Nitric Acid → 3-(3-Chloro-1,4-dihydronaphthalen-2-yl)-2-methylacrylic acid

HRID 1527708Notes

Reaction equation

HRID 1527708 reaction equation
[Cl:1][C:2]1[C:3](/[CH:16]=[C:17](\[CH3:21])/[C:18]([OH:20])=[O:19])=[C:4]([O:14]C)[C:5]2[C:10]([C:11]=1[O:12]C)=[CH:9][CH:8]=[CH:7][CH:6]=2.[N+]([O-])(O)=O.O>O1CCOCC1.C(Cl)Cl>[Cl:1][C:2]1[C:11](=[O:12])[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[C:4](=[O:14])[C:3]=1/[CH:16]=[C:17](\[CH3:21])/[C:18]([OH:20])=[O:19]

Participants

6

Reactant 3

HCID 944Nitric AcidHCID 962WaterHCID 46180319(E)-3-(3-chloro-1,4-dimethoxynaphthalen-2-yl)-2-methylpropenoic acid

Product 1

HCID 252354263-(3-Chloro-1,4-dihydronaphthalen-2-yl)-2-methylacrylic acid

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 312751,4-DioxaneSolvent

Procedure

Following a modified procedure by Snyder et al.,33 dimethoxynaphthalene 42a (0.146 g, 0.476 mmol) and Ag(II)O (0.434 g, 3.51 mmol) were combined in a 5 mL round bottom flask and suspended in dioxane (1.5 mL). To the black suspension was added 6 M HNO3 (1.0 mL, 6.0 mmol) at room temperature. The black Ag(II)O quickly dissolved with gas evolution resulting in a yellow solute with yellow precipitate. The reaction was stirred for 10 minutes at room temperature and TLC showed no starting material present. The suspension was first filtered and the filter cake was suspended in CH2Cl2, treated with water, separated, washed with brine, dried, filtered, and condensed. The yellow reaction filtrate was likewise diluted with CH2Cl2, treated with water, separated, washed with brine, dried over MgSO4, filtered, and condensed. The filter cake provided pure 43a that was then purified by recrystallization from acetone/hexane (0.0601 g, 0.22 mmol, 47%). The filtrate provided a less pure 43a that was first purified by flash chromatography (1:4 EtOAc:hexanes 0.5% AcOH) and then recrystallized from acetone/hexane (0.027 g, 0.099 mmol, 21%).

Workup

  1. customwere combined in a 5 mL round bottom flask
  2. customresulting in a yellow solute with yellow precipitate
  3. filtrationThe suspension was first filtered
  4. additiontreated with water
  5. customseparated
  6. washwashed with brine
  7. customdried
  8. filtrationfiltered
  9. customcondensed
  10. customseparated
  11. washwashed with brine
  12. dry with materialdried over MgSO4
  13. filtrationfiltered
  14. customcondensed

Sources & evidence

ORD record
ord-ed345b420931443a9ed27b5eb41efd2f
Source dataset
uspto-grants-2015_07
Patent number
US09089605B2

Reaction notes

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