Phenothiazine → Ethyl Acrylate

HRID 2291144Notes

Reaction equation

HRID 2291144 reaction equation
[OH:1][CH2:2][CH2:3][O:4][CH:5]1[CH2:10][CH:9]2[C:11]([CH3:13])([CH3:12])[C:6]1([CH3:14])[CH2:7][CH2:8]2.[C:15]([O:19][CH2:20][CH3:21])(=[O:18])[CH:16]=[CH2:17].C1C2NC3C(=CC=CC=3)SC=2C=CC=1.[N+](C1C=CC=CC=1)([O-])=O>CC([O-])C.CC([O-])C.CC([O-])C.CC([O-])C.[Ti+4]>[CH3:14][C:6]12[C:11]([CH3:13])([CH3:12])[CH:9]([CH2:8][CH2:7]1)[CH2:10][CH:5]2[O:4][CH2:3][CH2:2][O:1][C:15](=[O:18])[CH:16]=[CH2:17].[CH2:20]([O:19][C:15](=[O:18])[CH:16]=[CH2:17])[CH3:21]

Participants

7

Reactant 4

HCID 7108PhenothiazineHCID 7416NitrobenzeneHCID 8821Ethyl Acrylate2×HCID 13750367HCID 13750367, compound2×

Product 2

HCID 8821Ethyl AcrylateHCID 13750370HCID 13750370, compound

Reagents, catalysts & solvents 1

HCID 11026Titanium isopropoxideCatalyst

Procedure

2-(1,7,7-trimethylbicyclo[2.2.1]hept-2-yloxy)ethyl-2-propenoate (IX) was prepared by trans-esterification of 2-(Beta-hydroxyethoxy)-bornane (VII) with ethyl acrylate (VIII) using tetraisopropyl titanate catalyst. 125 g. of (VII), 221 g. ethyl acrylate (VIII), 0.90 g. phenothiazine, and 0.23 g. nitrobenzene were charged to a 500 ml. glass reactor equipped with magnetic stirrer, thermometer, 1"×12" packed column (stainless steel ProPac) and a distillation head equipped with a reflux control connected to a timer and temperature controller. A nitrogen stream was maintained in the condenser to prevent moisture from entering the system. The reactor was heated to reflux to remove any water as an ethanol/water azeotrope. After 2 hours refluxing, the reaction was cooled to 30° and 1.0 g. of tetraisopropyl titanante was added to the still pot. The reaction was heated to reflux at atmospheric pressure and ethanol removed as formed as its azeotrope with ethylacrylate up to 88° C. boiling range. When the boiling range reached 100° C. at atm., a cut was taken at 100 mm to 125° pot, then 10 mm to 125° pot. The product (IX) was distilled at 1 mm to 180° pot. 113 g. product (IX) analyzing at 98.4% by VPC was obtained. Structure was verified by NMR. Theory yield was 71%.

Workup

  1. customglass reactor equipped with magnetic stirrer
  2. customa distillation head equipped with a reflux control
  3. temperatureA nitrogen stream was maintained in the condenser
  4. temperatureThe reactor was heated
  5. temperatureto reflux
  6. customto remove any water as an ethanol/water
  7. temperatureAfter 2 hours refluxing
  8. temperaturethe reaction was cooled to 30°
  9. additionof tetraisopropyl titanante was added to the still pot
  10. temperatureThe reaction was heated
  11. temperatureto reflux at atmospheric pressure and ethanol
  12. customremoved

Sources & evidence

ORD record
ord-71b8f7537f1d40b9b126d817536d4d16
Source dataset
uspto-grants-1986_10
Patent number
US04620028

Reaction notes

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