Putrescine → 3-Butylcyclohexanone

HRID 1390700Notes

Reaction equation

HRID 1390700 reaction equation
P(OC)(OC)OC.[CH2:8]([Li])[CH2:9][CH2:10][CH3:11].[C:13]1(=[O:19])[CH2:18][CH2:17][CH2:16][CH:15]=[CH:14]1.N[CH2:21][CH2:22][CH2:23][CH2:24]N.[C:26](OC(=O)C)(=[O:28])[CH3:27]>C(OCC)C.CCCCCC>[CH2:8]([CH:15]1[CH2:16][CH2:17][CH2:18][C:13](=[O:19])[CH2:14]1)[CH2:9][CH2:10][CH3:11].[C:26]([CH:14]1[CH:15]([CH2:21][CH2:22][CH2:23][CH3:24])[CH2:16][CH2:17][CH2:18][C:13]1=[O:19])(=[O:28])[CH3:27]

Participants

9

Reactant 5

HCID 1045PutrescineHCID 7918Acetic AnhydrideHCID 8472Trimethyl phosphiteHCID 135942-Cyclohexen-1-oneHCID 178418339Butyllithium

Product 2

HCID 5661933-ButylcyclohexanoneHCID 11310101Cyclohexanone, 2-acetyl-3-butyl-

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent2×HCID 8058HexaneSolvent

Procedure

To 30 ml of anhydrous diethyl ether were added 1.5 g (10 mmol) of cuprous bromide and 2.5 g (20 mmol) of trimethyl phosphite, and the mixture stirred for about 1 hour at room temperature in an atmosphere of nitrogen. The mixture was cooled to -78° C., and 12.8 ml (20 mmol) of a 15% by weight hexane solution of n-butyllithium was added, followed by further stirring the mixture for 30 minutes. Then, 960 mg (10 mmol) of 2-cyclohexenone was added and reacted for 1 hour. After the reaction, 5 ml of tetramethylenediamine was added, and the mixture was stirred for about 10 minutes. The resulting solution was added dropwise at 0° C. to a solution prepared by adding 2.84 g (20 mmol) of a boron trifluoride-diethyl ether complex and 2.04 g (20 mmol) of acetic anhydride to 20 ml of anhydrous diethyl ether, and stirring the mixture at 0° C. for about 30 minutes in an atmosphere of nitrogen. Then, the mixture was stirred for an additional 3 hours at room temperature, and then, post-treated, extracted, washed with dilute hydrochloric acid, and dried in the same way as in Example 4 to afford 5.432 g of a crude product. The crude product was purified by distillation at reduced pressure to afford 370 mg (2.4 mmol) of 3-n-butylcyclohexanone in a yield of 24% and 170 mg (0.9 mmol) of 2-acetyl-3-n-butylcyclohexanone in a yield of 9%.

Workup

  1. temperatureThe mixture was cooled to -78° C.
  2. stirringby further stirring the mixture for 30 minutes
  3. customreacted for 1 hour
  4. additionwas added
  5. stirringthe mixture was stirred for about 10 minutes
  6. additionThe resulting solution was added dropwise at 0° C. to a solution
  7. customprepared
  8. stirringstirring the mixture at 0° C. for about 30 minutes in an atmosphere of nitrogen
  9. stirringThen, the mixture was stirred for an additional 3 hours at room temperature
  10. additionpost-treated
  11. extractionextracted
  12. washwashed with dilute hydrochloric acid
  13. customdried in the same way as in Example 4
  14. customto afford 5.432 g of a crude product
  15. distillationThe crude product was purified by distillation at reduced pressure

Sources & evidence

ORD record
ord-c7ef4dea631346e88a53728bca6cb464
Source dataset
uspto-grants-1979_02
Patent number
US04139717

Reaction notes

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