Sodium Carbonate → 5-Trimethylsilylethynyl-2,3-bis-(2-methyl-3-benzo[3,2-b]thienyl)thiophene

HRID 2355987Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2355987
[CH3:1][Si:2]([C:5]#[CH:6])([CH3:4])[CH3:3].[CH3:7][C:8]1[S:12][C:11]2[CH:13]=[CH:14][CH:15]=[CH:16][C:10]=2[C:9]=1[C:17]1[S:18][CH:19]=[CH:20][C:21]=1[C:22]1[C:23]2[CH:31]=[CH:30][CH:29]=[CH:28][C:24]=2[S:25][C:26]=1[CH3:27].[CH3:32][C:33]1SC2C=CC=CC=2C=1B(O)O.BrC1SC=CC=1Br.C(=O)([O-])[O-].[Na+].[Na+].C(=O)([O-])[O-].[K+].[K+]>[Pd].ClCCl.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1COCC1.O>[CH3:1][Si:2]([C:5]#[C:6][C:19]1[S:18][C:17]([C:9]2[C:10]3[CH:16]=[CH:15][CH:14]=[CH:13][C:11]=3[S:12][C:8]=2[CH3:7])=[C:21]([C:22]2[C:23]3[CH:31]=[CH:30][CH:29]=[CH:28][C:24]=3[S:25][C:26]=2[CH3:27])[CH:20]=1)([CH3:4])[CH3:3].[C:32]([C:20]1[C:21]([C:22]2[C:23]3[CH:31]=[CH:30][CH:29]=[CH:28][C:24]=3[S:25][C:26]=2[CH3:27])=[C:17]([C:9]2[C:10]3[CH:16]=[CH:15][CH:14]=[CH:13][C:11]=3[S:12][C:8]=2[CH3:7])[S:18][CH:19]=1)#[CH:33]

Komponenten

13

Edukt 6

HCID 10340Sodium CarbonateHCID 11430Potassium CarbonateHCID 66111TrimethylsilylacetyleneHCID 765902,3-DibromothiopheneHCID 58933004(2-Methyl-1-benzothiophen-3-yl)boronic acidHCID 667041632,3-Bis(2-methylbenzothiophen-3-yl)thiophene

Produkt 2

HCID 667043115-Trimethylsilylethynyl-2,3-bis-(2-methyl-3-benzo[3,2-b]thienyl)thiopheneHCID 87118226Ethynyl-2,3-bis-(2-methyl-3-benzo[3,2-b]thienyl)thiophene

Reagenzien, Katalysatoren, Lösungsmittel 5

HCID 23938PalladiumKatalysatorHCID 178418397HCID 178418397, VerbindungKatalysatorHCID 962WaterLösungsmittelHCID 6344DichloromethaneLösungsmittelHCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

5-Trimethylsilylethynyl-2,3-bis-(2-methyl-3-benzo[3,2-b]thienyl)thiophene is synthesized by the Sonogashira coupling reaction of trimethylsilylacetylene and the bromo-derivative of 2,3-bis-(2-methyl-3-benzo[3,2-b]thienyl)thiophene, which is also prepared from the Suzuki cross-coupling reaction of 2.5 equivalents of 2-methyl-3-benzo[3,2-b]thienylboronic acid and 2,3-dibromothiophene in the presence of the palladium catalyst, Pd(PPh3)4, and sodium carbonate in a heterogeneous mixture of water and THF according to the procedure similar to that of (L1). Subsequent deprotection of the trimethylsilyl group using potassium carbonate in dichloromethane solution gives the target ligand ethynyl-2,3-bis-(2-methyl-3-benzo[3,2-b]thienyl)thiophene (L5). The synthetic route is shown in FIG. 12. Excitation of the ligand with λ≦352 nm light resulted in the formation of the close form, corresponding to the photocyclization product.

Quellen und Nachweise

ORD-Eintrag
ord-59020c9e77b44d5bbd63a4bad352dd7e
Quelldatensatz
uspto-grants-2010_07
Patentnummer
US07755826B2

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