1,1,3,3-Tetramethylguanidine → (3E)-3-[[3,5-dimethyl-4-(phenylmethoxy)phenyl]methylene]-1,4-dioxaspiro[4.5]decan-2-one

HRID 642907

Reaction equation

HRID 642907 reaction equation
[Cl-].[Li+].[CH2:3]([O:10][C:11]1[C:18]([CH3:19])=[CH:17][C:14]([CH:15]=O)=[CH:13][C:12]=1[CH3:20])[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.C(OP([CH:29]1[C:33](=[O:34])[O:32][C:31]2([CH2:39][CH2:38][CH2:37][CH2:36][CH2:35]2)[O:30]1)(=O)OCC)C.CN(C)C(=N)N(C)C>O1CCCC1.C(OC)(C)(C)C>[CH3:20][C:12]1[CH:13]=[C:14](/[CH:15]=[C:29]2\[C:33](=[O:34])[O:32][C:31]3([CH2:39][CH2:38][CH2:37][CH2:36][CH2:35]3)[O:30]\2)[CH:17]=[C:18]([CH3:19])[C:11]=1[O:10][CH2:3][C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1

Participants

7

Reactant 4

HCID 664601,1,3,3-TetramethylguanidineHCID 433294Lithium ChlorideHCID 5635574-(Benzyloxy)-3,5-dimethylbenzaldehydeHCID 59259703Diethyl(3-oxo-1,4-dioxaspiro[4.5]dec-2-yl)-phosphonate

Product 1

HCID 59259697(3E)-3-[[3,5-dimethyl-4-(phenylmethoxy)phenyl]methylene]-1,4-dioxaspiro[4.5]decan-2-one

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 15413tert-Butyl methyl etherSolvent

Conditions

Temperature
-20 °C

Procedure

4.2 g lithium chloride (0.1 Mol), 20.0 g (83.2 mmol) of 4-benzyloxy-3,5-dimethylbenzaldehyde (D) and 31.62 g (108.2 mmol) of diethyl (3-oxo-1,4-dioxaspiro[4.5]dec-2-yl)-phosphonate (C) are suspended in 130 mL tetrahydrofuran and cooled to −20° C. At this temperature 12.5 mL (0.1 Mol) tetramethylguanidine are added dropwise. After the addition has ended the suspension formed is heated to ambient temperature and stirred for 1 hour. After the addition of 190 mL tert.butyl-methylether the organic phase is washed with 150 mL water and 30 mL saturated saline solution, dried and evaporated down. The resulting yellow oil is taken up in 145 mL methanol and stirred intensively for 1 hour at −10° C., during which time a white solid is formed. The solid formed is suction filtered, washed twice with 20 mL methanol/water (1:1) and dried at 45° C. Yield: 26.0 g (86% of theory)

Workup

  1. additionAfter the addition
  2. customformed
  3. temperatureis heated to ambient temperature
  4. washis washed with 150 mL water and 30 mL saturated saline solution
  5. customdried
  6. customevaporated down
  7. stirringstirred intensively for 1 hour at −10° C., during which time a white solid
  8. customis formed
  9. customThe solid formed
  10. filtrationfiltered
  11. washwashed twice with 20 mL methanol/water (1:1)
  12. customdried at 45° C

Sources & evidence

ORD record
ord-16fd93c7bd8a42bfa0db4fd191f28a52
Source dataset
uspto-grants-2010_04
Patent number
US07696346B2

Linked notes

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