3-Chloro-2-methyl-1-propene → HCID 22914082, compound

HRID 1377449Notes

Reaction equation

HRID 1377449 reaction equation
[CH3:1][C:2]([CH3:5])([O-])[CH3:3].[K+].[CH:7]([CH:9]1[CH:14]([CH3:15])[CH2:13][CH2:12][CH:11]2[C:16]([CH3:18])([CH3:17])[CH:10]12)=[O:8].C(Cl)C(=C)C>CN(C=O)C.[Cl-].[Na+].O>[CH3:1][C:2](=[CH2:5])[CH2:3][C:9]1([CH:7]=[O:8])[CH:14]([CH3:15])[CH2:13][CH2:12][CH:11]2[CH:10]1[C:16]2([CH3:17])[CH3:18]

Participants

6

Reactant 3

HCID 112413-Chloro-2-methyl-1-propeneHCID 229141493,7,7-Trimethylbicyclo[4.1.0]heptane-2-carbaldehydeHCID 23665647Potassium tert-butoxide

Product 1

HCID 22914082HCID 22914082, compoundYield 80%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolvent3×HCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
0 °C

Procedure

A 4 neck 2 liter round bottomed flask was charged with 500 ml of DMF and 78.0 g of potassium t-butoxide (0.66 mole). The flask was cooled to 0° C. and 100.0 g of 2-formylcarane at a purity of 75% (0.45 mole) in 75 ml of DMF were added dropwise over 30 minutes at 0°-5° C. The mixture was stirred for 20 minutes at 0°-5° C. Then 60.0 g of methallyl chloride (0.66 mole) in 50 ml of DMF were added dropwise over about 25 minutes between 5°-12° C. The batch was poured with stirring into 2 liters of cold brine and extracted with 3×250 ml of hexane. The hexane extracts were washed with 3×500 ml of water and 500 ml of brine. The hexane was dried with sodium sulfate, filtered, and concentrated in vacuo. In this way 127.8 g of crude product were obtained. The crude product was charged into a 250 ml 3 neck flask and heated under nitrogen at 165°-180° C. for 4.5 hours. The crude aldehyde was distilled to afford 88.4 g of purified product (80% yield). BP 79° C./0.1 mmHg; 1H-NMR (300 MHz), δ 0.6-1.0 (3H, m), 1.04 (3H, s), 1.06 (3H, s), 1.0-1.12 (2H, m), 1.2-1.4 (3H, m), 1.6-1.8 (2H, m), 1.82 (3H, s), 2.44 (2H, m), 4.83 (2H, m), 9.63 (1H, s); 13C-NMR (75 MHz), δ 16.44, 17.68, 20.06, 20.31, 24.66, 27.04, 28.76, 31.24, 33.36, 40.74, 45.73, 49.66, 115.93, 141.89, 204.41; IR (Neat), 2970, 2730, 1725, 1645, 1460, 1380, 895 cm-1 ; MS (m/e), 220 (M+), 205, 191, 177, 165, 147, 135, 121, 107, 93, 81, 69, 55, 41 (Base);

Workup

  1. additionThe batch was poured
  2. extractionextracted with 3×250 ml of hexane
  3. washThe hexane extracts were washed with 3×500 ml of water and 500 ml of brine
  4. dry with materialThe hexane was dried with sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customIn this way 127.8 g of crude product were obtained
  8. temperatureheated under nitrogen at 165°-180° C. for 4.5 hours
  9. distillationThe crude aldehyde was distilled

Sources & evidence

ORD record
ord-0a1c56649cda4b6b840443328f225c83
Source dataset
uspto-grants-1997_09
Patent number
US05665696

Reaction notes

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