Hydrochloric Acid → (Z)-3-(4-methoxyphenyl)-3-(3-pyridinyl)-2-propenal

HRID 1110551Notes

Reaction equation

HRID 1110551 reaction equation
[CH3:1][O:2][C:3]1[CH:16]=[CH:15][C:6]([C:7]([C:9]2[CH:10]=[N:11][CH:12]=[CH:13][CH:14]=2)=O)=[CH:5][CH:4]=1.C(NC(C)C)(C)C.C([Li])CCC.Cl.[CH2:30]([O:32]P(Cl)(=O)OCC)[CH3:31]>CCCCCC.C(N=CC)(C)(C)C.O1CCCC1>[CH3:1][O:2][C:3]1[CH:16]=[CH:15][C:6](/[C:7](/[C:9]2[CH:10]=[N:11][CH:12]=[CH:13][CH:14]=2)=[CH:31]/[CH:30]=[O:32])=[CH:5][CH:4]=1

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 7912DiisopropylamineHCID 13139Diethyl chlorophosphateHCID 32108(4-Methoxyphenyl)-3-pyridinylmethanoneHCID 178418339Butyllithium

Product 1

HCID 14994117(Z)-3-(4-methoxyphenyl)-3-(3-pyridinyl)-2-propenal

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolventHCID 138901N-Ethylidene-2-methylpropan-2-amineSolvent

Procedure

The compounds were prepared according to the procedure described in Example 84 except that the reaction was worked up after 17 hours. The following reagents were used: 3-(4-methoxybenzoyl)pyridine (22 g), diisopropylamine (32.2 mL), 1.55M n-butyl lithium in hexane (148 mL), acetaldehyde N-tert-butylimine (14.75 mL), diethylchlorophosphonate (16.6 mL) and tetrahydrofuran (200 mL). The work up, varied only in that the hydrolysis step was done by treating the intermediate imine with 2N HCl (300 ml) for 9 hours at 70° C. furnished, after basification and extraction, 24 g of crude material made up of a mixture of (E)-3-(4-methoxyphenyl)-3-(3-pyrdinyl)-2-propenal and (Z)-3-(4-methoxyphenyl)-3-(3-pyridinyl)-2-propenal. Purification of the crude by HPLC (ether; 3 recycles) provided 5.45 g of the less polar aldehyde, (E)-3-(4-methoxyphenyl)-3-(3-pyridinyl)-2-propenal along with 11 g of the isomer (Z)-3-(4-methoxyphenyl)-3-(3-pyridinyl)-2-propenal as oils.

Workup

  1. customThe compounds were prepared
  2. customThe work up, varied only in that the hydrolysis step
  3. customfurnished
  4. extractionafter basification and extraction, 24 g of crude material
  5. additionmade up of a mixture of (E)-3-(4-methoxyphenyl)-3-(3-pyrdinyl)-2-propenal and (Z)-3-(4-methoxyphenyl)-3-(3-pyridinyl)-2-propenal
  6. customPurification of the crude by HPLC (ether; 3 recycles)

Sources & evidence

ORD record
ord-fb022968e5e54523997717b40c3bd400
Source dataset
uspto-grants-1990_12
Patent number
US04975438

Reaction notes

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