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Russ.Chem.Bull., Int.Ed., Vol. 63, No. 9, September, 2014
Laptev et al.
(dd, 1 H, H(4); J = 7.1 Hz, J = 1.1 Hz); 7.19 (td, 1 H, H(6),
J = 7.7 Hz, J = 1.1 Hz); 7.79 (d, 1 H, H(5´), J = 2.0 Hz); 7.81
(dd, 1 H, H(7´), J = 8.3 Hz, J = 2.0 Hz). LC/MS (column II),
m/z (ret/min): 350.6 [M + 1]+ (7.09). Found (%): C, 75.42;
H, 6.71; N, 4.05. C22H23NO3. Calculated (%): C, 75.62; H, 6.63;
N, 4.01.
6´ꢀMethoxycarbonylꢀ1,3,3ꢀtrimethylspiro[indolineꢀ2,2´ꢀ
(2H)chromene] (13). Rf 0.48 (A), m.p. 109—111 C (cf. Ref. 18:
m.p. 109 C and Ref. 19: m.p. 106—108 C). 1H NMR (CDCl3),
: 1.18, 1.31 (both s, 3 H each, C(3)Me); 2.73 (s, 3 H, C(1)Me);
3.86 (s, 3 H, OCH3); 5.73 (d, 1 H, H(3´), J = 10.3 Hz); 6.54
(d, 1 H, H(7), J = 7.7 Hz); 6.72 (d, 1 H, H(8´), J = 9.4 Hz); 6.87
(td, 1 H, H(5), J = 7.3 Hz, J = 0.8 Hz); 6.88 (d, 1 H, H(4´),
J = 10.3 Hz); 7.09 (dd, 1 H, H(4), J = 7.3 Hz, J = 0.8 Hz); 7.19
(td, 1 H, H(6), J = 7.3 Hz, J = 0.8 Hz); 7.78 (s, 1 H, H(5´)); 7.82
(dd, 1 H, H(7´), J = 7.3 Hz, J = 2.1 Hz). LC/MS (column I),
m/z (ret/min): 336.5 [M + 1]+ (2.29). Found (%): C, 75.03;
H, 6.41; N, 4.25. C21H21NO3. Calculated (%): C, 75.20; H, 6.31;
N, 4.18.
Diethyl (2E,2´´´ E)ꢀ3ꢀ{1,3,3ꢀtrimethylspiro[indolineꢀ2,2´ꢀ
(2H)chromeneꢀ5,6´ꢀdiyl]}bispropenoate (26). Method A.
C2ꢀPhosphonate (180 mg, 0.8 mmol) was added dropwise using
a syringe to a suspension of sodium hydride (36 mg, 0.9 mmol;
a 60% suspension in mineral oil) in anhydrous THF (10 mL) cooled
to 0 C with vigorous stirring. The mixture was stirred until comꢀ
plete dissolution of sodium hydride (1 h). Then, a solution of
5,6´ꢀdiformylꢀ1,3,3ꢀtrimethylspiro[indolineꢀ2,2´ꢀ(2H)chromꢀ
ene] (20) (100 mg, 0.3 mmol) in THF (2 mL) was added dropꢀ
wise with stirring. After 1 h of stirring, a distilled water (20 mL)
was added dropwise to the mixture (pH 10), which was then
acidified with 0.1 M HCl to pH 6 and extracted with dichloroꢀ
methane. The extracts were dried with anhydrous Na2SO4, the
solvent was evaporated in vacuo. The target product was isolated
by flashꢀchromatography on Al2O3. The fractions containing
the target compound were combined, the solvent was evaporatꢀ
ed in vacuo to obtain compound 26 (125 mg, 88%), Rf 0.18 (A),
m.p. 53—55 C. 1H NMR (CDCl3), : 1.16, 1.30 (both s, 3 H each,
C(3)Me); 1.31 (both t, 3 H each, OCH2CH3, J = 7.1 Hz); 2.75
(s, 3 H, C(1)Me); 4.25 (q, 4 H, OCH2Me, J = 7.1 Hz); 5.71
(d, 1 H, H(3´), J = 10.3 Hz); 6.27, 6.28 (both d, 1 H each,
(O)CH, J = 15.9 Hz); 6.49 (d, 1 H, H(7), J = 8.1 Hz), 6.70
(d, 1 H, H(8´), J = 8.4 Hz), 6.87 (d, 1 H, H(4´), J = 10.3 Hz);
7.22 (d, 1 H, H(5´), J = 2.1 Hz); 7.26 (dd, 1 H, H(7´), J = 8.4 Hz,
J = 2.1 Hz); 7.27 (d, 1 H, H(4), J = 1.6 Hz); 7.34 (dd, 1 H, H(6),
J = 8.1 Hz, J = 1.6 Hz); 7.59, 7.67 (both d, 1 H each, C(O)CHCH,
J = 15.9 Hz). LC/MS (column II), m/z (ret/min): 474.4 [M + 1]+
(7.64). Found (%): C, 73.32; H, 6.73; N, 3.09. C29H31NO5.
Calculated (%): C, 73.55; H, 6.60; N, 2.96.
376.6 [M + 1]+ (7.28). Found (%): C, 76.62; H, 6.81; N, 3.63.
C24H25NO3. Calculated (%): C, 76.77; H, 6.71; N, 3.73.
Ethyl (2E)ꢀ3ꢀ{1,3,3ꢀtrimethylꢀ6´ꢀnitrospiro[indolineꢀ2,2´ꢀ
(2H)chromenꢀ5ꢀyl]}propenoate (22).11 Rf 0.34 (A), m.p.
132—134 C. LC/MS (column I), m/z (ret/min): 421.4 [M + 1]+
(3.78). 1H NMR (CDCl3), : 1.18, 1.30 (both s, 3 H each,
C(3)Me); 1.32 (t, 3 H, OCH2CH3, J = 7.0 Hz); 2.77 (s, 3 H,
C(1)Me); 4.24 (q, 2 H, CH3CH2O, J = 7.0 Hz); 5.84 (d, 1 H,
H(3´), J = 10.3 Hz); 6.29 (d, 1 H, C(O)CH, J = 16.0 Hz); 6.33
(d, 1 H, H(7), J = 8.1 Hz); 6.76 (d, 1 H, (8´), J = 9.8 Hz); 6.94
(d, 1 H, H(4´), J = 10.3 Hz); 7.28 (d, 1 H, H(4), J = 1.5 Hz);
7.34 (dd, 1 H, H(6), J = 8.1 Hz, J = 1.5 Hz); 7.66 (d, 1 H,
C(O)CHCH, J = 16.0 Hz); 8.0 (s, 1 H, H(5´)); 8.01 (dd, 1 H,
H(7´), J = 9.8 Hz, J = 1.7 Hz). Found (%): C, 68.42; H, 5.91;
N, 6.55. C24H24N2O5. Calculated (%): C, 68.56; H, 5.75; N, 6.66.
Ethyl (2E)ꢀ3ꢀ{6´ꢀethoxycarbonylꢀ1,3,3ꢀtrimethylspiro[indꢀ
olineꢀ2,2´ꢀ(2H)chromenꢀ5ꢀyl]}propenoate (23). Rf 0.21 (A), m.p.
1
42—44 C. H NMR (CDCl3), : 1.17, 1.29 (both s, 3 H each,
C(3)Me); 1.32, 1.36 (both t, 3 H each, OCH2CH3, J = 7.1 Hz);
2.76 (s, 3 H, C(1)Me); 4.24, 4.33 (both q, 2 H each, OCH2CH3,
J = 7.1 Hz); 5.71 (d, 1 H, H(3´), J = 10.3 Hz); 6.28 (d, 1 H,
C(O)CH, J = 15.9 Hz); 6.50 (d, 1 H, H(7), J = 8.1 Hz); 6.72
(d, 1 H, H(8´), J = 8.4 Hz); 6.91 (d, 1 H, H(4´), J = 10.2 Hz);
7.28 (d, 1 H, H(4), J = 1.6 Hz); 7.34 (dd, 1 H, H(6), J = 8.1 Hz,
J = 1.6 Hz); 7.66 (d, 1 H, C(O)CHCH, J = 15.9 Hz); 7.78
(d, 1 H, H(5´), J = 2.1 Hz); 7.81 (dd, 1 H, H(7´), J = 8.4 Hz,
J = 2.1 Hz). LC/MS (column II), m/z (ret/min): 448.6 [M + 1]+
(7.47). Found (%): C, 72.23; H, 6.70; N, 3.20. C27H29NO5.
Calculated (%): C, 72.46; H, 6.53; N, 3.13.
Ethyl (2E)ꢀ3ꢀ{6´ꢀmethoxycarbonylꢀ1,3,3ꢀtrimethylspiroꢀ
[indolineꢀ2,2´ꢀ(2H)chromenꢀ5ꢀyl]}propenoate (24). Rf 0.20 (A),
m.p. 44—45 C. 1H NMR (CDCl3), : 1.17, 1.29 (both s, 3 H each,
C(3) Me); 1.32 (t, 3 H, OCH2CH3, J = 7.1 Hz); 2.76 (s, 3 H,
C(1)Me); 3.87 (s, 3 H, OCH3); 4.24 (q, 2 H, OCH2CH3,
J = 7.1 Hz); 5.71 (d, 1 H, H(3´), J = 10.2 Hz); 6.27 (d, 1 H,
C(O)CH, J = 15.9 Hz); 6.50 (d, 1 H, H(7), J = 8.1 Hz); 6.72 (d,
1 H, H(8´), J = 8.3 Hz); 6.91 (d, 1 H, H(4´), J = 10.2 Hz); 7.27
(d, 1 H, H(4), J = 1.7 Hz); 7.34 (dd, 1 H, H(6), J = 8.1 Hz,
J = 1.7 Hz); 7.66 (d, 1 H, C(O)CHCH, J = 15.9 Hz); 7.77 (d, 1 H,
H(5´), J = 2.1 Hz); 7.80 (dd, 1 H, H(7´), J = 8.3 Hz, J = 2.1 Hz).
LC/MS (column I), m/z (ret/min): 434.4 [M + 1]+ (2.87).
Found (%): C, 71.81; H, 6.41; N, 3.42. C26H27NO5. Calculatꢀ
ed (%): C, 72.04; H, 6.28; N, 3.23.
Diethyl (2E,2´´´ E)ꢀ3ꢀ{6´ꢀmethoxycarbonylꢀ1,3,3ꢀtrimethꢀ
ylspiro[indolineꢀ2,2´ꢀ(2H)chromeneꢀ5,8´ꢀdiyl]}bispropenoate
(25). Rf 0.16 (A). 1H NMR (CDCl3), : 1.12 (t, 3 H,
C(5)CH=CHCOOCH2CH3, J = 7.1 Hz); 1.19, 1.27 (both s, 3 H
each, C(3)Me); 1.31 (t, 3 H, C(8´)CH=CHCOOCH2CH3,
J = 7.1 Hz); 2.73 (s, 3 H, C(1)Me); 3.87 (s, 3 H, OCH3); 4.02,
4.23 (both q, 2 H each, OCH2CH3, J = 7.1 Hz); 5.80 (d, 1 H,
H(3´), J = 10.3 Hz); 6.18 (d, 1 H, C(5)CH=CH, J = 16.2 Hz);
6.28 (d, 1 H, C(8´)CH=CH, J = 15.9 Hz); 6.52 (d, 1 H, H(7),
J = 8.0 Hz); 6.93 (d, 1 H, H(4´), J = 10.3 Hz); 7.29 (d, 1 H, H(4),
J = 1.6 Hz); 7.34 (dd, 1 H, H(6), J = 8.0 Hz, J = 1.6 Hz); 7.49
(d, 1 H, C(5)CH=CH, J = 16.2 Hz); 7.65 (d, 1 H, C(8´)CH=CH,
J = 15.9 Hz); 7.76 (d, 1 H, H(5´), J = 2.1 Hz); 7.98 (d, 1 H, H(7´),
J = 2.1 Hz). LC/MS (column I), m/z (ret/min): 532.3 [M + 1]+
(3.01). Found (%): C, 70.30; H, 6.11; N, 3.02. C31H33NO7.
Calculated (%): C, 70.04; H, 6.26; N, 2.63.
Compounds 21—25 were obtained similarly.
Ethyl (2E)ꢀ3ꢀ{1,3,3ꢀtrimethylspiro[indolineꢀ2,2´ꢀ(2H)ꢀ
chromenꢀ6´ꢀyl]}propenoate (21). Rf 0.45 (A), m.p. 99—101 C.
1H NMR (CDCl3), : 1.17, 1.30 (both s, 3 H each, C(3)Me);
1.33 (t, 3 H, OCH2CH3, J = 7.1 Hz); 2.73 (s, 3 H, C(1)Me); 4.25
(q, 2 H, OCH2CH3, J = 7.1 Hz); 5.74 (d, 1 H, H(3´), J = 10.3 Hz);
6.28 (d, 1 H, C(O)CH, J = 16.0 Hz); 6.53 (d, 1 H, H(7),
J = 7.7 Hz); 6.71 (d, 1 H, H(8´), J = 8.4 Hz); 6.85 (td, 1 H, H(5),
J = 7.4 Hz, J = 0.9 Hz); 6.86 (d, 1 H, H(4´), J = 10.3 Hz); 7.07
(dd, 1 H, H(4), J = 7.3 Hz, J = 0.8 Hz); 7.18 (td, 1 H, H(6),
J = 7.6 Hz, J = 1.3 Hz); 7.22 (d, 1 H, H(5´), J = 2.1 Hz); 7.28
(dd, 1 H, H(7´), J = 8.5 Hz, J = 2.2 Hz); 7.60 (d, 1 H,
C(O)CHCH, J = 16.0 Hz). LC/MS (column II), m/z (ret/min):
(2E)ꢀ3ꢀ{6´ꢀCarboxyꢀ1,3,3ꢀtrimethylspiro[indolineꢀ2,2´ꢀ
(2H)chromenꢀ5ꢀyl]}propenoic acid (29). Method B. A 4 M soluꢀ