Reaction #1193173

ord-dd40096dcadc499ea0ced13881c75567

Reaction equation

COC(=O)CC(C)=O
methyl acetoacetate
C=CC(C)(C)O
3-methyl-but-1-en-3-ol
C=CC(C)(O)CCC=C(C)C
linalool
COC(=O)CC(C)=O
methyl acetoacetate
C=CC(C)(C)O
3-methyl-but-1-en-3-ol
CC(C)[O-].CC(C)[O-].CC(C)[O-].[Al+3]
aluminum isopropylate
→
CC(=O)CC/C=C(\C)CCC=C(C)C
geranylacetone
C=CC(C)(C)O
3-methyl-but-1-en-3-ol
CC(=O)CCC=C(C)C
2-methyl-hept-2-en-6-one

Reactants

COC(=O)CC(C)=O
methyl acetoacetate
C=CC(C)(C)O
3-methyl-but-1-en-3-ol
C=CC(C)(O)CCC=C(C)C
linalool
COC(=O)CC(C)=O
methyl acetoacetate
C=CC(C)(C)O
3-methyl-but-1-en-3-ol
CC(C)[O-].CC(C)[O-].CC(C)[O-].[Al+3]
aluminum isopropylate

Reagents

None

Conditions

Temperature
165°CELSIUS
Detailed conditions
See reaction.notes.procedure_details.

Workup

  1. 1
    workup.ADDITIONwere added dropwise in the course of 10 hours
  2. 2
    Temperaturewhilst maintaining a reaction temperature of 165° C.
  3. 3
    Otherbeing kept at about 100° C
  4. 4
    OtherAfter a further 4 hours' reaction time at 165° C.
  5. 5
    workup.DISTILLATIONthe mixture was worked up by distillation

Procedure

A mixture of 637 g of linalool (91% pure), 36 g of methyl acetoacetate, 6 g of 3-methyl-but-1-en-3-ol and 8.6 g of aluminum isopropylate was heated to 165° C. in the apparatus described in Example 12, and 642 g of methyl acetoacetate and 211 g of 3-methyl-but-1-en-3-ol were added dropwise in the course of 10 hours whilst maintaining a reaction temperature of 165° C., the temperature at the 2nd theoretical plate being kept at about 100° C. After a further 4 hours' reaction time at 165° C., the mixture was worked up by distillation. 681 g of geranylacetone, 212 g of 2-methyl-hept-2-en-6-one and 37 g of unconverted 3-methyl-but-1-en-3-ol were obtained. The selectivities achieved are accordingly as follows: 87% based on 3-methyl-but-1-en-3-ol, 94%, based on linalool, and 88%, based on methyl acetoacetate.

Source

DOI: 10.6084/m9.figshare.5104873.v1Patent: US04310705uspto-grants-1982_01