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Triethylamine → methyl 2-(4-methylbenzyloxy)-6,7-dihydro-5H-benzocycloheptene-8-carboxylate

HRID 1169321
Notes
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Reaction equation

HRID 1169321 reaction equation
[CH3:1][C:2]1[CH:25]=[CH:24][C:5]([CH2:6][O:7][C:8]2[CH:23]=[CH:22][C:11]3[CH2:12][CH2:13][CH2:14][CH:15]([C:18]([O:20][CH3:21])=[O:19])[C:16](=O)[C:10]=3[CH:9]=2)=[CH:4][CH:3]=1.[BH4-].[Na+].C(N(CC)CC)C.CS(Cl)(=O)=O.C1CCN2C(=NCCC2)CC1>ClCCl.CO.O>[CH3:1][C:2]1[CH:3]=[CH:4][C:5]([CH2:6][O:7][C:8]2[CH:23]=[CH:22][C:11]3[CH2:12][CH2:13][CH2:14][C:15]([C:18]([O:20][CH3:21])=[O:19])=[CH:16][C:10]=3[CH:9]=2)=[CH:24][CH:25]=1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

9

Reactant 5

HCID 8471TriethylamineHCID 31297Methanesulfonyl chlorideHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 4311764Sodium borohydrideHCID 22990087methyl 3-(4-methylbenzyloxy)-5-oxo-6,7,8,9-tetrahydro-5H-benzocycloheptene-6-carboxylate

Product 1

HCID 22990047
methyl 2-(4-methylbenzyloxy)-6,7-dihydro-5H-benzocycloheptene-8-carboxylate
Yield 91%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-40 °C

Procedure

To methyl 3-(4-methylbenzyloxy)-5-oxo-6,7,8,9-tetrahydro-5H-benzocycloheptene-6-carboxylate (2.77 g, 8.19 mmol) dissolved in a mixed solvent of dichloromethane (40 ml) and methanol (10 ml) was added at −40° C. (inner temperature) sodium borohydride (465 mg, 12.3 mmol), and the resulting mixture was stirred at −20° C. to −10° C. for 2 hours. The reaction mixture was cooled to −40° C., was mixed with water (20 ml) and extracted with dichloromethane (40 ml, 10 ml×2). The combined organic layers were dried with anhydrous magnesium sulfate and were then concentrated under reduced pressure. To the residue dissolved in THF (30 ml) were added at 0° C. triethylamine (5.70 ml, 40.9 mmol) and methanesulfonyl chloride (0.95 ml, 12.3 mmol), and the resulting mixture was stirred at room temperature for 12 hours. In order to complete the reaction, DBU (3.67 ml, 24.5 mmol) and dichloromethane (30 ml) were added, and the resulting mixture was stirred at room temperature for 3 hours. The reaction mixture was concentrated under reduced pressure, was mixed with water (30 ml) and was extracted with ethyl acetate (30 ml×3). The combined organic layers were washed with 1 N hydrochloric acid (5 ml×3), were dried with anhydrous magnesium sulfate and were then concentrated under reduced pressure, and the residue was subjected to column chromatography (silica gel: 60 g, ethyl acetate/hexane=1/30→1/9). The objective fractions were concentrated under reduced pressure to obtain methyl 2-(4-methylbenzyloxy)-6,7-dihydro-5H-benzocycloheptene-8-carboxylate (2.40 g, 7.44 mmol, 91%).

Workup

  1. extractionextracted with dichloromethane (40 ml, 10 ml×2)
  2. dry with materialThe combined organic layers were dried with anhydrous magnesium sulfate
  3. concentrationwere then concentrated under reduced pressure
  4. dissolutionTo the residue dissolved in THF (30 ml)
  5. stirringthe resulting mixture was stirred at room temperature for 12 hours
  6. additionwere added
  7. stirringthe resulting mixture was stirred at room temperature for 3 hours
  8. concentrationThe reaction mixture was concentrated under reduced pressure
  9. additionwas mixed with water (30 ml)
  10. extractionwas extracted with ethyl acetate (30 ml×3)
  11. washThe combined organic layers were washed with 1 N hydrochloric acid (5 ml×3)
  12. dry with materialwere dried with anhydrous magnesium sulfate
  13. concentrationwere then concentrated under reduced pressure
  14. concentrationThe objective fractions were concentrated under reduced pressure

Sources & evidence

ORD record
ord-762a7d153a874ea89409d385abd7c018
Source dataset
uspto-grants-2003_09
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US06627651B1

Reaction notes

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