Heteroatom participation during addition-rearrangement reactions of 2-thia- and 2-azanorbornenes

Raasch, Maynard S.

doi:10.1021/jo00890a003

Cited by 58 publications

(25 citation statements)

References 23 publications

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“…The formation of sulfones 16-18 is consistent with result on oxidation of the cycloadduct of bis(trifluoromethyl)thioketene and cyclopentadiene by MCPBA reported to proceed with formation of the corresponding unsaturated sulfone [11].…”

Section: Oxidation Reactionssupporting

confidence: 86%

Reactivity of fluorinated sulfur-containing heterocycles towards nucleophilic and oxidizing reagents

Петров¹,

Lustig²,

Marshall³

2007

Journal of Fluorine Chemistry

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Section: Oxidation Reactionssupporting

confidence: 86%

Reactivity of fluorinated sulfur-containing heterocycles towards nucleophilic and oxidizing reagents

Петров¹,

Lustig²,

Marshall³

2007

Journal of Fluorine Chemistry

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“…The precipitated orange solid was filtered off, washed with a small amount of CCl 4 , and dried in a vacuum desiccator to constant mass. 13 C NMR spectrum (63 MHz), δ, ppm : 83.95 (C (1) ); 66.62 (C (2) ); 64.84 (C (4) ); 84.84 (C (5) ); 47.58 (C (6) ); 75.27 (C (7) ); 35.79 (C (8) ); 31.34 (C (9) ); 57.98 (CH 2 ); 8.59 (CH 3 1.73 (2H, m, CH 2 CH 2 CH 3 ); 0.93 (3H, t, J = 7.32, CH 2 CH 2 CH 3 ); 3.59 (3H, s, CH 3 ). 13 C NMR spectrum (63 MHz), δ, ppm: 83.09 (C (1) ); 67.16 (C (2) ); 65.25 (C (4) ); 84.89 (C (5) ); 47.49 (C (6) ); 75.96 (C (7) ); 35.79 (C (8) ); 31.25 (C (9) ); 63.43 (NCH 2 ); 16 …”

Section: Preparation Of Tribromides 2a-l (General Method)mentioning

confidence: 99%

“…It is impossible to exclude the possibility of the reaction also proceeding through the formation at the first stage of a classical carbocation of type C, which assists polarization of the double bond under the action of an allylic nitro group. However in this case the stereoselectivity of the process is significantly less [9].…”

mentioning

confidence: 91%

“…A starting point for interpreting the NMR spectra may be served by the low field broadened doublet (5.73 ppm, 3 J = 6.62 Hz) of the H-6 proton at the carbon atom directly linked with halogen, and the singlet of the N-methyl group protons at 3.59 ppm, which have correlation peaks 1 J CH in the 2D HSQC spectrum with the signals of the carbon atoms at 53.06 and 55.01 respectively, and also cross peaks 2 J CH in the HMBC spectrum H-6/C (7) , H-6/C (5) and 3 J CH H-6/C (9) , H-6/C (8) , Me/C (4) , Me/C (2) , and Me/C (7) ( Table 2). The presence of a vicinal coupling constant between the protons of the methyl group and the C (7) atom indicates the formation in the molecule of a covalent bond between the C (7) -N (3) atoms.…”

mentioning

confidence: 99%

“…the product of anti addition. Consequently the cation formed on attack by bromine of the azabicyclononene molecule may be assigned to the bridge structure A [9]. In the 6,7-dibromo derivative B the spatial structure of the cyclohexane fragment is reduced as a result of saturation.…”

mentioning

confidence: 99%

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Study of the bromination of 1,5-dinitro-3-azabicyclo-[3.3.1]non-6-enes

Shakhkel'dyan

Atroshchenko

Melekhina

et al. 2008

Chem Heterocycl Comp

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Derivatives of azabicyclo[3.3.1]nonane possess various biological activities [1][2][3], consequently broadening the range of compounds of this class is urgent and offers promise for the directed synthesis of biologically active substances and the study of structure-activity relationships. One of the methods of functionalizing the derivatives of 1,5-dinitro-3-azabicyclo[3.3.1]non-6-enes previously synthesized by us [4][5][6][7][8] may be the addition of electrophilic reagents at the double bond. It was shown previously that electrophilic addition of halogenating agents to 2-azanorborn-5-ene leads to the formation of rearranged products [9, 10], and addition of bromine and dihalogen iodates to 2-alkyl-2-azabicyclo[2.2.1]hept-5-ene and 2-alkyl-2-azabicyclo-[2.2.2]oct-5-ene leads to a quaternary ammonium salt containing an aziridinium ring [11,12]. The reactivity of the double bond towards electrophilic interaction in 1,5-dinitro-3-azabicyclo[3.3.1]non-6-enes is reduced due to the influence of the electron-withdrawing 5-NO 2 group. In addition, steric factors characteristic of the framework of the system introduce their own contribution to deactivation. In this connection, as a model permitting study of the reactivity of the C=C double bond of the cyclohexene fragment of the bicyclic system, we selected the bromination reaction which has not been described for compounds of this type up to the present time.It was established that in the reaction of an excess of bromine with 1,5-dinitro-3-azabicyclo[3.3.1]non-6-enes 1a-l in CCl 4 , 3-R-6-bromo-1,5-dinitro-3-azoniatricyclo[3.3.1.0 3,7 ]nonane tribromides 2a-l were isolated in quantitative yield as orange solids readily soluble in water, in place of the expected products of addition of halogen at the double bond, 3-R-6,7-dibromo-1,5-dinitro-3-azabicyclo[3.3.1]nonanes (B). The obtained compounds 2a-l have the structure of quaternary salts and contain the complex tribromide anion,as indicated by __________________________________________________________________________________________

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