O-Xylene → HCID 66691917, compound

HRID 2176386Notes

Reaction equation

HRID 2176386 reaction equation
I[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH:8]1[C:16]2[C:15]3[CH:17]=[CH:18][CH:19]=[CH:20][C:14]=3[S:13][C:12]=2[C:11]([C:21]2[CH:33]=[CH:32][C:31]3[C:30]4[C:25](=[CH:26][C:27]([C:34]5[C:39]6[S:40][C:41]7[CH:46]=[CH:45][CH:44]=[CH:43][C:42]=7[C:38]=6[CH:37]=[CH:36][CH:35]=5)=[CH:28][CH:29]=4)[NH:24][C:23]=3[CH:22]=2)=[CH:10][CH:9]=1.CC(C)([O-])C.[Na+].C1(C)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.[Pd].C(P(C(C)(C)C)C(C)(C)C)(C)(C)C.C1(C)C=CC=CC=1>[CH:37]1[C:38]2[C:42]3[CH:43]=[CH:44][CH:45]=[CH:46][C:41]=3[S:40][C:39]=2[C:34]([C:27]2[CH:28]=[CH:29][C:30]3[C:31]4[C:23](=[CH:22][C:21]([C:11]5[C:12]6[S:13][C:14]7[CH:20]=[CH:19][CH:18]=[CH:17][C:15]=7[C:16]=6[CH:8]=[CH:9][CH:10]=5)=[CH:33][CH:32]=4)[N:24]([C:2]4[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=4)[C:25]=3[CH:26]=2)=[CH:35][CH:36]=1

Participants

8

Reactant 4

HCID 7237O-XyleneHCID 11575IodobenzeneHCID 23676156Sodium t-butoxideHCID 66691957HCID 66691957, compound

Product 1

HCID 66691917HCID 66691917, compoundYield 97.7%

Reagents, catalysts & solvents 3

HCID 83681Tris(1,1-dimethylethyl)phosphineCatalystHCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
120 °C

Procedure

In a 200-mL three-neck flask were mixed 0.7 g (4.3 mmol) of iodobenzene, 1.7 g (3.2 mmol) of 2,7-di-(dibenzothiophen-4-yl)-9H-carbazole, 0.6 g (5.5 mmol) of sodium tert-butoxide, and 36 mg (0.1 mmol) of bis(dibenzylideneacetone)palladium(0), and the air in the flask was replaced with nitrogen. Then, 5 mL of dehydrated xylene was added to this mixture. After the mixture was degassed while being stirred under reduced pressure, 0.7 mL (0.3 mmol) of tri(tert-butyl)phosphine (10 wt % hexane solution) was added to the mixture. This mixture was stirred at 120° C. for 5 hours in a nitrogen atmosphere to be reacted. After the reaction, 300 mL of toluene was added to this reaction mixture solution, and this suspension was filtered through Florisil and Celite. The resulting filtrate was concentrated, followed by purification by silica gel column chromatography (toluene as the developing solvent). The fraction thus obtained was concentrated, acetone and methanol were added thereto, and the mixture was irradiated with ultrasonic waves. Then, recrystallization gave 1.9 g of a white powder in 93% yield. The above synthesis method is illustrated in (E-8) below.

Workup

  1. customAfter the mixture was degassed
  2. additionwas added to the mixture
  3. customto be reacted
  4. additionwas added to this reaction mixture solution
  5. filtrationthis suspension was filtered through Florisil and Celite
  6. concentrationThe resulting filtrate was concentrated
  7. customfollowed by purification by silica gel column chromatography (toluene as the developing solvent)
  8. customThe fraction thus obtained
  9. concentrationwas concentrated
  10. additionacetone and methanol were added
  11. customthe mixture was irradiated with ultrasonic waves
  12. customThen, recrystallization

Sources & evidence

ORD record
ord-10895d7067094fcda3f1dbf2a4fa5cef
Source dataset
uspto-grants-2015_06
Patent number
US09065058B2

Reaction notes

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