Dabco → HCID 86739438, compound

HRID 544697Notes

Reaction equation

HRID 544697 reaction equation
[OH-].[K+].[Cl:3][C:4]1[CH:9]=[C:8]([NH:10][CH:11]([CH:15]([CH3:17])[CH3:16])[C:12]([OH:14])=[O:13])[CH:7]=[CH:6][C:5]=1[C:18]([F:21])([F:20])[F:19].C1N2CCN(CC2)C1.CC1C=CC(S(O[CH2:41][C:42]2[C:47]3[CH2:48][CH2:49][CH2:50][C:51]4[CH:56]=[CH:55][CH:54]=[CH:53][C:52]=4[C:46]=3[CH:45]=[CH:44][CH:43]=2)(=O)=O)=CC=1>O.CCCCCCC.C(#N)C>[Cl:3][C:4]1[CH:9]=[C:8]([NH:10][CH:11]([CH:15]([CH3:17])[CH3:16])[C:12]([O:14][CH2:41][C:42]2[C:47]3[CH2:48][CH2:49][CH2:50][C:51]4[CH:56]=[CH:55][CH:54]=[CH:53][C:52]=4[C:46]=3[CH:45]=[CH:44][CH:43]=2)=[O:13])[CH:7]=[CH:6][C:5]=1[C:18]([F:19])([F:20])[F:21]

Participants

8

Reactant 4

HCID 9237DabcoHCID 14797Potassium HydroxideHCID 20038950HCID 20038950, compoundHCID 86739439HCID 86739439, compound

Product 1

HCID 86739438HCID 86739438, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolvent2×HCID 6342AcetonitrileSolventHCID 8900HeptaneSolvent

Procedure

A solution of potassium hydroxide (1.03 grams, 0.016 mole) in water (6.0 ml) was added to a stirred mixture of 2-(2-chloro-α,α,α-trifluoro-p-toluidino)-3-methylbutyric acid (4.62 grams, 0.016 mole, prepared by the method of C. A. Henrick, et al., Pest. Sci. 11, 224-41 (1980) in n-heptane (75.0 ml). The mixture was stirred until all the acid dissolved, at which time the water was distilled from the mixture. Additional n-heptane (50.0 ml) was added, followed by a solution of 1,4-diazobicyclo[2.2.2]octane (0.12 gram, 0.00097 mole) and (6,7-dihydro-5H-dibenzo[a,c]cycloheptene-4-yl)methyl p-methylphenylsulfonate in acetonitrile (40.0 ml). After complete addition, the mixture was stirred and heated at reflux for approximately 18 hours. The mixture was cooled, then evaporated to dryness under reduced pressure to leave a residue. The residue was partitioned between diethyl ether (250 ml) and water (150 ml) and the phases separated. The organic phase was washed in succession with aqueous 2% hydrochloric acid (two 50 ml portions), water (two 25 ml portions), aqueous 10% sodium carbonate (two 25 ml portions), and saturated aqueous sodium chloride (25 ml). The washed organic phase was dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated under reduced pressure to leave an oil. The oil was purified by column chromatography on silica gel (250 grams), n-heptane:toluene (30:70) as the eluant, to yield (6,7-dihydro-5H-dibenzo[a,c]cyclohepten-4-yl)methyl 2-(2-chloro-α,α,α-trifluoro-p-toluidino)-3-methylbutyrate (4.95 grams) as an oil.

Workup

  1. customprepared by the method of C
  2. distillationwas distilled from the mixture
  3. additionAdditional n-heptane (50.0 ml) was added
  4. additionAfter complete addition
  5. stirringthe mixture was stirred
  6. temperatureheated
  7. temperatureat reflux for approximately 18 hours
  8. temperatureThe mixture was cooled
  9. customevaporated to dryness under reduced pressure
  10. customto leave a residue
  11. customThe residue was partitioned between diethyl ether (250 ml) and water (150 ml)
  12. customthe phases separated
  13. washThe organic phase was washed in succession with aqueous 2% hydrochloric acid (two 50 ml portions), water (two 25 ml portions), aqueous 10% sodium carbonate (two 25 ml portions), and saturated aqueous sodium chloride (25 ml)
  14. dry with materialThe washed organic phase was dried over anhydrous magnesium sulfate
  15. filtrationfiltered
  16. customthe filtrate evaporated under reduced pressure
  17. customto leave an oil
  18. customThe oil was purified by column chromatography on silica gel (250 grams), n-heptane:toluene (30:70) as the eluant

Sources & evidence

ORD record
ord-5cef4042724e419a92ba7f48c86e78a5
Source dataset
uspto-grants-1984_05
Patent number
US04451484

Reaction notes

Loading…