1-Butanol → 2,1,3-Benzothiadiazole

HRID 1050706

Reaction equation

HRID 1050706 reaction equation
Br[C:2]1[C:10]2[C:6](=[N:7][S:8][N:9]=2)[C:5](Br)=[CH:4][CH:3]=1.C1(N(C2C=CC(B(O)O)=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(=O)([O-])[O-].[Na+].[Na+].C(O)CCC>O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1(C)C=CC=CC=1>[N:7]1[S:8][N:9]=[C:10]2[CH:2]=[CH:3][CH:4]=[CH:5][C:6]=12

Participants

8

Reactant 4

HCID 2631-ButanolHCID 10340Sodium CarbonateHCID 6263614,7-Dibromo-2,1,3-benzothiadiazoleHCID 121669344-(Diphenylamino)phenylboronic Acid (contains varying amounts of Anhydride)

Product 1

HCID 675022,1,3-Benzothiadiazole

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolvent2×HCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of 4,7-dibromobenzo[2,1,3]thiadiazole (13.2 g, 45 mmol), 4-(N,N-diphenylamino)phenylboronic acid (30.0 g, 104 mmol), a solution of sodium carbonate (21.2 g, 200 mmol) in water (80 mL), tetrakis(triphenylphosphine)palladium(0) (5.0 g, 4.3 mmol), n-butanol (800 mL), and toluene (400 mL) was stirred under argon and heated at 100° C. for 20 hours. After cooling to room temperature, the mixture was diluted with water (600 mL) and stirred for 2 hours. Finally, the reaction mixture was extracted with toluene (2 L), and the volatiles were removed under reduced pressure. The residue was chromatographed using silica gel and hexane/dichloromethane (1:1) as an eluent to give 26.96 g (43.3 mmol, 96%) of 4,7-bis[(N,N-diphenylamino)phenyl)]benzo[2,1,3]thiadiazole (Intermediate M).

Workup

  1. temperatureAfter cooling to room temperature
  2. extractionFinally, the reaction mixture was extracted with toluene (2 L)
  3. customthe volatiles were removed under reduced pressure
  4. customThe residue was chromatographed

Sources & evidence

ORD record
ord-367db1714ccb420ea4bf501fceef4da4
Source dataset
uspto-grants-2016_07
Patent number
US09382424B2

Linked notes

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