A new anionic cyclization reaction: Condensation of benzoate esters with nitriles to give 3-amino-2-inden-1-ones

Tetrahedron Letters

Volumn 38, Issue 47, 1997, Pages 8121-8124

  Kayaleh, Nadim E ^a   Gupta, Ramesh C ^a   Morrissey, John F ^a   Johnson, Francis ^a  

^a STONY BROOK UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

3 AMINO 2 INDEN 1 ONE DERIVATIVE; ANION; ANTICOAGULANT AGENT; BENZOIC ACID DERIVATIVE; INDAN DERIVATIVE; NITRILE; UNCLASSIFIED DRUG;

ARTICLE; CYCLIZATION; REACTION ANALYSIS;

EID: 0030697329     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)10181-2     Document Type: Article

References (22)

1. The synthesis of methyl benzoate, for example, was first reported in 1828 (Dumas, J; Boullay, R. Ann. Chim. 1828, [273], 20: ibid Ann Physik, 1828, 12, 435) and of propionitrile in 1869 (Gautier, M., Ann. Chim. 1869, [4], 17, 181).
2. The synthesis of methyl benzoate, for example, was first reported in 1828 (Dumas, J; Boullay, R. Ann. Chim. 1828, [273], 20: ibid Ann Physik, 1828, 12, 435) and of propionitrile in 1869 (Gautier, M., Ann. Chim. 1869, [4], 17, 181).
3. The synthesis of methyl benzoate, for example, was first reported in 1828 (Dumas, J; Boullay, R. Ann. Chim. 1828, [273], 20: ibid Ann Physik, 1828, 12, 435) and of propionitrile in 1869 (Gautier, M., Ann. Chim. 1869, [4], 17, 181).
4. A preliminary account of this work was presented at the 211th ACS National Meeting at New Orleans, LA, 1996, Abstr. Pt II., ORGN 239.
5. A by-product of the reaction is the formation of the N,N-diisopropylamide derived from the benzoate. This was significant in quantity when a methyl ester was employed but diminished greatly when the ethyl ester was used.
6. The following are representative examples of both the one-step and the two-step procedures for entry 1. a) One-step method: Methyl 4-methoxybenzoate (1) (1.23 g; 7.40 mmol) and 4-methoxy phenylacetonitrile (2) (1.08 g, 7.37 mmol) were dissolved in dry THF and the mixture was added slowly to 22.0 mL of 2.0 M LDA at - 10°C (44.0 mmol). The reaction was left to stir overnight and allowed to warm to room temperature. It was then quenched with water and most of the THF was evaporated under reduced pressure. The crude 3-aminoindenone (4) was then filtered, dried, and recrystallized from isopropanol to give the pure material (1.18 g). b) Two-step method : 4-methoxy phenylacetonitrile (2) (5.42 g, 36.8 mmol) was dissolved in dry THF, and NaH (60% in oil; 2.98 g) was added to the mixture. Neat methyl 4-methoxybenzoate (1) (6.14 g, 36.9 mmol) was added to the solution, which was boiled. After 5 hours, the solution was cooled and quenched with water. Most of the THF was evaporated under reduced pressure. Acidification gave a precipitate which was extracted with dichloromethane. The extract was washed with bicarbonate followed by brine. The solution was then dried with magnesium sulfate, filtered, and concentrated under reduced pressure to afford the keto-nitrile (3; 7.60 g). It was then dissolved in dry THF and the mixture was added to 61.0 mL of 2.0 M LDA at -10°C. The procedure then followed exactly that described in a) above. The weight of 4 was 6.10 g.
7. Accurate mass determinations (HRMS) or elemental analyses were obtained for all compounds.
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