Butylamine → (E)-N-ethyl-6,6-dimethyl-N-[[3-[(4-thiophen-3-ylthiophen-2-yl)methoxy]phenyl]methyl]hept-2-en-4-yn-1-amine

HRID 1756309Notes

Reaction equation

HRID 1756309 reaction equation
Cl/[CH:2]=[CH:3]/[CH2:4][N:5]([CH2:8][C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([O:15][CH2:16][C:17]2[S:18][CH:19]=[C:20]([C:22]3[CH:26]=[CH:25][S:24][CH:23]=3)[CH:21]=2)[CH:10]=1)[CH2:6][CH3:7].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(N)CCC.[C:51]([C:55]#[CH:56])([CH3:54])([CH3:53])[CH3:52]>[Cu]I.[Pd](Cl)Cl.O1CCCC1>[CH3:52][C:51]([CH3:54])([CH3:53])[C:55]#[C:56]/[CH:2]=[CH:3]/[CH2:4][N:5]([CH2:8][C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([O:15][CH2:16][C:17]2[S:18][CH:19]=[C:20]([C:22]3[CH:26]=[CH:25][S:24][CH:23]=3)[CH:21]=2)[CH:10]=1)[CH2:6][CH3:7]

Participants

8

Reactant 4

HCID 8007ButylamineHCID 11776TriphenylphosphineHCID 135123,3-Dimethyl-1-butyneHCID 19917480HCID 19917480, compound

Product 1

HCID 6443223(E)-N-ethyl-6,6-dimethyl-N-[[3-[(4-thiophen-3-ylthiophen-2-yl)methoxy]phenyl]methyl]hept-2-en-4-yn-1-amineYield 72%

Reagents, catalysts & solvents 3

HCID 24290Palladium ChlorideCatalystHCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8028TetrahydrofuranSolvent

Procedure

To 10 ml of tetrahydrofuran were added 1.01 g (2.5 mmol) of (E)-N-(3-chloro-2-propenyl)-N-ethyl-3-[4-(3-thienyl)-2-thienylmethyoxy]benzylamine, 23.8 mg (0.125 mmol) of copper (I) iodide, 8.9 mg (0.05 mmol) of palladium chloride and 26.2 mg (0.1 mmol) of triphenylphosphine, and further, 0.50 ml (5.0 mmol) of n-butylamine and 0.37 ml (3.0 mmol) of tert-butylacetylene under ice cooling. The mixture was stirred for 17 hours at room temperature, and extracted with a mixture of 70 ml of ethyl acetate and 30 ml of water. The organic layer was separated, washed with a mixture of 40 ml of water and 4 ml of 2N hydrochloric acid, a mixture of 40 ml of water and 6 ml of saturated sodium bicarbonate aqueous solution and 20 ml of saturated sodium chloride aqueous solution and then dried over anhydrous magnesium sulfate. After ethyl acetate was evaporated under reduced pressure, the residue was treated with 3 ml of methanol, and stirred for 17 hours under ice cooling. The resulting crystals were collected by filtration, washed with 2 ml of methanol and dried under reduced pressure to obtain 0.81 g (yield: 72%) of the above identified compound as slightly yellowish brown crystalline powder.

Workup

  1. extractionextracted with a mixture of 70 ml of ethyl acetate and 30 ml of water
  2. customThe organic layer was separated
  3. washwashed with a mixture of 40 ml of water and 4 ml of 2N hydrochloric acid
  4. additiona mixture of 40 ml of water and 6 ml of saturated sodium bicarbonate aqueous solution and 20 ml of saturated sodium chloride aqueous solution
  5. dry with materialdried over anhydrous magnesium sulfate
  6. customAfter ethyl acetate was evaporated under reduced pressure
  7. additionthe residue was treated with 3 ml of methanol
  8. stirringstirred for 17 hours under ice cooling
  9. filtrationThe resulting crystals were collected by filtration
  10. washwashed with 2 ml of methanol
  11. customdried under reduced pressure
  12. customto obtain 0.81 g (yield: 72%) of the

Sources & evidence

ORD record
ord-b0aed7a0d23b42f6b998153404e89b10
Source dataset
uspto-grants-1995_08
Patent number
US05440049

Reaction notes

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