1,2-Dimethoxyethane → 1-Methyl-3-nitro-2-(3,3,5,5-tetramethylcyclohex-1-enyl)benzene

HRID 32189

Reaction equation

HRID 32189 reaction equation
CC1(C)C(C)(C)OB([C:9]2[CH2:14][C:13]([CH3:16])([CH3:15])[CH2:12][C:11]([CH3:18])([CH3:17])[CH:10]=2)O1.Br[C:21]1[C:26]([N+:27]([O-:29])=[O:28])=[CH:25][CH:24]=[CH:23][C:22]=1[CH3:30].P([O-])([O-])([O-])=O.[K+].[K+].[K+].COCCOC>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.O.C(OCC)(=O)C>[CH3:30][C:22]1[CH:23]=[CH:24][CH:25]=[C:26]([N+:27]([O-:29])=[O:28])[C:21]=1[C:9]1[CH2:14][C:13]([CH3:15])([CH3:16])[CH2:12][C:11]([CH3:18])([CH3:17])[CH:10]=1

Participants

8

Reactant 4

HCID 80711,2-DimethoxyethaneHCID 62657Potassium Phosphate, TribasicHCID 2318282-Bromo-3-nitrotolueneHCID 231420594,4,5,5-Tetramethyl-2-(3,3,5,5-tetramethylcyclohex-1-en-1-yl)-1,3,2-dioxaborolane

Product 1

HCID 231417171-Methyl-3-nitro-2-(3,3,5,5-tetramethylcyclohex-1-enyl)benzeneYield 99.9%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 4,4,5,5-tetramethyl-2-(3,3,5,5-tetramethylcyclohex-1-enyl)[1,3,2]dioxaborolane (3.96 g, 15 mmol) produced in Example (4b), 2-bromo-3-nitrotoluene (2.48 g, 11.5 mmol), tetrakis(triphenylphosphine)palladium(0) (1.33 g, 1.15 mmol), tripotassium phosphate (3.66 g, 17.3 mmol), 1,2-dimethoxyethane (30 mL) and water (10 mL) was stirred for 10 hours and 20 minutes at an external temperature of 80° C. under a nitrogen atmosphere. Ethyl acetate and water were added to the reaction mixture, and it was filtered through Celite. The filtrate was then extracted with ethyl acetate. The separated organic layer was washed with water and brine in that order and then dried over anhydrous magnesium sulfate. The desiccant was filtered off and the filtrate was concentrated under reduced pressure. The resultant residue was purified by NH silica gel column chromatography (hexane) to give 3.14 g of the title compound as a yellow oil.

Workup

  1. filtrationwas filtered through Celite
  2. extractionThe filtrate was then extracted with ethyl acetate
  3. washThe separated organic layer was washed with water and brine in that order
  4. dry with materialdried over anhydrous magnesium sulfate
  5. filtrationThe desiccant was filtered off
  6. concentrationthe filtrate was concentrated under reduced pressure
  7. customThe resultant residue was purified by NH silica gel column chromatography (hexane)

Sources & evidence

ORD record
ord-299819fdb16b49ff8fcf9fda975f7f35
Source dataset
uspto-grants-2008_09
Patent number
US07425554B2

Linked notes

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