O-Xylene → HCID 66691917, compound

HRID 2278681Notes

Reaction equation

HRID 2278681 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 under a nitrogen atmosphere at 120° C. for 5 hours 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 using silica gel column chromatography (the developing solvent was toluene). 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. A reaction scheme of the above synthesis method is shown in the following (B-2).

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
  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-f075ba3d6fa14a359dfca6d32ec8eeec
Source dataset
uspto-grants-2015_09
Patent number
US09133173B2

Reaction notes

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