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

HRID 442399

Reaktionsgleichung

Reaktionsgleichung von HRID 442399
[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]

Komponenten

6

Edukt 4

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 5943Carbon TetrachlorideLösungsmittel

Versuchsvorschrift

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).

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-9cb64cf5db6c46468b182334eb890f3a
Quelldatensatz
uspto-grants-1977_08
Patentnummer
US04045469

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