)C2C(C)=CC=CC=2)=CC=CC=1.CC(O)=O.CC(O)=O.[Pd].[Pd]>[CH2:13]([C:10]1[CH:11]=[CH:12][C:7]([C:6]2[CH:5]=[CH:4][S:3][C:2]=2[CH:35]=[CH:32][C:29]2[CH:30]=[CH:25][C:26]([N:50]([C:48]3[CH:47]=[CH:12][CH:11]=[CH:10][CH:9]=3)[C:52]3[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=3)=[CH:27][CH:28]=2)=[CH:8][CH:9]=1)[CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH3:20]

Participants

7

Reactant 5

HCID 10340Sodium CarbonateHCID 31374Dimethylacetamide2×HCID 21908982Water methylene chlorideHCID 59558255HCID 59558255, compoundHCID 666371922,6-Di-t-butylcresol

Product 1

HCID 117602575HCID 117602575, compoundYield 79%

Reagents, catalysts & solvents 1

HCID 11104995trans-Bis(acetato)bis[2-[bis(2-methylphenyl)phosphino]benzyl]dipalladium(II)Catalyst

Conditions

Temperature
90 °C

Procedure

In a three necked flask under argon, are introduced, in successive order, 1.20 g (3.41 mmol, 1 eq.) of YKP69, 34 mg (1%) of the catalyst trans-di(μ-acetato)bis[o-(di-o-tolylphosphino)benzyl] dipalladium(II), 159 mg (20%) of 2,6-di-tert-butylcresol and 795 mg (2.2 eq.) of sodium carbonate. The whole, after dissolution in 25 mL of previously degassed DMAC, is heated to 90° C. A solution of 15 mL of DMAC containing 1.855 g (6.86 mmol, 2 eq.) of YKP21 is added drop by drop to the mixture. After the addition, the whole is heated to 140° C. and stirred for 24 h. The next day after cooling, the contents of the three necked flask are added to 200 mL of mixture of [CH2Cl2/water: 50/50]. The organic phase is washed successively with a 2 mol·L−1 HCl solution, with water, with a saturated NaCl solution then dried on Na2SO4. After filtration and evaporation, the crude product is purified on chromatography column on alumina with hexane. After this Heck reaction, 1.47 g of the compound YKP70 are obtained in the form of a yellow viscous solid (yield of 79.0%).

Workup

  1. additionAfter the addition
  2. temperaturethe whole is heated to 140° C.
  3. temperatureThe next day after cooling
  4. washThe organic phase is washed successively with a 2 mol·L−1 HCl solution, with water, with a saturated NaCl solution
  5. customthen dried on Na2SO4
  6. filtrationAfter filtration and evaporation
  7. customthe crude product is purified on chromatography column on alumina with hexane
  8. customAfter this Heck reaction, 1.47 g of the compound YKP70

Sources & evidence

ORD record
ord-4acefb10243f493291d9bb164c8ee0de
Source dataset
uspto-grants-2015_10
Patent number
US09171676B2

Reaction notes

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