Hydrochloric Acid → Uniconazole

HRID 1902989Notes

Reaction equation

HRID 1902989 reaction equation
[H-].[H-].[H-].[H-].[Li+].[Al+3].C(NC1C=CC=CC=1)C.[Cl:16][C:17]1[CH:22]=[CH:21][C:20](/[CH:23]=[C:24](/[N:31]2[CH:35]=[N:34][CH:33]=[N:32]2)\[C:25](=[O:30])[C:26]([CH3:29])([CH3:28])[CH3:27])=[CH:19][CH:18]=1.Cl>C(OCC)C.C(Cl)(Cl)Cl>[Cl:16][C:17]1[CH:22]=[CH:21][C:20](/[CH:23]=[C:24](/[N:31]2[CH:35]=[N:34][CH:33]=[N:32]2)\[CH:25]([OH:30])[C:26]([CH3:29])([CH3:28])[CH3:27])=[CH:19][CH:18]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 7670N-EthylanilineHCID 10913254(E)-1-(4-chlorophenyl)-2-(1,2,4-triazol-1-yl)-4,4-dimethyl-1-penten-3-oneHCID 21226445Aluminium lithium hydride

Product 1

HCID 6436604UniconazoleYield 29.6%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent4×HCID 6212ChloroformSolvent

Procedure

To a solution of 1.08 g (0.0284 mole) of LiAlH4 in 85 cc of ethyl ether, while being cooled in ice, was added dropwise 22 cc of an ether solution containing 6.86 g (0.0284 mole) of (+)-2-N-benzyl-N-methylamino-1-phenylethanol followed by 40 cc of an ether solution containing 6.90 g (0.0564 mole) of N-ethylaniline. After having been stirred at room temperature for 3 hours, the mixture was cooled to -78° C. To the mixture was added dropwise 55 cc of an ether solution containing 2.75 g (0.0095 mole) of (E)-1-(4-chlorphenyl)-2-(1,2,4-triazol-1-yl)-4,4-dimethyl-1-penten-3-one. The mixture was stirred at said temperature for 3 hours and left standing overnight at room temperature. To the mixture was then added 105 cc of 2 N hydrochloric acid to effect decomposition. The organic layer was separated, washed successively with 100 cc of a saturated aqueous sodium hydrogencarbonate solution and 100 cc of ice-cooled water, then dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain 2.83 g of a crude product: [α]D24 -6.44 (c=1.05, CHCl3). A 2.8 g portion of the crude product was recrystallized three times from a cyclohexane-methanol mixture to obtain 0.82 g of (-)-(E)-1-(4-chlorophenyl)-2-(1,2,4-triazol-1-yl)-4,4-dimethyl-1-penten-3-ol: [α]D24 -14.9 (c=1.0, CHCl3).

Workup

  1. temperaturethe mixture was cooled to -78° C
  2. stirringThe mixture was stirred
  3. customfor 3 hours
  4. waitleft
  5. waitstanding overnight at room temperature
  6. customThe organic layer was separated
  7. washwashed successively with 100 cc of a saturated aqueous sodium hydrogencarbonate solution and 100 cc of ice-
  8. temperaturecooled water
  9. dry with materialdried over anhydrous sodium sulfate
  10. concentrationconcentrated under reduced pressure
  11. customto obtain 2.83 g of a crude product
  12. customA 2.8 g portion of the crude product was recrystallized three times from a cyclohexane-methanol mixture

Sources & evidence

ORD record
ord-db25aeb8c0534de5af958196b6bc2ded
Source dataset
uspto-grants-1984_03
Patent number
US04435203

Reaction notes

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