1,1',1''-(Chlorosilylidyne)tris(benzene) → (4-Triphenylsilyloxyimino-cyclohexa-2,5-dienylidene)-phenyl-acetonitrile

HRID 1018888

Reaktionsgleichung

Reaktionsgleichung von HRID 1018888
[OH:1][N:2]=[C:3]1[CH:8]=[CH:7][C:6](=[C:9]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[C:10]#[N:11])[CH:5]=[CH:4]1.[C:18]1([Si:24]([C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)([C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)Cl)[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1.C(N(CC)CC)C>C1COCC1.CC(O)C>[C:32]1([Si:24]([C:18]2[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=2)([C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[O:1][N:2]=[C:3]2[CH:8]=[CH:7][C:6](=[C:9]([C:12]3[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=3)[C:10]#[N:11])[CH:5]=[CH:4]2)[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=1

Komponenten

6

Edukt 3

HCID 64581,1',1''-(Chlorosilylidyne)tris(benzene)HCID 8471TriethylamineHCID 3468332-(4-(Hydroxyimino)cyclohexa-2,5-dien-1-ylidene)-2-phenylacetonitrile

Produkt 1

HCID 18398563(4-Triphenylsilyloxyimino-cyclohexa-2,5-dienylidene)-phenyl-acetonitrile

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 3776IsopropanolLösungsmittelHCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
5 °C

Versuchsvorschrift

7 g (31 mmol) of (4-Hydroxyimino-cyclohexa-2,5-dienylidene)-phenyl-acetonitrile, prepared as described in example 1.1, are dissolved in 80 ml of THF and cooled in an ice bath. After adding 10 g (34 mmol) of triphenylchlorosilane to the solution, 4.7 g (47 mmol) of triethylamine are added dropwise, keeping the temperature below 5° C. While the reaction mixture is stirred at 5° C. for 90 min, a precipitate is formed. The precipitate is filtered off and washed with THF. The filtrate is concentrated by a rotary evaporator to afford a red liquid. The residue is diluted with 2-PrOH and stirred at room temperature for 30 min. After cooling the mixture in an ice bath, the solid is isolated by filtration and washed with 2-PrOH. The product is obtained in the form of a pale yellow solid, mp 161-165° C. (Dec). The structure is confirmed by the 1H-NMR spectrum (CDCl3). δ [ppm]: 6.79(Z)/6.94(E) (dd, 1H), 7.04(Z)/7.15(E) (dd, 1H), 7.32-7.71 (m, 22H). 1H-NMR reveals that the product is a 77:23 mixture of Z and E isomers. The signals are tentatively assigned to Z and E isomers.

Aufarbeitung

  1. temperaturecooled in an ice bath
  2. additionare added dropwise
  3. customthe temperature below 5° C
  4. customa precipitate is formed
  5. filtrationThe precipitate is filtered off
  6. washwashed with THF
  7. concentrationThe filtrate is concentrated by a rotary evaporator
  8. customto afford a red liquid
  9. stirringstirred at room temperature for 30 min
  10. temperatureAfter cooling the mixture in an ice bath
  11. customthe solid is isolated by filtration
  12. washwashed with 2-PrOH
  13. customThe product is obtained in the form of a pale yellow solid, mp 161-165° C. (Dec)
  14. additiona 77:23 mixture of Z and E isomers

Quellen und Nachweise

ORD-Eintrag
ord-a76f4fab04cb480eae6716c7226edd0f
Quelldatensatz
uspto-grants-2002_11
Patentnummer
US06485886B1

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