Aliphatic nitro alcohols. Synthesis, chemical transformations and applications

“…Introduction of an adamantane fragment into organic molecules changes their properties and often enhances or modifies their biological activity [2]. The chemistry of hetaryl-substituted adamantanes was reviewed in [3,4]. Some adamantyl-substituted pyrazoles were synthesized from adamantyl-containing 1,3-diketones [4][5][6][7].…”

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confidence: 99%

Synthesis of 4-(1-adamantyl)-3-polyfluoromethyl-1H-pyrazoles

et al. 2010

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“…48 The known methods for the synthesis of polynitro compounds 13 in organic solvents require prolonged heating of the reaction mixture, 49 whereas in ILs, the same reactions occur at room temperature, which considerably reduces explosion risks.…”

Section: Organic Syntheses In Ionic Liquid Mediamentioning

confidence: 99%

Ionic liquids as substrate-specific recoverable solvents and catalysts of regio-, stereo- and enantioselective organic reactions

Zlotin

Махова

2010

Mendeleev Communications

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Adamantylation of azoles with 1,3-dehydroadamantane. Selective N-adamantylation of pyrazoles

et al. 2011

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The main procedure for the synthesis of N-and C-adamantyl-containing pyrazoles is based on acidcatalyzed adamantylation of pyrazoles with various functional derivatives of adamantane [1][2][3][4][5][6]. However, this method ensures fairly poor yields of the target products and requires strongly acidic medium. A promising method for the preparation of N-adamantylsubstituted pyrazoles involves as initial compound strained [3.3.1]propellane, 1,3-dehydroadamantane (I), which is characterized by a high proton affinity (pyrazoles are weak NH acids; pK a of unsubstituted pyrazole is 14.0 [7])We previously synthesized a series of N-adamantylsubstituted imidazoles by reaction of 1,3-dehydroadamantane with the corresponding imidazoles [8]. In the present communication we report for the first time on the N-adamantylation of pyrazole (IIa), 4-bromopyrazole (IIb), and 3,5-dimethylpyrazole (IIc) with 1,3-dehydroadamantane (I). The reactions were carried by heating equimolar amounts of compound I and pyrazoles IIa-IIc at 65-101°C over a period of 2-6 h, and the corresponding 1-adamantylpyrazoles IIIa-IIIc were obtained in 71-80% yield.Analysis of the products by gas chromatographymass spectrometry showed that the main reaction direction is adamantylation at the NH nitrogen atom of the pyrazole ring and that the contribution of C-adamantylation does not exceed 10%. The described procedure ensures preparation of N-adamantyl-substituted pyrazoles in good yields under relatively mild conditions. 1-(1-Adamantyl)-1H-pyrazole (IIIa).A solution of 2.92 g (0.041 mol) of pyrazole IIa in 20 ml of dioxane was added to a solution of 5 g (0.037 mol) of 1,3-dehydroadamantane (I) in 30 ml of dioxane. The mixture was heated for 2 h under reflux, the solvent was distilled off, and the residue was washed with water, dried under reduced pressure, and recrystallized from propan-2-ol. Yield 6.57 g (71%), colorless crystals, mp 52-54°C; published data [7]: mp 51-53°C. 1 H NMR spectrum, δ, ppm: 1.70 s (6H, CH 2 , Ad), 2.08 s (6H CH 2 , Ad), 2.15 s (3H, CH, Ad), 6.20 s (1H), 7.40 s (1H), 7.80 s (1H). Mass spectrum, m/z (I rel , %): 202 (100) [M] + , 145 (61) [M -C 4 H 9 ] + , 135 (26) [Ad] + , 119 (67) [Ad -C 3 H 6 ] + , 79 (25) [Ad -C 4 H 8 ] + . 1-(1-Adamantyl)-4-bromo-1H-pyrazole (IIIb).A solution of 5.44 g (0.037 mol) of pyrazole IIb in 15 ml of tetrahydrofuran was added to a solution of 5 g (0.037 mol) of 1,3-dehydroadamantane (I) in 20 ml of tetrahydrofuran. The mixture was heated for 4 h under R 1 = R 2 = R 3 = H (a); R 1 = R 3 = H, R 2 = Br (b); R 1 = R 3 = Me, R 2 = H (c).

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Aliphatic nitro alcohols. Synthesis, chemical transformations and applications

Cited by 35 publications

References 100 publications

Synthesis of 4-(1-adamantyl)-3-polyfluoromethyl-1H-pyrazoles

Synthesis of 4-(1-adamantyl)-3-polyfluoromethyl-1H-pyrazoles

Ionic liquids as substrate-specific recoverable solvents and catalysts of regio-, stereo- and enantioselective organic reactions

Adamantylation of azoles with 1,3-dehydroadamantane. Selective N-adamantylation of pyrazoles

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