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Bubnov et al.
CH2CH= and endo-HC(12)); 1.68 (br.s, 1 H, NH);
1.752.15 (m, 1 H, CH2CH=); 2.45 (m, 1 H, C(11)H);
2.82 (dd, 1 H, exo-HC(12)H, J = 14.44 Hz, J = 1.97 Hz);
3.45 (dd, 1 H, C(10)H, J = 10.50 Hz, J = 3.28 Hz); 3.90 (s,
1 H, C(8)H); 4.90 (m, 2 H, CH2=CH); 5.60 (m, 1 H,
CH=CH2); 7.05 (m, 1 H, CH arom.); 7.25 (m, 2 H,
CH arom.); 7.50 (m, 1 H, CH arom.). 13C NMR (CDCl3),
δ: 20.99 (CH3); 37.00, 39.78 (C(12) and CH2CH=); 40.28
(C(11)); 50.80 (C(10)); 62.27 (C(8)); 75.73 (C(1)); 117.65
(CH2=CH); 120.80, 126.88, 127.69, 128.02 (CH arom.);
134.77 (CH=CH2); 135.22, 141.93 (C(2), C(7)). Iso-
1R*,8S*,10S*,11S*-6 : 1R*,8S*,10S*,11R*-6 ≈ 7 : 3), 1H NMR
(CDCl3), δ: 0.62 and 1.21, respectively; 13C NMR (C(11)H2D),
1
δ: 21.15 and 18.55, respectively, triplets, JCD = 19 Hz.
9,10-Diallyl-11-methyl-9-azatricyclo[6.2.2.02.7]dodeca-
2,4,6-triene (7) the 1R*,8S*,10S*,11S* isomer (7a) and
the 1R*,8S*,10S*,11R* isomer (7b). A 1.2 M solution of
allylzinc bromide (77 mL, 93 mmol) in THF was added with
stirring to a solution of isoquinoline (4 g, 31 mmol) in THF
(15 mL) at 20 °C. The reaction mixture was refluxed for
30 min and cooled to 20 °C. Then allyl bromide (13.4 mL,
0.155 mol) was added. After one day, the reaction mixture was
decomposed with methanol (3.2 g, 0.1 mol). Then the reaction
mixture was treated as described for compound 2. Af-
ter distillation, a mixture of compounds 7a and 7b was
1
mer 5b. H NMR (CDCl3), δ: 1.051.30 (m, 1 H + 1 H,
CH2CH= + endo-HC(12)); 1.45 (d, 3 H, CH3,
3J = 6.58 Hz); 1.68 (br.s, 1 H, NH); 1.90 (m, 1 H,
CH2CH=); 2.45 (m, 1 H, C(11)H); 2.62 (dd, 1 H,
exo-HC(12)H, J = 14.44 Hz, J = 1.97 Hz); 3.65 (dd, 1 H,
C(10)H, J = 10.5 Hz, J = 2.63 Hz); 3.90 (s, 1 H, C(8)H); 4.90
(m, 2 H, CH2=CH); 5.60 (m, 1 H, CH=CH2); 7.05 (m,
1 H, CH arom.); 7.25 (m, 2 H, CH arom.); 7.65 (m, 1 H,
CH arom.). 13C NMR (CDCl3), δ: 19.21 (CH3); 37.37, 38.55
(C(12) and CH2CH=); 40.28 (C(11)); 51.17 (C(10));
54.69 (C(8)); 74.38 (C(1)); 117.67 (CH2=CH); 120.91,
126.28, 126.79, 127.51 (CH arom.); 134.77 (CH=CH2);
139.26, 142.04 (C(2), C(7)).
obtained in a yield of 6.7 g (86%), b.p. 131133 °C
23.5
(2 Torr), nD
1.5275. The ratio of the diastereomers
1R*,8S*,10S*,11S*-7 : 1R*,8S*,10S*,11R*-7 = 73 : 27 (deter-
mined by GLC-mass spectrometry). MS, m/z (Irel(%)):
253 [M]+ (1), 212 [M C3H5]+ (33), 170 [M (C3H5 +
C3H6)]+ (100), 128 [M (C3H5 + C3H6 + C3H6)]+ (11), 41
[C3H5]+ (34). Isomer 7a. 1H NMR (CDCl3), δ: 0.58 (d, 3 H,
CH3, 3J = 7.43 Hz); 0.63 (ddd, 1 H, endo-HC(12),
J = 13.52 Hz, J = 3.91 Hz, J = 2.65 Hz); 1.60 and 1.95
(both m, 1 H + 1 H, CH2 in 10-allyl); 1.90 (m, 1 H, C(11)H);
2.45 (m, 1 H, exo-HC(12)); 2.72 (s, 1 H, C(1)H); 3.30 (m,
1 H, C(10)H); 3.353.45 (m, 2 H, CH2 in N-allyl); 3.80 (m,
1 H, C(8)H); 4.905.00 (m, 2 H, CH2= in 10-allyl); 5.10,
5.23 (both m, 1 H + 1 H, CH2= in N-allyl); 5.70 (m, 1 H,
CH= in 10-allyl); 5.92 (m, 1 H, CH= in N-allyl); 7.07 and
7.16 (both m, 2 H + 2 H, CH arom.). 13C NMR (CDCl3),
δ: 21.87 (CH3); 29.80 (C(12)); 30.66 (C(11)); 40.77 (CH2 in
10-allyl); 44.47 (C(1)); 55.15 (C(10)); 57.61 (CH2 in N-allyl);
64.93 (C(8)); 116.41, 116.67 (CH2= in allyl); 122.07, 126.17,
126.38, 127.12 (CH arom.); 136.06, 137.33 (CH= in al-
lyls). Isomer 7b. 1H NMR (CDCl3), δ: 0.63 (ddd, 1 H,
endo-HC(12), J = 13.52 Hz, J = 3.91 Hz, J = 2.65 Hz);
1.18 (d, 3 H, CH3, 3J1 = 7.42 Hz); 1.60 and 1.95 (both m,
1 H + 1 H, CH2 in 10-allyl); 1.90 (m, 1 H, C(11)H); 2.67 (s,
1 H, C(1)H); 2.75 (m, 1 H, exo-HC(12)); 3.30 (m, 1 H,
C(10)H); 3.353.45 (m, 2 H, CH2 in N-allyl); 3.75 (m, 1 H,
CH(8)); 4.905.00 (m, 2 H, CH2= in 10-allyl); 5.10, 5.23
(both m, 1 H + 1 H, CH2= in N-allyl); 5.70 (m, 1 H, CH= in
10-allyl); 5.92 (m, 1 H, CH= in N-allyl); 7.07 and 7.16
(both m, 2 H + 2 H, CH arom.). 13C NMR (CDCl3), δ: 18.53
(CH3); 27.40 (C(12)); 30.37 (C(11)); 40.44 (CH2 in 10-allyl);
44.09 (C(1)); 55.89 (C(10)); 56.49 (CH2 in N-allyl); 64.93
(C(8)); 116.41, 116.67 (CH2= in allyls); 122.42, 124.70, 125.98,
126.49 (CH arom.); 136.06, 137.33 (CH= in allyls).
Picrate of compound 5, m.p. 153154 °C (from an ethyl
acetatemethanol mixture). Found (%): C, 48.37; H, 3.90;
N, 10.64. C21H21BrN4O7. Calculated (%): C, 48.38; H, 4.06;
N, 10.75.
Picrate of isomer 5b. 1H NMR (CDCl3), δ: 0.85 (d, 3 H,
CH3, 3J = 6.72 Hz); 1.35 (m, 1 H, endo-HC(12)); 1.75 (m,
1 H, CH2CH=); 2.75 (m, 1 H, C(11)H); 3.00 (m, 1 H,
CH2CH=); 3.10 (m, 1 H, exo-HC(12)H); 4.25 (dd,
1 H, C(10)H, J = 10.18 Hz, J = 3.47 Hz); 4.85 (m, 1 H,
C(8)H); 5.10 (m, 2 H, CH2=CH); 5.50 (m, 1 H, CH=CH2);
7.33 (d, 1 H, CH arom., 3J = 7.39 Hz); 7.50 (m, 2 H,
CH arom.); 7.72 (d, 1 H, CH arom., 3J = 7.47 Hz); 8.87 (s,
2 H, CH picrate anion). 13C NMR (DMF-d7), δ: 20.80
(CH3); 33.24, 36.04 (C(12) and CH2CH=); 38.83 (C(11));
51.68 (C(10)); 62.50 (C(8)); 70.33 (C(1)); 119.45 (CH2=CH);
126.01 (2 CH picrate anion); 126.31, 128.10, 129.39, 130.05
(CH arom.); 132.55 (CH=CH2); 133.66, 135.27 (C(2), C(7));
124.78, 142.50, 161.12 (picrate anion). Picrate of isomer 5a.
1H NMR (CDCl3), δ: 1.55 (d, 3 H, CH3, 3J = 6.54 Hz); 1.75
(m, 1 H, CH2CH=); 2.10 (m, 1 H, CH2CH=); 2.20
(m, 1 H, C(11)H); 2.35 (m, 1 H, endo-HC(12)); 3.10 (m,
1 H, exo-HC(12)H); 4.43 (dd, 1 H, C(10)H, J = 10.20 Hz,
J = 3.44 Hz); 4.85 (m, 1 H, C(8)H); 5.10 (m, 2 H,
CH2=CH); 5.50 (m, 1 H, CH=CH2); 7.36 (d, 1 H,
CH arom., 3J = 7.36 Hz); 7.50 (m, 2 H, CH arom.); 7.83 (d,
1 H, CH arom., 3J = 7.55 Hz); 8.87 (s, 2 H, CH picrate
anion). 13C NMR (DMF-d7), δ: 18.02 (CH3); 33.04, 36.22
(C(12) and CH2CH=); 38.15 (C(11)); 52.07 (C(10));
55.89 (C(8)); 69.55 (C(1)); 119.48 (CH2=CH); 126.01 (2 CH
picrate anion); 126.42, 128.10, 129.13, 130.05 (CH arom.);
132.55 (CH=CH2); 133.88, 139.06 (C(2), C(7)); 124.78,
142.50, 161.12 (picrate anion).
Picrate of amine 7a (16). A solution of a 7 : 3 mixture of
isomers 7a and 7b (1 g, 3.95 mmol) in MåOH (3 mL) was
added to a solution of picric acid (0.8 g) in methanol (20 mL)
heated to boiling. The solution was concentrated to 10 mL and
cooled to 0 °C. The crystals that precipitated were separated.
Picrate 16 was obtained by double crystallization from a
methanolethyl acetate mixture, m.p. 126126.5 °C (accord-
ing to the 1H NMR spectral data, an admixture of diaste-
reomer 7b was less than 4%). Found (%): C, 59.73; H, 5.66;
N, 11.89. C24H26N4O7. Calculated (%): C, 59.75; H, 5.43;
N, 11.61. The crystals of C24H26N4O7 (M = 482.49) are
monoclinic, at 20 °C a = 8.436(2) Å, b = 17.504(4) Å, c =
10-Allyl-11-(deuteromethyl)-9-azatricyclo[6.2.2.02.7]do-
deca-2,4,6-triene (6) the 1R*,8S*,10S*,11S* isomer (6a)
and the 1R*,8S*,10S*,11R* isomer (6b). Analogously to the
synthesis of 4, a mixture of 6a and 6b was obtained in a yield
of 7.15 g (84%) from a solution of isoquinoline (5 g, 38.8 mmol)
in THF (10 mL) and a 2.2 M solution of allylzinc bromide
(51 mL, 0.112 mol) in THF using MeOD (4 mL) for decom-
16.931(3) Å, β = 103.52(3)°, V = 2431.0(8) Å3, dcalc
=
3
1.318 g cm for Z = 4, space group P21/n.
9,10-Diallyl-9,11-dimethyl-9-azoniatricyclo[6.2.2.02.7]do-
deca-2,4,6-triene iodide was obtained analogously to the
N,N-dimethylated salt of amine 4a. The yield was 2.7 g (47%),
the diastereomeric purity was 97%, m.p. 156.5157 °C.
position of the reaction mixture, b.p. 117119 °C (1 Torr),
20
nD
1.5495. The 1H and 13C NMR spectra are simi-
lar to those of the mixture of 4a and 4b (the isomers