1,3-Propanediol → HCID 23087153, compound

HRID 2423614Notes

Reaction equation

HRID 2423614 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5](O)=[C:4]([N+:9]([O-:11])=[O:10])[CH:3]=1.FC(F)(F)S(OC1C=CC(F)=CC=1[N+]([O-])=O)(=O)=O.[CH3:30][O:31][C:32]1[CH:33]=[C:34]2[C:39](=[CH:40][CH:41]=1)[CH:38]=[C:37](B(O)O)[CH:36]=[CH:35]2.C(O)CCO.S([O-])([O-])(=O)=O.[Mg+2]>C(OCC)C.O1CCCC1>[F:1][C:2]1[CH:7]=[CH:6][C:5]([CH:37]2[CH2:36][CH2:35][C:34]3[C:39](=[CH:40][CH:41]=[C:32]([O:31][CH3:30])[CH:33]=3)[CH2:38]2)=[C:4]([N+:9]([O-:11])=[O:10])[CH:3]=1

Participants

8

Reactant 5

HCID 104421,3-PropanediolHCID 24083Sulfuric acid magnesium salt (1:1)HCID 1362364-Fluoro-2-nitrophenolHCID 46416926-Methoxy-2-naphthaleneboronic acidHCID 23087233HCID 23087233, compound

Product 1

HCID 23087153HCID 23087153, compoundYield 64.4%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

Synthesized from 4-fluoro-2-nitrophenol (3.0 g) according to an analogous synthetic method to Preparation Example 80 described below, 4-fluoro-2-nitrophenyl trifluoromethanesulfonate (5.5 g) was obtained. To a suspension of (6-methoxynaphthalen-2-yl)boronic acid (2.5 g) in diethyl ether (60 ml) was added 1,3-propanediol (0.9 ml), and the solution was stirred for 2 hours at room temperature. Tetrahydrofuran and anhydrous magnesium sulfate were sequentially added thereto, the solution was stirred, then filtered, and the filtrate was concentrated in vacuo. To a solution of the resulting 2-(6-methoxynaphthalen-2-yl)-[1,3,2]dioxaborinane (3.1 g) and 4-fluoro-2-nitrophenyl trifluoromethanesulfonate (2.8 g) in N,N-dimethylformamide (50 ml) were added tetrakis(triphenylphosphine)palladium(0) (350 mg) and cesium carbonate (6.0 g), and the solution was stirred for 2 hours at 100° C. under a nitrogen atmosphere. Ethyl acetate and tetrahydrofuran were sequentially added thereto, the solution was stirred, then insoluble material was removed by filtration, the solution was extracted with ethyl acetate, then sequentially washed with water and brine, dried over anhydrous magnesium sulfate, then the solvent was evaporated in vacuo, the resulting solid was washed with a hexane-diethyl ether system to provide 2-(4-fluoro-2-nitrophenyl)-6-methoxy-1,2,3,4-tetrahydronaphthalene (2.4 g). The total amount of this compound was used according to an analogous synthetic method to Example 22 to provide the title compound (1.6 g).

Workup

  1. customaccording to an analogous synthetic method to Preparation Example 80
  2. customwas obtained
  3. stirringthe solution was stirred
  4. filtrationfiltered
  5. concentrationthe filtrate was concentrated in vacuo
  6. additionTo a solution of the resulting 2-(6-methoxynaphthalen-2-yl)-[1,3,2]dioxaborinane (3.1 g) and 4-fluoro-2-nitrophenyl trifluoromethanesulfonate (2.8 g) in N,N-dimethylformamide (50 ml) were added tetrakis(triphenylphosphine)palladium(0) (350 mg) and cesium carbonate (6.0 g)
  7. stirringthe solution was stirred for 2 hours at 100° C. under a nitrogen atmosphere
  8. additionEthyl acetate and tetrahydrofuran were sequentially added
  9. stirringthe solution was stirred
  10. custominsoluble material was removed by filtration
  11. extractionthe solution was extracted with ethyl acetate
  12. washsequentially washed with water and brine
  13. dry with materialdried over anhydrous magnesium sulfate
  14. customthe solvent was evaporated in vacuo
  15. washthe resulting solid was washed with a hexane-diethyl ether system

Sources & evidence

ORD record
ord-e2211a00586d4ecc84d2538abccc6178
Source dataset
uspto-grants-2011_06
Patent number
US07960412B2

Reaction notes

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