tert-Butanol → Ethyl 2,2-dimethylspiro[2.4]hepta-4,6-diene-1-carboxylate

HRID 442399

Reaction equation

HRID 442399 reaction equation
[CH3:1][C:2]([CH3:8])=[C:3]1[CH:7]=[CH:6][CH:5]=[CH:4]1.Cl[CH2:10][C:11]([O:13][CH2:14][CH3:15])=[O:12].CC(C)([O-])C.[K+].C(O)(C)(C)C>C(Cl)(Cl)(Cl)Cl>[CH3:1][C:2]1([CH3:8])[C:3]2([CH:7]=[CH:6][CH:5]=[CH:4]2)[CH:10]1[C:11]([O:13][CH2:14][CH3:15])=[O:12]

Participants

6

Reactant 4

HCID 6386tert-ButanolHCID 7751Ethyl chloroacetateHCID 1374671,3-Cyclopentadiene, 5-(1-methylethylidene)-HCID 23665647Potassium tert-butoxide

Product 1

HCID 13307748Ethyl 2,2-dimethylspiro[2.4]hepta-4,6-diene-1-carboxylate

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

A well stirred, 10°-15° C. nitrogen blanketed mixture of 10.6 g. of 6,6-dimethylfulvene, prepared above, and 12.2 g. of ethyl chloroacetate was treated dropwise over 1.5 hr. with a solution of 11.7 g. of potassium t-butoxide in 75 ml. of dry t-butyl alcohol. The reaction was stirred an additional 1.5 hr. at 10° C. and most of the alcohol was then removed at reduced pressure. Ether extraction of an aqueous solution of the residual semisolid afforded 15.2 g. of yellow oil. Subsequent distillation afforded 2.5 g. (13%) of yellow ester, b.p. 75°-80° C. (0.25 mm.). Gas chromatographically purified ester exhibited the following spectral properties: ir (film) 5.77, 8.33, 8.69, 9.24, 12.0, 12.7 μ; nmr (CCl4) τ 3.38, 3.69, 3.99 (3m, 4, --CH=CH--CH=CH--), 5.99 (q, 2, J = 7 Hz, OCH2CH3), 7.41 (s, 1, CHCO2Et), 8.47, 8.60 (6, CH3 's), 8.80 (t, 3, J = 7 Hz, OCH2CH3).

Workup

  1. additionmixture of 10.6 g
  2. stirringThe reaction was stirred an additional 1.5 hr
  3. customat 10° C. and most of the alcohol was then removed at reduced pressure
  4. extractionEther extraction of an aqueous solution of the residual semisolid
  5. customafforded 15.2 g
  6. distillationSubsequent distillation
  7. customafforded 2.5 g

Sources & evidence

ORD record
ord-9cb64cf5db6c46468b182334eb890f3a
Source dataset
uspto-grants-1977_08
Patent number
US04045469

Linked notes

Loading…