Benzylamine → N-(7-methyl-1,4-dioxaspiro[4.5]dec-8-ylidene)-1-phenylmethanamine

HRID 1970976Notes

Reaction equation

HRID 1970976 reaction equation
CCN(CC)CC.[CH2:8]([NH2:15])[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.[CH3:16][CH:17]1[C:26](=O)[CH2:25][CH2:24][C:19]2([O:23][CH2:22][CH2:21][O:20]2)[CH2:18]1.CC(OC)(C)C>C(Cl)Cl.Cl[Ti](Cl)(Cl)Cl>[CH3:16][CH:17]1[C:26](=[N:15][CH2:8][C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)[CH2:25][CH2:24][C:19]2([O:20][CH2:21][CH2:22][O:23]2)[CH2:18]1

Participants

7

Reactant 4

HCID 7504BenzylamineHCID 8471TriethylamineHCID 15413tert-Butyl methyl etherHCID 2706287-Methyl-1,4-dioxaspiro[4.5]decan-8-one

Product 1

HCID 67536022N-(7-methyl-1,4-dioxaspiro[4.5]dec-8-ylidene)-1-phenylmethanamine

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 6344DichloromethaneSolvent2×

Procedure

To a solution of NEt3 (560 mL, 4.02 mol) and benzylamine (131 mL, 1.20 mol) in CH2Cl2 (500 mL) was added TiCl4 (500 mL of 1.0 M solution in CH2Cl2, 0.500 mol) over 30 min while the internal temperature was kept below −10° C. The resulting dark red suspension was stirred at −20° C. to −30° C. for 15 min, then a solution of 7-methyl-1,4-dioxaspiro[4.5]decan-8-one (170 g, 1.00 mmol) in CH2Cl2 (500 mL) was added at −10° C. The resulting grey-yellow suspension was allowed to warm to room temperature over 2 h, then stirred at room temperature for 16 h. MTBE (1.0 L) was added to the reaction mixture, and the yellow suspension was stirred at room temperature for 30 min and filtered through a pad of Solka Floc. The cake was washed with MTBE (4×500 mL), and the combined filtrates were concentrated to provide N-(7-methyl-1,4-dioxaspiro[4.5]dec-8-ylidene)-1-phenylmethanamine, which was used directly in the next step.

Workup

  1. customwas kept below −10° C
  2. stirringstirred at room temperature for 16 h
  3. stirringthe yellow suspension was stirred at room temperature for 30 min
  4. filtrationfiltered through a pad of Solka Floc
  5. washThe cake was washed with MTBE (4×500 mL)
  6. concentrationthe combined filtrates were concentrated

Sources & evidence

ORD record
ord-9c4e65b9df92429fa27ef8e2dcb0b653
Source dataset
uspto-grants-2013_04
Patent number
US08431569B2

Reaction notes

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