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Allyltributylstannane → 4-Allyl-2-chloro-5-(2,3-difluoro-6-methoxybenzyl-oxy)-1-nitrobenzene

HRID 1513012
Notes
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Reaction equation

HRID 1513012 reaction equation
Br[C:2]1[C:7]([O:8][CH2:9][C:10]2[C:15]([O:16][CH3:17])=[CH:14][CH:13]=[C:12]([F:18])[C:11]=2[F:19])=[CH:6][C:5]([N+:20]([O-:22])=[O:21])=[C:4]([Cl:23])[CH:3]=1.[CH2:24]([Sn](CCCC)(CCCC)CCCC)[CH:25]=[CH2:26]>O1CCOCC1.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>[CH2:26]([C:2]1[C:7]([O:8][CH2:9][C:10]2[C:15]([O:16][CH3:17])=[CH:14][CH:13]=[C:12]([F:18])[C:11]=2[F:19])=[CH:6][C:5]([N+:20]([O-:22])=[O:21])=[C:4]([Cl:23])[CH:3]=1)[CH:25]=[CH2:24]
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

5

Reactant 2

HCID 90628AllyltributylstannaneHCID 685153834-Bromo-2-chloro-5-(2,3-difluoro-6-methoxybenzyloxy)-1-nitrobenzene

Product 1

HCID 685148014-Allyl-2-chloro-5-(2,3-difluoro-6-methoxybenzyl-oxy)-1-nitrobenzene

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalyst
HCID 31275
1,4-Dioxane
Solvent

Conditions

Temperature
120 °C

Procedure

To a solution of 4-bromo-2-chloro-5-(2,3-difluoro-6-methoxybenzyloxy)-1-nitrobenzene (0.82 g) in 1,4-dioxane (40 mL) were added allyltri(n-butyl)tin (0.74 mL) and tetrakis(triphenylphosphine)palladium(0) (0.46 g), and the reaction vessel was equipped with a reflux condenser, and the reaction mixture was stirred at 120° C. under an argon atmosphere overnight. The reaction mixture was cooled to room temperature, and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate=9/1−3/1) to give 4-allyl-2-chloro-5-(2,3-difluoro-6-methoxybenzyl-oxy)-1-nitrobenzene (0.68 g). This material was dissolved in tetrahydrofuran (20 mL). To the solution were added water (10 mL), 50% aqueous N-methylmorpholine-N-oxide solution (0.96 mL) and osmium(VIII) oxide, microencapsulated (about 10%, 0.23 g), and the mixture was stirred at room temperature for 4 days. The reaction mixture was poured into water, and the resulting mixture was extracted with ethyl acetate. The extract was washed with brine, and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure, and the residue was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate=2/1−1/4) to give 2-chloro-5-(2,3-difluoro-6-methoxybenzyloxy)-4-(2,3-dihydroxy-propyl)-1-nitrobenzene (0.29 g). The title compound was prepared in a similar manner to that described in Reference Example 170 using this material instead of 2-chloro-5-(2,3-difluoro-6-methoxybenzyloxy)-4-(1,3-dihydroxy-2-propoxy)-1-nitrobenzene.

Workup

  1. customthe reaction vessel was equipped with a reflux condenser
  2. temperatureThe reaction mixture was cooled to room temperature
  3. concentrationconcentrated under reduced pressure
  4. customThe residue was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate=9/1−3/1)

Sources & evidence

ORD record
ord-17f82b5a8b324958809f9605bc37c4e8
Source dataset
uspto-grants-2012_07
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08217069B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes