Benzophenone → HCID 10585855, compound

HRID 437113Notes

Reaction equation

HRID 437113 reaction equation
[C:1]1([CH:7]2[C:16]3[C:11](=[CH:12][CH:13]=[CH:14][CH:15]=3)[C:10](=O)[CH2:9][CH2:8]2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C(C1C=CC=CC=1)(=O)C1C=CC=CC=1.[CH3:32][NH2:33]>C1C=CC=CC=1.[Ti](Cl)(Cl)(Cl)Cl>[CH3:32][N:33]=[C:10]1[C:11]2[C:16](=[CH:15][CH:14]=[CH:13][CH:12]=2)[CH:7]([C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)[CH2:8][CH2:9]1

Participants

6

Reactant 3

HCID 3102BenzophenoneHCID 6329MethylamineHCID 2968004-phenyl-3,4-dihydro-1(2H)-naphthalenone

Product 1

HCID 10585855HCID 10585855, compound

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 241BenzeneSolvent2×

Conditions

Temperature
50 °C

Procedure

In a dry 5-liter three-necked, round-bottomed flask equipped with dropping funnel, mechanical stirrer and thermometer, there were placed 133 g. (0.6 mole) of 4-phenyltetralone [prepared from benzophenone according to procedures described in the Journal of the American Chemical Society, Vol. 69, p. 77 (1947); ibid., Vol. 70, p. 1071 (1948); ibid., Vol. 72, p. 501 (1950); ibid., Vol. 76, p. 1642 (1954)] dissolved in two liters of benzene. Stirring commenced and the solution was then cooled to 50° C., at which point 111.6 g. (3.6 mole) of liquid methylamine were slowly added thereto, followed by the dropwise addition of 33 ml. (0.3 mole) of titanium tetrachloride in 500 ml. of benzene at 0° -5° C. The latter step was carried out during the course of a 30-minute period at such a rate that the temperature never exceeded 5° C. The resulting mixture was then allowed to warm slowly to room temperature (~25° C.), stirred continuously thereafter at said temperature for a period of four hours and finally, allowed to stand overnight (a period of approximately 16 hours) at ambient temperatures without any further stirring being necessary. At this point, the spent reaction mixture was filtered while under a dry nitrogen atmosphere and the solids that had been collected on the filter funnel in this manner were thereafter washed with a fresh portion of benzene. The combined benzene filtrate and washings were then evaporated to near dryness while under reduced pressure to give 135.1 g. (95%) of oily ketimine, i.e., an almost quantitative yield of N-methyl-4-phenyl-3,4-dihydro-1(2H)-naphthalenone imine (m.p. 69° -70° C. after crystallization from n-hexane). The oily product was used as such in the next reaction step.

Workup

  1. customIn a dry 5-liter three-necked, round-bottomed flask equipped
  2. additionfollowed by the dropwise addition of 33 ml
  3. customat 0° -5° C
  4. customwas carried out during the course of a 30-minute period
  5. customthat the temperature never exceeded 5° C
  6. temperatureto warm slowly to room temperature (~25° C.)
  7. stirringstirred continuously
  8. customof four hours
  9. stirring(a period of approximately 16 hours) at ambient temperatures without any further stirring
  10. customAt this point, the spent reaction mixture
  11. filtrationwas filtered while under a dry nitrogen atmosphere
  12. customthe solids that had been collected on the filter funnel in this manner
  13. washwere thereafter washed with a fresh portion of benzene
  14. customThe combined benzene filtrate and washings were then evaporated
  15. customto give 135.1 g

Sources & evidence

ORD record
ord-682d4d7c05714327bb80726dc8a439b7
Source dataset
uspto-grants-1977_06
Patent number
US04029731

Reaction notes

Loading…