Potassium Phosphate, Tribasic → 5-(3-Bromo-1,2,4-thiadiazol-5-yl)-2-[(1-methylethyl)oxy]benzonitrile

HRID 1942618Notes

Reaction equation

HRID 1942618 reaction equation
[CH3:1][CH:2]([O:4][C:5]1[CH:12]=[CH:11][C:10](B2OC(C)(C)C(C)(C)O2)=[CH:9][C:6]=1[C:7]#[N:8])[CH3:3].[Br:22][C:23]1[N:27]=[C:26](Cl)[S:25][N:24]=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+]>COCCOC.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>[Br:22][C:23]1[N:27]=[C:26]([C:10]2[CH:11]=[CH:12][C:5]([O:4][CH:2]([CH3:1])[CH3:3])=[C:6]([CH:9]=2)[C:7]#[N:8])[S:25][N:24]=1

Participants

7

Reactant 3

HCID 62657Potassium Phosphate, TribasicHCID 27250533-Bromo-5-chloro-1,2,4-thiadiazoleHCID 575060272-Isopropoxy-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzonitrile

Product 1

HCID 669817575-(3-Bromo-1,2,4-thiadiazol-5-yl)-2-[(1-methylethyl)oxy]benzonitrileYield 48.2%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolvent2×HCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
120 °C

Procedure

To a solution of 2-[(1-methylethyl)oxy]-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzonitrile (D39) (280 mg), 3-bromo-5-chloro-1,2,4-thiadiazole (194 mg) and tripotassium phosphate (517 mg) in 1,2-dimethoxyethane (DME) (4 mL) and water (1 mL) under nitrogen was added Pd(Ph3P)4 (113 mg). The reaction vessel was sealed and heated under microwave at 120° C. for 10 min. Water was added, the reaction mixture was filtered through the celite. The aqueous layer was extracted with EA for 3 times. the combined organic layers were washed with brine, dried over anhydrous sodium sulfate. The dried solution was concentrated and purified by column chromatography to give 5-(3-bromo-1,2,4-thiadiazol-5-yl)-2-[(1-methylethyl)oxy]benzonitrile (D44) (152 mg) as a white solid. MS (ES): C12H10BrN3OS requires 323. found 324.0 (M+H+).

Workup

  1. customThe reaction vessel was sealed
  2. filtrationthe reaction mixture was filtered through the celite
  3. extractionThe aqueous layer was extracted with EA for 3 times
  4. washthe combined organic layers were washed with brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationThe dried solution was concentrated
  7. custompurified by column chromatography

Sources & evidence

ORD record
ord-f1e5c5a11cc749eb91c1eba2da437af6
Source dataset
uspto-grants-2013_03
Patent number
US08389508B2

Reaction notes

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