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

HRID 426430

反応式

HRID 426430 の反応式
[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]

参加物

13

反応物 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

生成物 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

試薬・触媒・溶媒 5

HCID 23938Palladium触媒HCID 178418397HCID 178418397、化合物触媒HCID 962Water溶媒HCID 6344Dichloromethane溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

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.

出典と根拠

ORDレコード
ord-a5694d3d684a47aaa9adec4d64fca1ec
出典データセット
uspto-grants-2012_01
特許番号
US08107150B2

関連ノート

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