Synthesis of α-diaminomethylenebutyrolactams by the reaction of α-cyanobutyrolactams with N-trimethylsilylamines

Article abstract of DOI:10.1002/jhet.5570440137

(Chemical Equation Presented) Successive treatment of α- cyanobutyrolactams 1 with N-trimethylsilylamines and water gave the corresponding α-diaminomethylenebutyrolacatms 2 in good yields. In the NOESY spectra of 2, the E isomer, the NOE observed between

Full text of DOI:10.1002/jhet.5570440137

Jan-Feb 2007
227
Synthesis of ꢀ-Diaminomethylenebutyrolactams by the Reaction of
ꢀ-Cyanobutyrolactams with N-Trimethylsilylamines
Fumi Okabe, Syouhei Nakamura and Kenji Yamagata*
Faculty of Pharmaceutical Sciences, Fukuoka University, 8-19-1 Nanakuma,
Jounan-ku, Fukuoka 814-0180, Japan
e-mail: yamagata@fukuoka-u.ac.jp
Received March 3, 2006
R
R
N
O
CN
O
R
R
1)
NH2
N SiMe3
N
N
2) H2O
COR1
COR1
Successive treatment of ꢀ-cyanobutyrolactams 1 with N-trimethylsilylamines and water gave the
corresponding ꢀ-diaminomethylenebutyrolacatms 2 in good yields. In the NOESY spectra of 2, the E
isomer, the NOE observed between ꢁ-CH2 (butyrolactam) and N-CH2 (morpholine, pyrrolidine) or N-CH3
(dimethylamine) indicated a cis configuration of these groups.
J. Heterocyclic Chem., 44, 227 (2007).
R'
R'
N
ꢀ-Methylene- [1-3] and ꢀ-aminomethylenebutyro-
lactams [4-8] are well known with a number of
publications in the literature dealing with synthetic
aspects of these compounds. ꢀ-Methylenebutyrolactams
are also known as potential antitumor agents [2].
However, ꢀ-diaminomethylenebutyrolactams have been
the subject of very few studies. This has been due to the
relative difficulty of the synthesis of ꢀ-diaminomethyl-
enebutyrolactams in earlier years. On a search in the
literature only a single paper was found reporting the
synthesis of ꢀ-diaminomethylenebutyrolactam. Kantlehner
et al. reported the synthesis of 3-[bis(dimethylamino)-
methylene]-1-methyl-2-pyrrolidinone from the reaction of
1-methyl-2-pyrrolidinone with ethoxy-N,N,N',N',N'',N''-
hexamethylmethanetriamine [9]. One marked feature of
ꢀ-diaminomethylenebutyrolactams is the enhanced
enaminic reactivity. The nucleophilicity of the ꢁ-carbon
atom (C-3) is higher than that of the nitrogen atoms of
primary and tertiary amino moieties. In addition, the
carbon-carbon double bond of these species is highly
polarized. Furthermore, the amino substituents can also
participate in the reaction of the system by acting as either
the nucleophilic site or as a leaving group. For these
reason, we are interested in the development of new
method for the synthesis of ꢀ-diaminomethylenebutyro-
lactams.
R'
R'
CN
O
1)
N SiMe3
ClCH2CH2Cl
,
NH
N
2) H2O
N
O
COR
COR
1a-d
2a-o, A
R
1
a
Ph
4-Cl-Ph
Me
b
c
R'
R'
NOE
d
e
N
PhCH2
NH2
N
R'
N
R'
R'
O
N
2
R
Yield(%)
79
2
i
R
Yield(%)
R'
COR
(E)-B
Me
Me
Me
N
N
N
a
64
64
O
N
N
Ph
Ph
62
79
O
b
j
Me
Me
NH2
70
65
N
c
k
Ph
Me
Me
R'
N
75
62
83
68
60
O
N
N
N
N
N
d
4-Cl-Ph
l
N
R'
O
N
N
N
83
73
e
f
m
n
o
4-Cl-Ph
4-Cl-Ph
PhCH2
PhCH2
N
O
Me
Me
COR
Me
Me
O
PhCH2
70
(Z)-B
g
Me
Me
h
N-Trimethylsilylamines are well known as reagents for
silylation of alcohols [10] or amines [11], dealkylation of
esters [12], ring opening of oxiranes [13], synthesis of
silylenol ethers [14] or enamines [15] and carbon-carbon
bond forming reactions [16]. We have recently
reported on the reaction of 3-cyanobutyrolactones with
N-trimethylsilyl-morpholine to give 3-(amino(morpholino)-
methylene)-butyrolactones [17]. In an extension of this
work, this note describes a synthesis of ꢀ-diaminomethyl-
enebutyrolactams by the reaction of ꢀ-cyanobutyrolactams
1
with N-trimethylsilylamines. N-Trimethylsilylamines
used in this study include N-trimethylmorpholine, N-tri-
methylsilylpyrrolidine and N-trimethylsilyldimethylamine.
The starting compounds 1 were prepared by a procedure
described in the literature [18].

228
F. Okabe, S. Nakamura, K. Yamagata
Vol 44
was added to the residue. The precipitate was collected by
filtration, dried and recrystallized from an appropriate solvent to
yield 2.
When a mixture of 1-benzoyl-2-oxo-3-pyrrolidine-
carbonitrile (1a) and N-trimethylsilylmorpholine in 1,2-
dichloroethane was stirred at room temperature, 3-(amino-
(morpholino)methylene)-1-benzoyl-2-pyrrolidinone (2a)
was obtained in 79% yield. The ir spectrum of 2a reveals
two bands at 3385 and 3200 cm-1 due to a primary amino
group. The absorption band at near 2240 cm-1 due to a
non-conjugated cyano group is not observed. The 13C nmr
spectrum exhibits the signals at ꢀ = 76.6 and 169.8 ppm
due to olefinic carbon atoms of the enamine moiety.
These observations indicate that 2a exists in the enamine
(E)-3-(Amino(morpholino)methylene)-1-benzoyl-2-pyrroli-
dinone (2a). This compound was obtained as pale yellow
prisms (2.38 g, 79%), mp 204-205° (acetone); ir (potassium
bromide): ꢂ 3385, 3200 (NH), 1665 (C=O) cm-1; 1H nmr
(DMSO-d6): ꢀ 2.62-2.66 (m, 2H, 4-H), 3.22-3.26 (m, 4H,
2CH2(morpholine)), 3.58-3.63 (m, 4H, 2CH2(morpholine)),
3.64-3.68 (m, 2H, 5-H), 7.30-7.41 ppm (m, 7H, NH2, aryl H);
13C nmr (DMSO-d6): ꢀ 23.2 (4-C), 43.3 (5-C), 46.7 (NCH2), 66.0
(OCH2), 76.6 (3-C), 127.0, 128.2, 129.9, 136.7 (aryl C), 161.4,
169.4 (C=O), 169.8 ppm (=C(NH2)N); ms: m/z 302 [M+H]+.
Anal. Calcd. for C16H19N3O3 (MW 301.3): C, 63.77; H, 6.36; N,
13.94. Found: C, 63.70; H, 6.32; N, 13.82.
structure
B
rather than the imine structure A.
Furthermore, in the NOESY spectrum of 2a ((E)-B), the
presence of a NOE effect between the 4-H and N-CH2
(morpholine) indicated a cis configuration of these
groups, and the (Z)-isomer ((Z)-B) could be excluded.
(E)-3-(Amino(pyrrolidino)methylene)-1-benzoyl-2-pyrroli-
dinone (2b). This compound was obtained as yellow columns
(1.76 g, 62%), mp 203-204° (acetone); ir (potassium bromide):
1
ꢂ 3402, 3177 (NH), 1646 (C=O) cm-1; H nmr (DMSO-d6): ꢀ
1
Elemental analysis, mass and H nmr spectra of 2a are
1.79-1.86 (m, 4H, 2CH2(pyrrolidine)), 2.85-2.90 (m, 2H, 4-H),
3.39-3.48 (m, 4H, 2CH2(pyrrolidine)), 3.60-3.66 (m, 2H, 5-H),
7.29-7.58 ppm (m, 7H, NH2, aryl H); 13C nmr (DMSO-d6): ꢀ
23.1 (4-C), 24.7 (NCH2CH2), 42.9 (5-C), 47.9 (NCH2), 73.3 (3-
C), 126.9, 128.1, 129.5, 137.1 (aryl C), 158.7 (C=O), 168.0
(=C(NH2)N), 169.1 ppm (C=O); ms: m/z 286 [M+H]+. Anal.
Calcd. for C16H19N3O2 (MW 285.3): C, 67.35; H, 6.71; N, 14.73.
Found: C, 67.36; H, 6.69; N, 14.73.
consistent with the assigned structure. Compounds 1b-e
react with N-trimethylsilylmorpholine under the same
conditions to afford the corresponding ꢁ-diaminomethyl-
enebutyrolactams 2d, g, j,
m in good yields.
Subsequently, the reaction of 1a-e with N-trimethylsilyl-
pyrrolidine or N-trimethylsilyldimethylamine resulted in
the formation of the corresponding 3-(amino(pyrrolidino)-
methylene)-2-pyrrolidinones 2b, e, h, k, n or 3-(amino-
(dimethylamino)methylene)-2-pyrrolidinones 2c, f, i, l, o
in 60-83% yields. The stereochemistry of 2b-o was
assigned by means of NOE between the 4-H and NCH2
(morpholine or pyrrolidine) or N-CH3 (dimethylamine).
In the NOESY spectra of 2b-o, the NOE showed that
these groups are located on the same side of the carbon-
carbon double bond system of the enamine moiety.
Although the nucleophilic attack of N-trimethylsilyl-
amines to 1 might be expected to occur at three possible
positions of the lactam carbonyl, acyl carbonyl, or cyano
group, we have shown that for 1 studied in this work
nucleophilic attack takes place exclusively at cyano
group. In conclusion, the reaction of ꢁ-cyanobutyro-
lactams with N-trimethylsilylamines is a versatile new
access to ꢁ-diaminomethylenebutyrolactam compounds.
(E)-3-(Amino(dimethylamino)methylene)-1-benzoyl-2-pyrroli-
dinone (2c). This compound was obtained as pale brown
columns (2.04 g, 79%), mp 193-194° (acetone); ir (potassium
1
bromide): ꢂ 3373, 3208 (NH), 1655, 1635 (C=O) cm-1; H nmr
(DMSO-d6): ꢀ 2.72-2.78 (m, 2H, 4-H), 2.90 (s, 6H, 2CH3), 3.61-
3.66 (m, 2H, 5-H), 7.28-7.42 ppm (m, 7H, NH2, aryl H); 13C nmr
(DMSO-d6): ꢀ 23.6 (4-C), 39.0 (CH3), 43.1 (5-C), 74.5 (3-C),
126.9, 128.1, 129.7, 136.9 (aryl C), 162.1 (C=O), 168.6
(=C(NH2)N), 169.2 ppm (C=O); ms: m/z 260 [M+H]+. Anal.
Calcd. for C14H17N3O2 (MW 259.3): C, 64.85; H, 6.61; N, 16.20.
Found: C, 64.83; H, 6.63; N, 16.08.
(E)-3-(Amino(morpholino)methylene)-1-(4-chlorobenzoyl)-2-
pyrrolidinone (2d). This compound was obtained as colorless
needles (2.52 g, 75%), mp 221-222° (acetone); ir (potassium
1
bromide): ꢂ 3395, 3208 (NH), 1657, 1630 (C=O) cm-1; H nmr
(DMSO-d6): ꢀ 2.62-2.66 (m, 2H, 4-H), 3.23-3.27 (m, 4H,
2CH2(morpholine)), 3.58-3.63 (m, 4H, 2CH2(morpholine)), 3.63-
3.68 (m, 2H, 5-H), 7.34 (br. s, 2H, NH2), 7.36-7.45 ppm (m, 4H,
aryl H); 13C nmr (DMSO-d6): ꢀ 23.2 (4-C), 43.2 (5-C), 46.7
(NCH2), 66.0 (OCH2), 76.5 (3-C), 127.1, 130.0, 134.6, 135.5 (aryl
C), 161.5, 168.2 (C=O), 168.8 ppm (=C(NH2)N); ms: m/z 336
[M+H]+. Anal. Calcd. for C16H18N3O3Cl (MW 335.8): C, 57.23;
H, 5.40; N, 12.51. Found: C, 57.15; H, 5.41; N, 12.56.
EXPERIMENTAL
All melting points are uncorrected. Ir spectra were recorded
1
(E)-3-(Amino(pyrrolidino)methylene)-1-(4-chlorobenzoyl)-
2-pyrrolidinone (2e). This compound was obtained as yellow
prisms (1.97 g, 62%), mp 205-206° (acetone); ir (potassium
bromide): ꢂ 3393, 3200 (NH), 1640 (C=O) cm-1; 1H nmr
(DMSO-d6): ꢀ 1.80-1.87 (m, 4H, 2CH2(pyrrolidine)), 2.84-2.90
(m, 2H, 4-H), 3.40-3.48 (m, 4H, 2CH2(pyrrolidine)), 3.60-3.65
(m, 2H, 5-H), 7.39-7.60 ppm (m, 6H, NH2, aryl H); 13C nmr
(DMSO-d6): ꢀ 23.1 (4-C), 24.7 (NCH2CH2), 42.8 (5-C), 47.8
(NCH2), 73.3 (3-C), 127.0, 129.9, 134.2, 135.9 (aryl C), 158.8
(C=O), 167.8 (=C(NH2)N), 167.9 ppm (C=O); ms: m/z 320
[M+H]+. Anal. Calcd. for C16H18N3O2Cl (MW 319.8): C, 60.06;
H, 5.67; N, 13.14. Found: C, 60.11; H, 5.67; N, 13.09.
on a JASCO FT/IR-230 spectrometer. The H nmr and 13C nmr
spectra were measured with a JEOL JNM-A500 instrument
(500.00 MHz for 1H, 125.65 MHz for 13C) with TMS as internal
standard. 13C signal assignments were confirmed by the DEPT
techniques. FAB mass spectra were taken with a JEOL JMS-
HX100 instrument at 70 eV. Elemental analyses were performed
using a YANACO MT-6 elemental analyzer.
General Procedure for the Preparation of 2. A mixture of
1 (10 mmoles) and N-trimethylsilylamine (10 mmoles) in 1,2-
dichloroethane (20 ml) was stirred at room tempurature for 2
days. After removal of the solvent in vacuo, cold water (5 ml)

Jan-Feb 2007
Synthesis of ꢀ-Diaminomethylenebutyrolactams by the Reaction of
ꢀ-Cyanobutyrolactams with N-Trimethylsilylamines
229
3.36-3.50 (m, 7H, 5-H, CH, 2CH2(pyrrolidine)), 7.55 ppm (br. s,
2H, NH2); 13C nmr (DMSO-d6): ꢂ 8.3 (CH2), 12.0 (CH), 22.4 (4-
C), 24.6 (NCH2CH2), 42.1 (5-C), 47.8 (NCH2), 73.8 (3-C), 158.8
(C=O), 169.2 (=C(NH2)N), 173.1 ppm (C=O); ms: m/z 250
[M+H]+. Anal. Calcd. for C13H19N3O2 (MW 249.3): C, 62.63;
H, 7.68; N, 16.85. Found: C, 62.66; H, 7.71; N, 16.82.
(E)-3-(Amino(dimethylamino)methylene)-1-(4-chlorobenzoyl)-
2-pyrrolidinone (2f). This compound was obtained as yellow
prisms (2.43 g, 83%), mp 182-183° (acetone); ir (potassium
bromide): ꢁ 3411, 3165 (NH), 1650 (C=O) cm-1; 1H nmr
(DMSO-d6): ꢂ 2.73-2.77 (m, 2H, 4-H), 2.91 (s, 6H, 2CH3), 3.61-
3.66 (m, 2H, 5-H), 7.38-7.50 ppm (m, 6H, NH2, aryl H); 13C nmr
(DMSO-d6): ꢂ 23.6 (4-C), 39.0 (CH3), 43.0 (5-C), 74.4 (3-C),
127.1, 130.0, 134.4, 135.8 (aryl C), 162.1 168.1 (C=O), 168.3
(E)-3-(Amino(dimethylamino)methylene)-1-cyclopropane-
carbonyl-2-pyrrolidinone (2l). This compound was obtained
as colorless needles (1.45 g, 65%), mp 188-190° (acetone/
petroleum ether); ir (potassium bromide): ꢁ 3408, 3153 (NH),
ppm (=C(NH2)N); ms: m/z 294 [M+H]+.
Anal. Calcd. for
C14H16N3O2Cl (MW 293.8): C, 57.24; H, 5.49; N, 14.30. Found:
C, 57.10; H, 5.49; N, 14.21.
1
1645, 1630 (C=O) cm-1; H nmr (DMSO-d6): ꢂ 0.75-0.85 (m,
(E)-1-Acetyl-3-(Amino(morpholino)methylene)-2-pyrrol-
idinone (2g). This compound was obtained as colorless columns
(1.63g, 68%), mp 198-199° (acetone); ir (potassium bromide):
4H, CH2 (cyclopropane)), 2.65-2.75 (m, 2H, 4-H), 2.91 (s, 6H,
2CH3), 3.35-3.40 (m, 1H, CH), 3.47-3.53 (m, 2H, 5-H), 7.45
ppm (br. s, 2H, NH2); 13C nmr (DMSO-d6): ꢂ 8.3 (CH2), 12.1
(CH), 22.9 (4-C), 39.1 (CH3), 42.2 (5-C), 75.1 (3-C), 162.2
(C=O), 169.6 (=C(NH2)N), 173.2 ppm (C=O); ms: m/z 224
[M+H]+. Anal. Calcd. for C11H17N3O2 (MW 223.3): C, 59.17; H,
7.67; N, 18.82. Found: C, 59.07; H, 7.63; N, 18.80
1
ꢁ 3392, 3190 (NH), 1648 (C=O) cm-1; H nmr (DMSO-d6): ꢂ
2.33 (s, 3H, CH3), 2.51-2.56 (m, 2H, 4-H), 3.22-3.25 (m, 4H,
2CH2(morpholine)), 3.48-3.54 (m, 2H, 5-H), 3.59-3.64 (m, 4H,
2CH2(morpholine)), 7.38 ppm (br. s, 2H, NH2); 13C nmr (DMSO-
d6): ꢂ 22.3 (4-C), 23.7 (CH3), 41.7 (5-C), 46.8 (NCH2), 66.1
(OCH2), 77.1 (3-C), 161.4, 169.3 (C=O), 169.7 ppm (=C(NH2)N);
ms: m/z 240 [M+H]+. Anal. Calcd. for C11H17N3O3 (MW 239.3):
C, 55.22; H, 7.16; N, 17.56. Found: C, 55.09; H, 7.13; N, 17.50.
(E)-1-Acetyl-3-(Amino(pyrrolidino)methylene)-2-pyrrolidinone
(2h). This compound was obtained as colorless prisms (1.33 g,
60%), mp 201-202° (acetone); ir (potassium bromide): ꢁ 3404,
(E)-3-(Amino(morpholino)methylene)-1-phenylacetyl-2-pyrroli-
dinone (2m). This compound was obtained as colorless needles
(2.63 g, 83%), mp 154-155° (acetone); ir (potassium bromide):
1
ꢁ 3366, 3208 (NH), 1655, 1630 (C=O) cm-1; H nmr (DMSO-
d6):
ꢂ 2.52-2.57 (m, 2H, 4-H), 3.23-3.27 (m, 4H,
2CH2(morpholine)), 3.52-3.56 (m, 2H, 5-H), 3.60-3.63 (m, 4H,
2CH2(morpholine)), 4.24 (s, 2H, COCH2), 7.15-7.30 (m, 5H,
aryl H), 7.45 ppm (br. s, 2H, NH2); 13C nmr (DMSO-d6): ꢂ 22.2
(4-C), 41.1 (COCH2), 42.1 (5-C), 46.8 (NCH2), 66.1(5-C), 77.1
(3-C), 126.1, 128.0, 129.3, 136.3 (aryl C), 161.6 (C=O), 169.4
(=C(NH2)N), 170.2 (C=O) ppm; ms: m/z 316 [M+H]+. Anal.
Calcd. for C17H21N3O3 (MW 315.4): C, 64.74; H, 6.71; N, 13.32.
Found: C, 64.63; H, 6.78; N, 13.19.
1
3135 (NH), 1655 (C=O) cm-1; H nmr (DMSO-d6): ꢂ 1.81-1.85
(m, 4H, 2CH2(pyrrolidine)), 2.33 (s, 3H, CH3), 2.75-2.79 (m, 2H,
4-H), 3.40-3.46 (m, 4H, 2CH2(pyrrolidine)), 3.46-3.51 (m, 2H, 5-
H), 7.54 ppm (br. s, 2H, NH2); 13C nmr (DMSO-d6): ꢂ 22.3 (4-C),
23.6 (CH3), 24.7 (NCH2CH2), 41.4 (5-C), 47.8 (NCH2), 73.5 (3-
C), 158.7 (C=O), 168.9 (=C(NH2)N), 169.1 ppm (C=O); ms: m/z
224 [M+H]+. Anal. Calcd. for C11H17N3O2 (MW 223.3): C, 59.17;
H, 7.67; N, 18.82. Found: C, 59.09; H, 7.65; N, 18.78.
(E)-3-(Amino(pyrrolidino)methylene)-1-phenylacetyl-2-pyr-
rolidinone (2n).
This compound was obtained as colorless
(E)-1-Acetyl-3-(Amino(dimethylamino)methylene)-2-pyr-
rolidinone (2i). This compound was obtained as colorless
prisms (1.26 g, 64%), mp 168-169° (acetone); ir (potassium
bromide): ꢁ 3378, 3135 (NH), 1645 (C=O) cm-1; 1H nmr (DMSO-
d6): ꢂ 2.33 (s, 3H, CH3), 2.63-2.68 (m, 2H, 4-H), 2.90 (s, 6H,
2CH3), 3.47-3.52 (m, 2H, 5-H), 7.43 ppm (br. s, 2H, NH2); 13C
nmr (DMSO-d6): ꢂ 22.8 (4-C), 23.7 (COCH3), 39.1 (NCH3), 41.5
(5-C), 74.8 (3-C), 162.1 169.2 (C=O), 169.3 ppm (=C(NH2)N);
ms: m/z 198 [M+H]+. Anal. Calcd. for C9H15N3O2 (MW 197.2):
C, 54.81; H, 7.67; N, 21.30. Found: C, 54.83; H, 7.71; N, 21.27
(E)-3-(Amino(morpholino)methylene)-1-cyclpropancarbonyl-
2-pyrrolidinone (2j). This compound was obtained as colorless
prisms (1.70g, 64%), mp 170-171° (acetone); ir (potassium
bromide): ꢁ 3392, 3206 (NH), 1656 (C=O) cm-1; 1H nmr
(DMSO-d6): ꢂ 0.74-0.85 (m, 4H, 2CH2(cyclopropane)), 2.52-
2.56 (m, 2H, 4-H), 3.23-3.28 (m, 4H, 2CH2(morpholine)), 3.30-
3.36 (m, 1H, CH), 3.50-3.54 (m, 2H, 5-H), 3.60-3.65 (m, 4H,
2CH2(morpholine)), 7.42 ppm (br. s, 2H, NH2); 13C nmr
(DMSO-d6): ꢂ 8.5 (CH2), 12.2 (CH), 22.4 (4-C), 42.3 (5-C), 46.8
(NCH2), 66.1 (OCH2), 77.4 (3-C), 161.5(C=O), 170.0
(=C(NH2)N), 173.3 ppm (C=O),; ms: m/z 266 [M+H]+. Anal.
Calcd. for C13H19N3O3 (MW 265.3): C, 58.85; H, 7.22; N, 15.58.
Found: C, 58.91; H, 7.14; N, 15.84.
needles (2.20 g, 73%), mp 170-171° (acetone); ir (potassium
bromide): ꢁ 3381, 3181 (NH), 1655 (C=O) cm-1; 1H nmr
(DMSO-d6): ꢂ 1.80-1.86 (m, 4H, 2CH2(pyrrolidine)), 2.76-2.80
(m, 2H, 4-H), 3.41-3.46 (m, 4H, 2CH2(pyrrolidine)), 3.48-3.54
(m, 2H, 5-H), 4.26 (s, 2H, COCH2), 7.17-7.30 (m, 5H, aryl H),
7.50-7.70 ppm (br. s, 2H, NH2); 13C nmr (DMSO-d6): ꢂ 22.3 (4-
C), 24.7 (NCH2CH2), 40.9 (COCH2), 41.8 (5-C), 47.8 (NCH2),
73.3 (3-C), 126.0, 127.9, 129.3, 136.6 (aryl C), 158.9 (C=O),
168.6 (=C(NH2)N), 170.0 ppm (C=O); ms: m/z 300 [M+H]+.
Anal. Calcd. for C17H21N3O2 (MW 299.4): C, 68.20; H, 7.07; N,
14.04. Found: C, 68.29; H, 7.15; N, 14.02.
(E)-3-(Amino(dimethylamino)methylene)-1-phenylacetyl-
2-pyrrolidinone (2o).
This compound was obtained as pale
brown prisms (1.90g, 70%), mp 130-131° (acetone); ir
1
(potassium bromide): ꢁ 3425, 3153 (NH), 1650 (C=O) cm-1; H
nmr (DMSO-d6): ꢂ 2.64-2.67 (m, 2H, 4-H), 2.91 (s, 6H, 2CH3),
3.50-3.53 (m, 2H, 5-H), 4.25 (s, 2H, COCH2), 7.16-7.30 (m, 5H,
aryl H), 7.40-7.60 ppm (br. s, 2H, NH2); 13C nmr (DMSO-d6): ꢂ
22.7 (4-C), 39.1 (CH3), 41.0 (COCH2), 41.9 (5-C), 74.9 (3-C),
126.0, 127.9, 129.3, 136.5 (aryl C), 162.2 (C=O), 169.0
(=C(NH2)N), 170.1 ppm (C=O); ms: m/z 274 [M+H]+. Anal.
Calcd. for C15H19N3O2 (MW 273.3): C, 65.91; H, 7.01; N, 15.37.
Found: C, 65.98; H, 6.98; N, 15.34.
(E)-3-(Amino(pyrrolidino)methylene)-1-cyclpropanecarbonyl-
2-pyrrolidinone (2k).
This compound was obtained as
colorless prisms (1.73 g, 70%), mp 214-215° (acetone); ir
REFERENCES
1
(potassium bromide): ꢁ 3406, 3154 (NH), 1642 (C=O) cm-1; H
nmr (DMSO-d6): ꢂ 0.70-0.83 (m, 4H, 2CH2(cyclopropane)),
1.78-1.85 (m, 4H, 2CH2(pyrrolidine)), 2.75-2.80 (m, 2H, 4-H),
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