1-Chloromethylnaphthalene → HCID 86643579, compound

HRID 877283Notes

Reaction equation

HRID 877283 reaction equation
Cl[CH2:2][C:3]1[C:12]2[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=2)[CH:6]=[CH:5][CH:4]=1.[Mg].B(OC)(OC)OC.Br[C:22]1[CH:29]=[CH:28][CH:27]=[CH:26][C:23]=1[CH:24]=[O:25].C(=O)([O-])[O-].[Na+].[Na+]>CCOCC.C1(P([Pd-4](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)C=CC=CC=1.C1(C)C=CC=CC=1>[CH:24]([C:23]1([C:4]2[CH:5]=[CH:6][C:7]3[C:12](=[CH:11][CH:10]=[CH:9][CH:8]=3)[C:3]=2[CH3:2])[CH:22]=[CH:29][CH:28]=[CH:27][CH2:26]1)=[O:25]

Participants

9

Reactant 5

HCID 68451-ChloromethylnaphthaleneHCID 8470Trimethyl borateHCID 10340Sodium CarbonateHCID 811292-BromobenzaldehydeHCID 5462224Magnesium

Product 1

HCID 86643579HCID 86643579, compound

Reagents, catalysts & solvents 3

HCID 178420553HCID 178420553, compoundCatalystHCID 1140TolueneSolventHCID 3283Diethyl EtherSolvent

Conditions

Temperature
-78 °C

Procedure

The corresponding Grignard compound is prepared from 88.3 g (500 mmol) of 1-chloromethylnaphthalene and 12.2 g (500 mmol) of magnesium in 500 ml of ether. After the Grignard solution has been cooled to −78° C., 59 ml (530 mmol) of trimethyl borate are added, the mixture is then allowed to warm to room temperature, the solvent is removed in vacuo, 500 ml of toluene, 92.5 g (500 mmol) of 2-bromobenzaldehyde, 2.9 g (2.5 mmol) of tetrakis(triphenylphosphino)palladium(0) and 300 ml of 2 M sodium carbonate solution are added to the residue, and the reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated off, washed twice with 500 ml of water each time, filtered through silica gel and then evaporated to dryness, and the residue is recrystallised from toluene/acetonitrile. Yield: 93.1 g (378 mmol), 75.6%, purity about 97% (NMR).

Workup

  1. temperatureto warm to room temperature
  2. additionare added to the residue
  3. temperaturethe reaction mixture is heated
  4. temperatureunder reflux for 16 h
  5. temperatureAfter cooling
  6. customthe organic phase is separated off
  7. washwashed twice with 500 ml of water each time
  8. filtrationfiltered through silica gel
  9. customevaporated to dryness
  10. customthe residue is recrystallised from toluene/acetonitrile

Sources & evidence

ORD record
ord-c9cd1f172a4e45e198d38347cc28a901
Source dataset
uspto-grants-2015_03
Patent number
US08986852B2

Reaction notes

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