p-(2-(Dimethylamino)ethoxy)benzaldehyde → 2-[p-[(E)-2-(3,4-dihydro-4,4-dimethyl-2H--benzothiopyran-6-yl)propenyl]phenoxy]-N,N-dimethylethylamine

HRID 1463422Notes

Reaction equation

HRID 1463422 reaction equation
[Br-].[CH3:2][C:3]1([CH3:34])[C:12]2[C:7](=[CH:8][CH:9]=[C:10]([CH:13]([P+](C3C=CC=CC=3)(C3C=CC=CC=3)C3C=CC=CC=3)[CH3:14])[CH:11]=2)[S:6][CH2:5][CH2:4]1.C([Li])CCC.[CH3:40][N:41]([CH3:53])[CH2:42][CH2:43][O:44][C:45]1[CH:52]=[CH:51][C:48]([CH:49]=O)=[CH:47][CH:46]=1>O1CCCC1>[CH3:34][C:3]1([CH3:2])[C:12]2[CH:11]=[C:10](/[C:13](/[CH3:14])=[CH:49]/[C:48]3[CH:51]=[CH:52][C:45]([O:44][CH2:43][CH2:42][N:41]([CH3:40])[CH3:53])=[CH:46][CH:47]=3)[CH:9]=[CH:8][C:7]=2[S:6][CH2:5][CH2:4]1

Participants

5

Reactant 3

HCID 84823p-(2-(Dimethylamino)ethoxy)benzaldehydeHCID 19935432[1-(4,4-Dimethyl-6-thiochromanyl)ethyl]triphenylphosphonium bromideHCID 178418339Butyllithium

Product 1

HCID 677834662-[p-[(E)-2-(3,4-dihydro-4,4-dimethyl-2H--benzothiopyran-6-yl)propenyl]phenoxy]-N,N-dimethylethylamineYield 44.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

32 g of [1-(4,4-dimethyl-6-thiochromanyl)ethyl]triphenylphosphonium bromide were suspended in 130 ml of tetrahydrofuran and treated at 0° C. with 37 ml of n-butyllithium (1.6 molar in hexane). After stirring at 0° C. for 45 minutes, a solution of 10 g of 4-(2-dimethylaminoethoxy)benzaldehyde in 60 ml of tetrahydrofuran was added dropwise to the orange reaction mixture. The mixture was stirred at room temperature for an additional 1 hour, poured on to ice/water and extracted with ether. The organic phases were washed with water, dried and evaporated. After filtration of the crude product over neutral Alox (eluting agent ether) and recrystallization from hexane/ether, there were obtained 8.7 g of 2-[p-[(E)-2-(3,4-dihydro-4,4-dimethyl-2H-1-benzothiopyran-6-yl)propenyl]phenoxy]-N,N-dimethylethylamine, melting point 81°-82° C.

Workup

  1. stirringThe mixture was stirred at room temperature for an additional 1 hour
  2. extractionextracted with ether
  3. washThe organic phases were washed with water
  4. customdried
  5. customevaporated
  6. filtrationAfter filtration of the crude product
  7. washover neutral Alox (eluting agent ether) and recrystallization from hexane/ether

Sources & evidence

ORD record
ord-28026b00c7de472ab3b68feed16f84b2
Source dataset
uspto-grants-1994_04
Patent number
US05300522

Reaction notes

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