MUKHAMETYANOVA et al.
648
26.18 (C3'H2), 27.35 (C5'H2), 33.77 (C2'H2), 37.99
(C6'H2), 44.8 (C3a,7aH), 45.61 (C4,7H), 52.15 (C8H2),
134.33 (C5,6H), 177.95 (C1,3=O), 178.51 (C1'=O).
Found, %: С 64.98, H 6.93, N 5.03. Calculated
C15H19NO4 (М 277.32), %: С 64.97; H 6.91; O 23.08;
N 5.05.
and С10'H2), 3.58 br m (2H, C4'H2), 5.91 s (1H, =C7'H),
6.03 m (2H, C5,6H), 7.31 s (2H, C3'',5''H), 7.26 s (1H,
C4''H), 7.46 s (2H, C2'',6''H). 13С NMR spectrum, δ,
ppm: 24.91 (C9'H2), 26.40 (C10'H2), 32.99 (C8'H2),
37.30 (C4'H), 44.88 (C4,7H), 45.68 (C3a,7aH), 52.21
(C8H2), 95.26 (=С5'), 98.78 (=С7'H), 126.43 (C3'',5''H),
128.55 (C4''H), 129.08 (C2'',6''H), 132.13 (C1''), 134.42
(C5,6H), 168.53 (С1'), 172.68 (C3'), 177.63 (С1,3=О),
204.45 (=С=). Found, %: С 71.61; H 5.53, N 6.96.
C24H22N2O4. Calculated, %: С 71.63; H 5.51; O 15.90;
N 6.96. М 402.44.
Synthesis of allenes by the Wittig reaction
(general procedure). A five-fold excess of oxalyl
chloride was added to a suspension of 1 g of acid in
10 mL of anhydrous methylene chloride. The mixture
was left to stand overnight and then the solvent and
excess oxalyl chloride were removed on a rotary
evaporator. The resulting chloride was further reacted
without purification. Triethylmine was added dropwise
to a solution of an equimolar amount of methyl
(triphenylphosphoranylidene)acetate in CH2Cl2. The
resulting solution was cooled to–5°С, and a cold
solution of N-substituted amino acid chloride was
slowly added dropwise to it. The reaction mixture was
stirred for 2 h, after which the solvent was removed,
and the residue was subjected to column chromatog-
raphy (eluent petroleum ether–ethyl acetate, 4 : 1) to
isolate the reaction product.
2-[6-(2,5-Dioxo-1-phenylpyrrolidin-3-ylidene)-
hex-5-en-1-yl]-3a,4,7,7a-tetrahydro-1H-4,7-metha-
noisoindole-1,3(2H)-dione (1c). Yield 1.16 g (78%).
Yellow oil. IR spectrum, ν, cm–1: 730, 1192, 1377,
1
1436, 1695, 1768, 1948. H NMR spectrum (CDCl3),
δ, ppm: 1.41 d (1Ha, C8H2, J 8.6 Hz), 1.49 m (4H,
C9',10'H2), 1.65 d (1Hb, С8H2, J 8.6 Hz), 2.13 s (2H,
C8'H2), 3.18 s (2H, С3a,7aH), 3.31 m (4H, C4,7H,
С11'H2), 3.55 br.m (2H, С4'H2), 5.88 m (1H, =C7'H),
6.05 m (2H, C5,6H), 7.26 s (2H, C3'',5''H), 7.33 s (1H,
C4''H), 7.45 s (2H, C2'',6''H). 13С NMR spectrum, δ,
ppm: 25.68(C9'H2), 26.78 (C10'H2), 30.91 (C8'H2), 33.00
(C4'H2), 37.84 (C11'H2), 44.86 (C4,7H), 45.71 (C3a,7aH),
52.21 (C8H2), 94.34 (=С5'), 99.31 (=С7'H),126.57
(C3'',5''H), 128.53 (C4''H), 129.06 (C2'',6''H), 132.10
(C1''), 134.36 (C5,6H), 168.39 (С1'), 172.56 (C3'), 177.71
(С1,3=О), 204.65 (=С=). Found, %: С 72.12; H 5.81, N
6.71. C25H24N2O4. Calculated, %: С 72.10; H 5.81; O
15.37; N 6.73. М 416.47.
2-[4-(2,5-Dioxo-1-phenylpyrrolidin-3-ylidene)but-
3-en-1-yl]-3a,4,7,7a-tetrahydro-1H-4,7-metha-
noisoindole-1,3(2H)-dione (1a). Yield 1.09 g (70%),
yellow oil. IR spectrum, ν, cm–1: 724, 1166, 1377,
1
1456, 1653, 1767, 1952. H NMR spectrum (CDCl3),
δ, ppm: 1.53 d (1Ha, C8H2, J 8.6 Hz), 1.69 d (1Hb,
C8H2, J 8.6 Hz), 2.43 s (2H, C8'H2), 3.26 s (2H,
С3a,7aH), 3.35 m (4H, C4,7H and С9'H2), 3.54 br.m (2H,
C4'H2), 5.81 s (1H, =C7'H), 6.08 m (2H, C5,6H), 7.32 s
(2H, C3'',5''H), 7.32 s (1H, C4''H), 7.46 s (2H, C2'',6''H).
13С NMR spectrum, δ, ppm: 26.11 (C8'H2), 32.64
(C4'H2), 36.61 (C9'H2), 44.62 (C4,7H), 45.47 (C3a,7aH),
51.92 (C8H2), 91.31 (=С5'), 96.06 (=С7'H), 126.26
(C3'',5''H), 128.41 (C4''H), 128.84 (C2'',6''H), 131.77
(C1''), 134.19 (C5,6H), 167.96 (С1'), 172.13 (C3'), 177.63
(С1,3=О), 204.43 (=С=). Found, %: С 71.14; H 5.17, N
7.20. C23H20N2O4. Calculated, %: С 71.12; H 5.19; O
16.48; N 7.21. М 388.42.
ACKNOWLEDGMENTS
The spectral part of the research was performed on
the equipment of the Center for Collective Use, Ufa
Institute of Chemistry, Russian Academy of Sciences
(RAS).
FUNDING
The work was performed in the framework of the
program for research of the Ufa Institute o Chemistry
RAS on the subject “Synthesis of Biologically Active
Heterocyclic and Terpenoid Compounds” (State regist-
ration no. АААА-А17-117011910025-6) and State
orders of the Ministry for Education and Science (State
registration no. АААА-А17-117011910027-0).
2-[5-(2,5-Dioxo-1-phenylpyrrolidin-3-ylidene)-
pent-4-en-1-yl]-3a,4,7,7a-tetrahydro-1H-4,7-metha-
noisoindole-1,3(2H)-dione (1b). Yield 1.22 g (80%),
orange oil. IR spectrum, ν, cm–1: 724, 1161, 1362,
1
1456, 1661, 1761, 1973. H NMR spectrum (CDCl3),
δ, ppm: 1.49 d (1Ha, C8H2, J 8.5 Hz), 1.58 m (2H,
C9'H2), 1.65 d (1Hb, С8H2, J 8.5 Hz), 2.12 m (2H,
C8'H2), 3.19 s (2H, С3a,7aH), 3.32–3.36 m (4H, C4,7H
CONFLICT OF INTEREST
The authors declare no conflict of interest.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 55 No. 5 2019