2-Bromobenzyl cyanide → 1-(1,3-dioxolan-2-ylidene)-1H-indene-3-carbonitrile

HRID 1181657

Reaktionsgleichung

Reaktionsgleichung von HRID 1181657
C(O[CH:4]=[CH:5][C:6]([O:8][CH2:9][CH3:10])=[O:7])C.Br[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[CH2:18][C:19]#[N:20].C1(P(C2CCCCC2)C2CCCCC2)CCCCC1.CC(C)([O-])C.[Na+]>CC(O)=O.CC(O)=O.[Pd].C(O)CO.O1CCCC1>[O:8]1[CH2:9][CH2:10][O:7][C:6]1=[C:5]1[C:12]2[C:13](=[CH:14][CH:15]=[CH:16][CH:17]=2)[C:18]([C:19]#[N:20])=[CH:4]1

Komponenten

8

Edukt 4

HCID 296252-Bromobenzyl cyanideHCID 75806TricyclohexylphosphineHCID 221780Ethyl 3-ethoxy-2-propenoateHCID 23676156Sodium t-butoxide

Produkt 1

HCID 98343201-(1,3-dioxolan-2-ylidene)-1H-indene-3-carbonitrile

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 4144353Palladium (II) acetateKatalysatorHCID 174Ethylene GlycolLösungsmittelHCID 8028TetrahydrofuranLösungsmittel2×

Reaktionsbedingungen

Temperatur
5 °C

Versuchsvorschrift

Ethyl 3-ethoxyacrylate (36.9 kg, 255.0 moles), 2-bromophenyl acetonitrile (50 kg, 255. 1 moles), and tetrahydrofuran (57 L) were combined in reactor 1 and the resultant solution was stirred at 25° C. until needed (4 hours.). Palladium II acetate (1.3 kg, 5.7 moles), tricyclohexylphosphine (1.9 kg, 6.7 moles), and tetrahydrofuran (148 L) were combined in reactor 2 and the resultant mixture was stirred for 30 minutes at 25° C. The mixture was then cooled to 5° C. and sodium t-butoxide (61.3 kg, 637.7 moles ) was added to reactor 2 at 5° C. The resulting mixture was warmed to 15° C. and stirred for 15 minutes and then cooled back to 5° C. The contents in reactor 1 were then slowly charged to reactor 2 over 2 hours. at 10° C. and then the contents in reactor 2 were stirred for 15 minutes at 10° C. Reactor 2 was then slowly heated to 60° C. at a rate of 8 to 2° C. per hour (5 hours.) and then held at 60° C. for 4 hours. The reaction was then cooled to 5° C. and ethylene glycol was added at 5° C. The Tetrahydrofuran in the reaction was then distilled off. The reaction was again cooled to 10° C. and sulfuric acid (88.4 kg) added over 1.5 hours at 10° C. The reaction was heated to 40° C. at a rate of 8 to 12° C. per hour (3 hours) and held at 40° C. for 8 hours. The reaction was cooled to 10° C. and ammonium hydroxide (44.8 kg) and water (201 L) were added. The slurry was warmed to 20° C. and granulated for 2 hours. The solid was filtered and washed with water (61 L). The crude solid was recharged to the reactor and water (220 L) added. The slurry was granulated at 20° C. for 4.5 hours and then filtered. The filter cake was washed with water (61 L) and the product dried at 55° C.

Aufarbeitung

  1. custom(4 hours.)
  2. temperatureThe resulting mixture was warmed to 15° C.
  3. temperaturecooled back to 5° C
  4. additionThe contents in reactor 1 were then slowly charged to reactor 2 over 2 hours
  5. stirringat 10° C. and then the contents in reactor 2 were stirred for 15 minutes at 10° C
  6. temperatureReactor 2 was then slowly heated to 60° C. at a rate of 8 to 2° C. per hour (5 hours.)
  7. waitheld at 60° C. for 4 hours
  8. temperatureThe reaction was then cooled to 5° C.
  9. distillationThe Tetrahydrofuran in the reaction was then distilled off
  10. temperatureThe reaction was again cooled to 10° C.
  11. additionsulfuric acid (88.4 kg) added over 1.5 hours at 10° C
  12. temperatureThe reaction was heated to 40° C. at a rate of 8 to 12° C. per hour (3 hours)
  13. waitheld at 40° C. for 8 hours
  14. temperatureThe reaction was cooled to 10° C.
  15. additionammonium hydroxide (44.8 kg) and water (201 L) were added
  16. temperatureThe slurry was warmed to 20° C.
  17. waitgranulated for 2 hours
  18. filtrationThe solid was filtered
  19. washwashed with water (61 L)
  20. additionadded
  21. waitThe slurry was granulated at 20° C. for 4.5 hours
  22. filtrationfiltered
  23. washThe filter cake was washed with water (61 L)
  24. customthe product dried at 55° C.

Quellen und Nachweise

ORD-Eintrag
ord-7abf34ac6a93421b9b24db77ea5d03df
Quelldatensatz
uspto-grants-2007_10
Patentnummer
US07285686B2

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