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Hydroquinone → 4-((2-(Acryloyloxy)-4-ethylcyclohexyl)oxy)-4-oxobutanoic acid

HRID 931404
ノート
印刷プレビュー

反応式

HRID 931404 の反応式
[CH2:1]=[CH:2][CH:3]1[CH2:8][CH:7]2[O:9][CH:6]2[CH2:5][CH2:4]1.CC1(C)N([O])C(C)(C)CCC1.[C:21]([OH:25])(=[O:24])[CH:22]=[CH2:23].[C:26]1(=[O:32])[O:31][C:29](=[O:30])[CH2:28][CH2:27]1.C1(C=CC(O)=CC=1)O>C1(C)C(C)=CC=CC=1.ClCCl.CC(C)[O-].[Ti+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].C(N(CC)CC)C.C1(C)C=CC=CC=1>[C:21]([O:25][CH:7]1[CH2:8][CH:3]([CH2:2][CH3:1])[CH2:4][CH2:5][CH:6]1[O:9][C:26](=[O:32])[CH2:27][CH2:28][C:29]([OH:31])=[O:30])(=[O:24])[CH:22]=[CH2:23]
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

11

反応物 5

HCID 785HydroquinoneHCID 6581Acrylic AcidHCID 78327-Oxabicyclo(4.1.0)heptane, 3-ethenyl-HCID 7922Succinic anhydrideHCID 2724126Tempo

生成物 1

HCID 1181173724-((2-(Acryloyloxy)-4-ethylcyclohexyl)oxy)-4-oxobutanoic acid

試薬・触媒・溶媒 5

HCID 11026
Titanium isopropoxide
触媒
HCID 1140Toluene溶媒
HCID 6344Dichloromethane溶媒
HCID 7237O-Xylene溶媒
HCID 8471Triethylamine溶媒

反応条件

温度
72.5 °C

実験手順

A round-bottom flask equipped with a stirring bar, a reflux condenser and a dropping funnel was charged with 1.6 g of 4-vinyl-1-cyclohexene 1,2-epoxide, and was heated to 70-75° C. At this point catalytic amount of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex solution in xylene, (Pt around 2%) was added and the reaction mixture was further heated to 90° C. To this reaction mixture, 10 g of monohydride functionalized polydimethylsiloxane, was added drop-wise. After completion of reaction, the reaction mixture was cooled down to 70-75° C. and 20 mL of Toluene, and a catalytic amount of Titanium isopropoxide and TEMPO (2,2,6,6-Tetramethylpiperidine 1-oxyl) was added and the reaction mixture was further heated to 90-95° C. To this reaction mixture, 1.7 g of acrylic acid, was added drop-wise over a period of two hours. The reaction was monitored using 1H-NMR spectroscopy. After completion of reaction, the reaction mixture was cooled down again to 75° C. and 2.5 g of succinic anhydride, 2.5 g of triethylamine, and 300 ppm of hydroquinone was added. The reaction was monitored using 1H-NMR spectroscopy. After completion the product was vacuum striped, re-dissolved in dichloromethane and washed with hot brine solution. The organic phase was passed over Tulsion T66-MP resin to remove traces of triethylamine and decolorized using activated charcoal. The organic layer was filtered over Celite column to remove charcoal and then stirred along with Dowex WBA resin to remove traces of acrylic acid. The organic phase was further filtered and concentrated to yield pale yellow color viscous product.

後処理

  1. customA round-bottom flask equipped with a stirring bar, a reflux condenser and a dropping funnel
  2. temperaturethe reaction mixture was further heated to 90° C
  3. customAfter completion of reaction
  4. temperaturethe reaction mixture was cooled down to 70-75° C.
  5. temperaturethe reaction mixture was further heated to 90-95° C
  6. customAfter completion of reaction
  7. temperaturethe reaction mixture was cooled down again to 75° C.
  8. washwashed with hot brine solution
  9. customto remove traces of triethylamine
  10. filtrationThe organic layer was filtered over Celite column
  11. customto remove charcoal
  12. customto remove traces of acrylic acid
  13. filtrationThe organic phase was further filtered
  14. concentrationconcentrated
  15. customto yield pale yellow color viscous product

出典と根拠

ORDレコード
ord-a7048d3bbfa14efa84ad26e2922eac4e
出典データセット
uspto-grants-2016_03
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US09296764B2

反応ノート

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