Efficient tandem synthesis of 3-alkylaminoprop-2-enamides from 3-trimethylsilylprop-2-ynamides

Article abstract of DOI:10.1134/S1070428013060031

A tandem synthetic approach to previously unknown 3-aminoprop-2-enamides has been developed. It is based on Si-C _sp desilylation of 3-trimethylsilylprop-2-ynamides and subsequent addition of an amine to the triple bond of intermediate terminal

Full text of DOI:10.1134/S1070428013060031

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 6, pp. 822–827. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © M.V. Andreev, A.S. Medvedeva, L.P. Safronova, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49, No. 6,
pp. 839–844.
Efficient Tandem Synthesis of 3-Alkylaminoprop-2-enamides
from 3-Trimethylsilylprop-2-ynamides
M. V. Andreev, A. S. Medvedeva, and L. P. Safronova
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: amedved@irioch.irk.ru
Received September 19, 2012
Abstract—A tandem synthetic approach to previously unknown 3-aminoprop-2-enamides has been developed.
It is based on Si–Csp desilylation of 3-trimethylsilylprop-2-ynamides and subsequent addition of an amine to
the triple bond of intermediate terminal propynamides. The effects of the reaction conditions and amine nature
on the efficiency of the process have been studied.
DOI: 10.1134/S1070428013060031
α,β-Unsaturated enamide moiety constitutes the key
structural fragment of natural antibiotics exhibiting
a broad spectrum of antimicrobial [1] and antitumor
activity [2] and 2′,3′-dideoxy-2′,3′-didehydro nucleo-
sides of the uracil series, which are efficient against
human immunodeficiency (HIV-1) and hepatitis B
viruses [3]. α,β-Unsaturated enamides can be used as
intermediate products in the synthesis of natural prod-
ucts, e.g., doubly unsaturated amides [4], biologically
important polycyclic alkaloids containing a 2-oxo-
piperidine ring [5], pharmacologically valuable
β-amino amides [6], and isoxazolidines [7]; they are
also promising as ligands [8] and monomers. β-Amino
enamides may be regarded as poorly explored com-
pounds. There are very limited published data on the
synthesis and application of β-amino enamides.
Efficient procedures for the synthesis of 2-alkylidene-
1,3-dicarbonyl compounds [9], 1,2,3-triazolecarbox-
amides [10], and β-amino acid derivatives [11] have
been developed on the basis of “push–pull” amino en-
amides; they can also be used as bidentate ligands [9].
β-enamino esters as by-products, especially under
acidic conditions [15].
An alternative method for the synthesis of β-amino-
acrylamides is based on the addition of amines to
terminal propynamides. Secondary amines readily add
to propynamides in acetonitrile to give the correspond-
ing amino enamides in high yield [16]. However, pre-
paration of the initial terminal propynamides requires
the use of inflammable propiolic acid or its highly
toxic derivatives [17]. We recently developed an ef-
ficient one-step procedure for the synthesis of tri-
methylsilylpropynamides from accessible and safe
trimethylsilylpropynoic acid [18]. The presence of
trimethylsilyl group in silicon-containing acetylene
derivatives stabilizes the triple bond and increases the
solubility in organic solvents [19].
The present study was aimed at developing a gen-
eral procedure for the synthesis of β-amino enamides
containing primary, secondary, or tertiary amide group
from accessible trimethylsilylpropynamides via tan-
dem desilylation–amination reaction and elucidating
the effects of the reactant nature and reaction condi-
tions on the efficiency of the process.
The synthesis of β-amino enamides via aminolysis
of β-keto esters [12] and subsequent reaction of β-keto
amides with amines [9] is known. However, this
procedure involves some difficulties. Amination of
β-keto esters requires fairly severe conditions (elevated
temperature, sometimes above 200°C), base catalyst
[13], and the absence of a solvent [14]. In addition,
only tertiary keto amides can be obtained in this way,
and the reaction is accompanied by formation of
We previously reported on highly efficient Si–Csp-
desilylation of 3-trimethylsilylprop-2-ynamides, which
ensured preparation of terminal acetylenic amides in
high yield under mild conditions (in methanol) [20].
Our attempt to synthesize the corresponding β-amino
enamide by reaction of 1-(morpholin-4-yl)-3-tri-
822

EFFICIENT TANDEM SYNTHESIS OF 3-ALKYLAMINOPROP-2-ENAMIDES
823
Scheme 1.
O
O
R3R4NH, MeOH
NR1R2
R3R4N
NR1R2
Me3Si
Ia–Ic
IIa–IIe
Ia, IIa, R1 = R2 = H; Ib, IIb, R1 = H, R2 = Ph; Ic, IIc–IIe, R1R2N = morpholin-4-yl; IIa–IIc, R3 = H, R4 = Me;
IId, R3 = H, R4 = PhCH2; IIe, R3R4N = morpholin-4-yl.
Scheme 2.
O
O
Et3N, MeOH
MW (420 W), 15 min
O
MeO
+
N
N
N
NH2·HCl
H
MeO
O
O
Me3Si
O
Ic
III
methylsilylprop-2-yn-1-one (Ic) with morpholine in
anhydrous acetonitrile at room temperature was un-
successful, and only the initial amide was isolated.
Presumably, unlike terminal analog [16], weak polar-
ization of the triple bond due to oppositely directed
and comparable in strength electron-withdrawing
effects of the trimethylsilyl and amide groups and
steric effect of the trimethylsilyl group strongly reduce
the reactivity of propynamide Ic.
we synthesized previously unknown methyl (Z,E)-
(morpholin-4-yl-3-oxoprop-1-en-1-ylamino)acetate
(III) in 44% yield (isomer ratio 0.64:0.36; Scheme 2).
Amide Ic was also converted in one-pot reaction
into polyfunctional diamide V containing both double
and triple bonds. Tandem desilylation–addition and
subsequent acylation of the amino nitrogen atom gave
methyl [(E)-3-(morpholin-4-yl)-3-oxoprop-1-en-1-yl]-
3-(trimethylsilyl)prop-2-ynamide (V) in an overall
yield of 37% (after column chromatography; inter-
mediate IIc was not isolated; Scheme 3).
Tandem transformation of trimethylsilylpropyn-
amides Ia–Ic into previously unknown “push–
pull” (Z,E)-3-aminoprop-2-enamides IIa–IIc smoothly
occurred in methanol at room temperature by the
action of primary and secondary amines (yield 60–
76%; Scheme 1; Table 1, run nos. 1–5). (Z,E)-3-(Ben-
zylamino)-1-(morpholin-4-yl)prop-2-en-1-one (IId)
was obtained at 65°C.
Using 1-(morpholin-4-yl)-3-trimethylsilylprop-2-
yn-1-one (Ic) as model substrate we examined how the
reactant nature and reaction conditions affect the
efficiency of the formation of enamides IIc–IIe. The
reactivity of amines toward amide Ic in methanol
(25°C, 1 h) depended on the pKa value of amines and
changed in the following series: methylamine
(pKa 10.66) > benzylamine (pKa 9.34) > morpholine
(pKa 8.70) > ammonia (pKa 9.25) ≈ pyridin-2-amine
(pKa 6.86) (Table 2). On the whole, this series is
consistent with the pKa values [21], except for
Amino acid derivatives can also be subjected to
tandem Si–Csp-desilylation–amination. By reaction of
1-(morpholin-4-yl)-3-trimethylsilylprop-2-yn-1-one
(Ic) with glycine methyl ester hydrochloride in the
presence of triethylamine under microwave irradiation
Table 1. Synthesis of β-amino enamides R3R4NCH=CHCONR1R2 (IIa–IIe, III) in MeOH
Run no.
Compound no.
Reaction conditions
Yield,a %
Z/E Isomer ratio (1H NMR)
1
2
3
4
5
6
IIa
IIb
IIc
IId
IIe
III
25°C, 1 h
25°C, 1 h
25°C, 1 h
65°C, 1 h
25°C, 7 h
MW, 15 min
69
72
76
60
75
44
0.16:0.84
0.75:0.25
0.79:0.21
0.97:0.03
0.00:1.00
0.64:0.36
a
Yield of purified product.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 6 2013

ANDREEV et al.
824
Scheme 3.
O
O
MeNH2, MeOH
N
MeNH
N
Me3Si
O
O
Ic
IIc
O
O
Me3Si
CHCl3
C(O)Cl (IV)
N
N
Me3Si
Me
V
O
ammonia. The reaction of the latter with amide Ic
resulted in protodesilylation of amide (Ic) (Table 2, run
no. 6). Increase of the reaction time from 1 to 7 h and
elevated temperature (65°C) favored quantitative
formation of aminopropenamides IId and IIe (Table 2,
run nos. 2–5).
Being a weak base, pyridin-2-amine in methanol
induced only protodesilylation of substrate Ic (1 h,
reflux) with formation of propynamide VI (Scheme 4;
Table 2, run no. 7). When the reaction was carried out
under microwave irradiation (420 W, 15 min),
β-methoxypropenamide VII was formed in quantita-
tive yield as a result of addition of methanol to the
triple bond (Table 2, run no. 8). Obviously, the ad-
dition was preceded by desilylation of initial amide Ic,
as followed from the data of IR (2100 cm–1, C≡C) and
1H NMR spectroscopy (δ 2.9–3.12 ppm, HC≡) [20].
to trimethylsilylpropynamide Ic was stereoselective
only in the reaction with morpholine, which afforded
(E)-1,3-bis(morpholin-4-yl)prop-2-en-1-one (IIe). This
is consistent with published data on the addition of
secondary amines to terminal tertiary propynamides
[16]. Predominant formation of the E isomer was also
observed in the reaction of primary amide Ia with
methylamine (Z/E ratio 0.16:0.84). The reactions of
amides Ic and Ib with primary amines gave the
corresponding Z isomers as major products (Table 1);
their formation is likely to be favored by intramolec-
ular hydrogen bond NH···O=C–N.
To conclude, we have developed a highly efficient
procedure for the synthesis of 3-aminoprop-2-en-
amides via tandem desilylation–amination of acces-
sible trimethylsilylpropynamides. The procedure is
advantageous due to its experimental simplicity, mild
conditions (room temperature), the possibility of using
various initial amides and amines, including amino
acid esters, and high yields of the target products. We
The structure of 3-aminoprop-2-enamides IIa–IId
and III was confirmed by elemental analyses and IR
1
13
and H and C NMR spectra. The addition of amines
Table 2. Reaction of 1-(morpholin-4-yl)-3-trimethylsilylprop-2-yn-1-one (Ic) with amines R3R4NH
Amine
Run no.
Reaction conditions
Product (yield,a %)
R3
R4
b1b
2
(CH2)2O(CH2)2
(CH2)2O(CH2)2
(CH2)2O(CH2)2
25°C, MeCN, 1 h
25°C, MeOH, 1 h
25°C, MeOH, 7 h
25°C, MeOH, 1 h
65°C, MeOH, 1 h
25°C, MeOH, 1 h
65°C, MeOH, 1 h
MW, MeOH, 15 min
25°C, MeOH, 1 h
–
IIe (50), VI (50)
IIe (100)
3
4
H
H
H
H
H
H
PhCH2
PhCH2
H
IId (66), VI (34)
IId (100)
5
6
IIc (14), VI (86)
VI (100)
7
Pyridin-2-yl
Pyridin-2-yl
Me
8
VII (100)
9
IIc (100)
a
According to the 1H NMR data.
Initial amide Ic was recovered.
b
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 6 2013

EFFICIENT TANDEM SYNTHESIS OF 3-ALKYLAMINOPROP-2-ENAMIDES
825
Scheme 4.
O
65°C, 1 h
N
H
O
VI
O
O
2-Aminopyridine, MeOH MW (700 W), 15 min
MeO
N
N
O
Me3Si
O
Ic
VII
O
N
N
N
H
O
also have demonstrated the possibility for one-pot
transformation of initial propynamide into polyfunc-
tional diamides containing both double and triple
bonds. Polyfunctionalized aminopropenamides can be
used as building blocks in fine organic synthesis, bio-
logically active substances, and multidentate ligands
for metal-complex catalysis.
4.53 d (1H, =CHCO, J = 12.56 Hz, E), 6.36 m (1H,
NCH=, J = 8.36 Hz, Z), 7.17 m (1H, NCH=, J =
12.96 Hz, E), 6.27 br.s (3H, NH, NH2, E), 6.53 br.s
(2H, NH2, Z), 7.97 br.s (1H, NH, Z); Z/E ratio
0.16:0.84. 13C NMR spectrum (DMSO-d6), δC, ppm:
30.64 (CH3N, E), 35.13 (CH3N, Z), 85.7 (=CHCO, Z),
88.10 (=CHCO, E), 147.96 (NCH=, E), 151.53
(NCH=, Z), 171.04 (C=O, E), 173.50 (C=O, Z). Found,
%: C 47.84; H 8.02; N 28.30. C4H8N2O. Calculated,
%: C 47.99; H 8.05; N 27.98.
EXPERIMENTAL
The IR spectra were recorded on a Bruker IFS-25
1
(Z,E)-3-(Methylamino)-N-phenylprop-2-enamide
(IIb). Yield 60 mg (72%), mp 123–125°C. IR spec-
trum (KBr), ν, cm–1: 1660 (C=O), 1590, 1580, 1560
spectrometer. The H and 13C NMR spectra were
measured on a Bruker DPX-400 instrument from solu-
tions in CDCl3 using hexamethyldisiloxane as internal
reference. Microwave-assisted reactions were carried
out in an unmodified LG MS-1904H microwave
furnace (700 W); the reaction mixture was placed into
a 25-ml Teflon high-pressure reactor. Initial 3-trimeth-
ylsilylprop-2-ynamides were synthesized according to
the procedure described in [18].
1
(C=C, C=Carom), 1530 (C–N, δNH). H NMR spectrum
(CDCl3), δ, ppm: 2.76 d (3H, CH3N, J = 4.92 Hz, E),
2.95 d (3H, CH3N, J = 4.59 Hz, Z), 4.43 d (1H,
=CHCO, J = 7.68 Hz, Z), 4.76 d (1H, =CHCO, J =
12.56 Hz, E), 6.49 m (1H, NCH=, J = 7.92 Hz, Z),
7.58 m (1H, NCH=, J = 12.72 Hz, E), 6.73 br.s (1H,
NHPh, Z), 6.87 br.s (1H, NHPh, E), 6.99 t (1H, p-H,
J = 7.08 Hz), 7.24 t (2H, m-H, J = 7.12 Hz), 7.42 d
(2H, o-H, J = 8.08 Hz, Z), 7.48 d (2H, o-H, J =
8.04 Hz, E), 7.76 br.s (1H, NHMe, E), 8.23 br.s (1H,
NHMe, Z); Z/E ratio 0.75:0.25. 13C NMR spectrum
(CDCl3), δC, ppm: 30.71 and 35.10 (CH3N), 84.72
(=CHSO, E), 88.45 (=CHCO, Z); 119.98, 123.25,
129.05, 139.27, 139.50 (Carom); 148.77 (NCH=, E),
152.34 (NCH=, Z), 169.65 (C=O, E), 167.50 (C=O, Z).
Found, %: C 67.75; H 6.89; N 15.93. C10H12N2O.
Calculated, %: C 68.16; H 6.86; N 15.90.
3-(Methylamino)prop-2-enamides IIa–IIc (gen-
eral procedure). Gaseous methylamine was passed
over a period of 1 h at room temperature through a so-
lution of 0.47 mmol of 3-trimethylsilylprop-2-ynamide
Ia–Ic in 10 ml of methanol. The solvent was removed
under reduced pressure, and the residue was recrystal-
lized from 1,4-dioxane.
(Z,E)-3-(Methylamino)prop-2-enamide (IIa).
Yield 33 mg (69%), mp 89–91°C. IR spectrum (KBr),
ν, cm–1: 1650 (C=O), 1550 (C–N, δ NH, C=C).
1H NMR spectrum (DMSO-d6), δ, ppm: 2.56 d (3H,
CH3N, J = 4.88 Hz, E), 2.81 d (3H, CH3N, J =
4.88 Hz, Z), 4.29 d (1H, =CHCO, J = 8.04 Hz, Z),
(Z,E)-3-(Methylamino)-1-(morpholin-4-yl)prop-
2-en-1-one (IIc). Yield 61 mg (76%), mp 135–136°C.
IR spectrum (KBr), ν, cm–1: 1650 (C=O), 1580 (C=C),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 6 2013

ANDREEV et al.
826
1
1530 (C–N, δNH). H NMR spectrum (CDCl3), δ,
ppm: 2.74 d (3H, CH3N, J = 5.04, E), 2.90 d (3H,
CH3N, J = 4.92 Hz, Z), 3.46 m (4H, NCH2, Z), 3.54 m
(4H, NCH2, E), 3.62 m (4H, OCH2, Z, E), 4.56 d (1H,
=CHCO, J = 8.08 Hz, Z), 4.92 d (1H, =CHCO, J =
12.52 Hz, E), 6.50 m (1H, NCH=, J = 8.20 Hz, Z),
7.60 m (1H, NCH=, J = 12.52 Hz, E), 8.41 br.s (1H,
Methyl 2-[(Z,E)-3-(morpholin-4-yl)-3-oxoprop-1-
en-1-ylamino]acetate (III). A mixture of 70 mg
(0.33 mmol) of amide Ic, 42 mg (0.33 mmol) of
methyl 2-aminoacetate hydrochloride, and 33 mg
(0.33 mmol) of triethylamine in 5 ml of methanol was
placed into a Teflon reactor and was subjected to
microwave irradiation (420 W) over a period of
15 min. The mixture was then treated with 5 ml of
water and extracted with diethyl ether, and the extract
was dried over MgSO4 and evaporated to isolate 36 mg
(44%) of III with mp 131–132°C. IR spectrum (film),
ν, cm–1: 1720 (C=O, ester), 1620 (C=O, amide), 1570
(C=C), 1530 (C–N, δ NH), 1510, 1090 (C–O).
1H NMR spectrum (CDCl3), δ, ppm: 3.53 m (4H,
NCH2), 3.67 m (4H, OCH2), 3.76 s (3H, CH3O, Z),
3.81 s (3H, CH3O, E), 3.90 d (2H, CH2CO, J =
6.36 Hz), 4.78 d (1H, =CHCO, J = 8.56 Hz, Z), 5.02 d
(1H, =CHCO, J = 12.72 Hz, E), 6.53 m (1H, NCH=,
J = 8.56 Hz, Z), 7.64 m (1H, NCH=, J = 12.48 Hz, E),
8.82 br.s (NH); Z/E ratio 0.64:0.36. 13C NMR spec-
trum (CDCl3), δC, ppm: 45.40 (NCH2), 49.27 (CH2CO),
52.27 (OCH3), 66.82 and 66.98 (OCH2), 82.87
(=CHCO), 150.35 (NCH=), 169.74 and 170.60 (C=O).
Found, %: C 48.28; H 7.07; N 10.98. C10H16N2O4·
H2O. Calculated, %: C 48.77; H 7.37; N 11.38.
13
NH); Z/E ratio 0.79:0.21. C NMR spectrum (CDCl3),
δC, ppm: 34.82 (CH3N), 42.34 and 43.98 (NCH2),
66.91 and 66.98 (OCH2), 80.18 (=CHCO, E), 83.61
(=CHCO, Z), 149.86 (NCH=, Z), 152.32 (NCH=, E),
168.62 (C=O, Z), 170.48 (C=O, E). Found, %:
C 56.60; H 8.64; N 16.70. C8H14N2O2. Calculated, %:
C 56.45; H 8.29; N 16.46.
(Z,E)-3-(Benzylamino)-1-(morpholin-4-yl)prop-
2-en-1-one (IId). A mixture of 0.5 g (2.4 mmol) of
4-(3-trimethylsilyl-1-oxoprop-2-yn-1-yl)morpholine
(Ic) and 0.25 g (2.4 mmol) of benzylamine in methanol
was heated for 1 h at 65°C. The solvent was removed
under reduced pressure, and the residue was purified
by column chromatography using methanol–chloro-
form (1:40) as eluent. Yield 0.35 g (60%), oily sub-
stance. IR spectrum (film), ν, cm–1: 1630 (C=O), 1570
1
(C=C, C–N, δNH). H NMR spectrum (CDCl3), δ,
ppm: 3.49 m (4H, NCH2), 3.65 m (4H, OCH2), 4.21 d
(2H, CH2Ph, J = 5.04 Hz, E), 4.30 d (2H, CH2Ph, J =
6.08 Hz, Z), 4.65 d (1H, =CHCO, J = 8.16 Hz, Z),
5.04 d (1H, =CHCO, J = 12.72 Hz, E), 6.63 m (1H,
NCH=, J = 8.32 Hz, Z), 7.67 m (1H, NCH=, J =
12.60 Hz, E), 7.24–7.31 m (5H, Ph), 8.94 br.s (1H,
N-Methyl-N-[(E)-3-(morpholin-4-yl)-3-oxoprop-
1-en-1-yl]-3-trimethylsilylprop-2-ynamide (V).
Gaseous methylamine was passed over a period of 1 h
at room temperature through a solution of 0.97 g
(4.6 mmol) of compound Ic in 10 ml of methanol. The
solvent was removed under reduced pressure, the
residue was dissolved in 20 ml of chloroform, a solu-
tion of 0.74 g (4.6 mmol) of 3-trimethylsilylprop-2-
ynoyl chloride (IV) in 10 ml of chloroform was added
dropwise, and the mixture was stirred for 1 h. The
mixture was then treated with a 5% solution of sodium
hydrogen carbonate and extracted with diethyl ether,
the extract was dried over MgSO4 and evaporated
under reduced pressure, and the residue, 1.13 g (84%),
was purified by column chromatography using ethyl
acetate–methanol (100:1) as eluent. Yield 0.5 g (37%),
mp 83–84°C. IR spectrum (KBr), ν, cm–1: 1630 (C=O),
13
NH); Z/E ratio 0.97:0.03. C NMR spectrum (CDCl3),
δC, ppm: 43.00–46.50 (NCH3), 48.88 (CH2Ph, Z),
52.11 (CH2Ph, E), 66.88 (OCH2), 81.18 (=CHCO, E),
85.35 (=CHCO, Z); 127.15, 127.42, 128.36, 128.69,
139.02 (Carom, E, Z), 148.61 (NCH=, Z), 150.94
(NCH=, E), 170.22 (C=O, E). Found, %: C 67.81;
H 7.33; N 10.86. C14H18N2O2. Calculated, %: C 68.27;
H 7.37; N 11.37.
(2E)-1,3-Bis(morpholin-4-yl)prop-2-en-1-one
(IIe). A mixture of 100 mg (0.47 mmol) of compound
Ic and 41 mg (0.47 mmol) of morpholine in methanol
was stirred for 7 h at 25°C. The solvent was removed
under reduced pressure, and the crystalline residue was
washed with diethyl ether. Yield 80 mg (75%),
mp 131–132°C (no melting point was given in [16]).
1H NMR spectrum (CDCl3), δ, ppm: 3.18 m (4H,
3-NCH2, J = 4.64 Hz); 3.53 m, 3.64 m, and 3.70 m
(12H, OCH2, NCH2, J = 4.76 Hz); 4.93 (1H, =CHCO,
J = 12.60 Hz), 7.38 d (1H, NCH=, J = 12.60 Hz).
Found, %: C 58.65; H 8.13; N 12.31. C11H18N2O3. Cal-
culated, %: C 58.39; H 8.02; N 12.38.
1
1580 (C=C), 1250, 830 (Si–C). H NMR spectrum
(CDCl3), δ, ppm: 3.13 s (3H, CH3N), 3.61 m (4H,
NCH2), 3.68 m (4H, OCH2), 5.66 d and 5.74 d* (1H,
=CHCO, J = 13.08 Hz, E), 8.60 d (1H, NCH=, J =
13.08 Hz, E). 13C NMR spectrum (CDCl3), δC, ppm
29.40 (CH3N), 41.94–47.15 (NCH2), 66.92 (OCH2),
98.98 (=CHCO); 94.02, 100.81, 102.66 [C≡C,
* Rotamer concentration 15%.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 6 2013

EFFICIENT TANDEM SYNTHESIS OF 3-ALKYLAMINOPROP-2-ENAMIDES
827
11. Hsiao, Y., Rivera, N.R., Rosner, T., Krska, S.W.,
Njolito, E.,Wang, F., Sun, Y., Armstrong, J.D., Grabow-
ski, E.J.J., Tillyer, R.D., Spindler, F., and Malan, C.,
J. Am. Chem. Soc., 2004, vol. 126, p. 9918.
=CHCO (rotamer)]; 143.27 (NCH=), 153.52
(≡C–C=O), 163.12 (=C–C=O). 29Si NMR spectrum
(CDCl3): δSi –14.78 ppm. Found, %: C 57.63; H 7.82;
N 9.65; Si 9.19. C14H22N2O3Si. Calculated, %:
C 57.11; H 7.53; N 9.51; Si 9.54.
12. Kibler, C.J. and Weissberger, A., Organic Syntheses,
Horning, E.C., Ed., New York: Wiley, 1955, collect.
vol. 3, p. 108.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 6 2013