Phosphorus oxychloride → 2-Chloro-9-formylanthracene

HRID 862718

Reaktionsgleichung

Reaktionsgleichung von HRID 862718
CN([CH:9]=[O:10])C1C=CC=CC=1.P(Cl)(Cl)(Cl)=O.[Cl:16][C:17]1[CH:30]=[CH:29][C:28]2[C:19](=[CH:20][C:21]3[C:26]([CH:27]=2)=[CH:25][CH:24]=[CH:23][CH:22]=3)[CH:18]=1>ClC1C=CC=CC=1Cl>[Cl:16][C:17]1[CH:30]=[CH:29][C:28]2[C:19](=[C:20]([CH:9]=[O:10])[C:21]3[C:26]([CH:27]=2)=[CH:25][CH:24]=[CH:23][CH:22]=3)[CH:18]=1

Komponenten

5

Edukt 3

HCID 24813Phosphorus oxychlorideHCID 283082-ChloroanthraceneHCID 66737N-Methylformanilide

Produkt 1

HCID 133753992-Chloro-9-formylanthraceneAusbeute 56,9 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 72391,2-DichlorobenzeneLösungsmittel

Versuchsvorschrift

N-methylformanilide (2.45 kg, 18.12 moles) was treated with phosphorus oxychloride (2.66 kg, 17.35 moles) over a 40 min. period at ambient temperature. The intermediate Vilsmeier complex was stirred for 2 h at room temperature, then treated with 2-chloroanthracene (963 g, 4.53 moles), and o-dichlorobezene (1.0 L). The resulting bright yellow mixture was heated gradually over 1.5 h to 90° C. at which point an exotherm ensued raising the reaction temperature to 115° C. The heat was removed until the exotherm subsided (45 min.), after which time the mixture was heated for 9 h at 90° C., then cooled. TLC analysis [silica gel/ethyl acetate:hexane (1:4)] showed a small amount of unreacted anthracene (Rf =0.90), a small amount of the 3-chloro isomer (Rf =0.65), and the 2-chloro isomer (Rf =0.58) as the major component. The cooled reaction mixture was poured into ice/water (27 L) precipitating a dark brown tar. The aqueous layer was decanted away from the tar and extracted with methylene chloride (5×2 L). The combined extracts were used to redissolve the tar. The methylene chloride solution was washed with 3N hydrochloric acid (4×1.5 L), followed by water (2 L), then dried over magnesium sulfate. The extracts were filtered, then pressure-filtered through a bed of silica gel, eluting with methylene chloride until all of the desired compound had passed through. The eluate was concentrated on the rotary evaporator to give a slurry of bright yellow crystals (in o-dichlorobenzene). The crystals were collected by filtration, washed with diethyl ether (2×500 ml), then vacuum dried to afford 619.7 g (56.9%) of the desired 2-chloro-9-anthraldehyde (mp 148°-150° C.). 1H NMR (CDCl3): δ11.35 (s, 1H), 9.02 (d, J=0.9 Hz, 1H), 8.81 (d, J=8.9 Hz, 1H), 8.56 (s, 1H), 7.98 (m, 1H), 7.90 (d, J=8.9 Hz, 1H), 7.66 (m, 1H), 7.53 (m, 1H), 7.42 (m, 1H).

Aufarbeitung

  1. temperatureThe resulting bright yellow mixture was heated gradually over 1.5 h to 90° C. at which point an exotherm
  2. temperatureensued raising the reaction temperature to 115° C
  3. customThe heat was removed until the exotherm
  4. custom(45 min.)
  5. temperatureafter which time the mixture was heated for 9 h at 90° C.
  6. temperaturecooled
  7. customThe cooled reaction mixture
  8. customprecipitating a dark brown tar
  9. customThe aqueous layer was decanted away from the tar
  10. extractionextracted with methylene chloride (5×2 L)
  11. dissolutionto redissolve the tar
  12. washThe methylene chloride solution was washed with 3N hydrochloric acid (4×1.5 L)
  13. dry with materialdried over magnesium sulfate
  14. filtrationThe extracts were filtered
  15. filtrationpressure-filtered through a bed of silica gel
  16. washeluting with methylene chloride until all of the desired compound
  17. concentrationThe eluate was concentrated on the rotary evaporator
  18. customto give a slurry of bright yellow crystals (in o-dichlorobenzene)
  19. filtrationThe crystals were collected by filtration
  20. washwashed with diethyl ether (2×500 ml)
  21. customvacuum dried

Quellen und Nachweise

ORD-Eintrag
ord-7896c9997914428d964aa2fb7deb5bfd
Quelldatensatz
uspto-grants-1998_02
Patentnummer
US05719166

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