6-Bromo-2,2,4,4-tetrafluoro-1,3-benzodioxane → 2,2,4,4-tetrafluoro-4H-benzo[1,3]dioxine-6-carboxylic acid methyl ester

HRID 1255570ノート

反応式

HRID 1255570 の反応式
Br[C:2]1[CH:3]=[CH:4][C:5]2[O:10][C:9]([F:12])([F:11])[O:8][C:7]([F:14])([F:13])[C:6]=2[CH:15]=1>CO.CC#N.CCN(CC)CC.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>[CH3:7][O:8][C:9]([C:2]1[CH:3]=[CH:4][C:5]2[O:10][C:9]([F:12])([F:11])[O:8][C:7]([F:14])([F:13])[C:6]=2[CH:15]=1)=[O:10]

参加物

6

反応物 1

HCID 27734106-Bromo-2,2,4,4-tetrafluoro-1,3-benzodioxane

生成物 1

HCID 591661662,2,4,4-tetrafluoro-4H-benzo[1,3]dioxine-6-carboxylic acid methyl ester収率 169.8%

試薬・触媒・溶媒 4

HCID 178418397HCID 178418397、化合物触媒HCID 887Methanol溶媒HCID 6342Acetonitrile溶媒HCID 8471Triethylamine溶媒

反応条件

温度
75 °C

実験手順

A suspension of 6-bromo-2,2,4,4-tetrafluoro-4H-benzo[1,3]dioxine (4.75 g, 16.6 mmol) and Pd(PPh3)4 (950 mg, 8.23 mmol) in MeOH (20 mL), MeCN (30 mL) and Et3N (10 mL) was stirred under carbon monoxide atmosphere (55 psi) at 75° C. (oil bath temperature) overnight. The cooled reaction mixture was filtered and the filtrate was concentrated. The residue was purified by silica gel column (Petroleum Ether) to give 2,2,4,4-tetrafluoro-4H-benzo[1,3]dioxine-6-carboxylic acid methyl ester (3.75 g, 85%). 1H NMR (CDCl3, 300 MHz) δ 8.34 (s, 1H), 8.26 (dd, J=2.1, 8.7 Hz, 1H), 7.22 (d, J=8.7 Hz, 1H), 3.96 (s, 3H).

後処理

  1. customThe cooled reaction mixture
  2. filtrationwas filtered
  3. concentrationthe filtrate was concentrated
  4. customThe residue was purified by silica gel column (Petroleum Ether)

出典と根拠

ORDレコード
ord-6a30282f89ca4f7cbd85bfd2d7b70021
出典データセット
uspto-grants-2013_06
特許番号
US08461156B2

反応ノート

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