Reactions of heterocumulenes with organometallic reagents: XII. Reaction of metallated vinyl ethers with isocyanates: Ingenious synthesis of pyruvic acid amides

Article abstract of DOI:10.1134/S1070428007080052

Acid hydrolysis of 2-alkoxy-N-substituted acrylamides easily obtained by reacting α-metallated vinyl ethers with isocyanates proceeded regiospecifically leading to the formation in a high yield of virtually undescribed and difficultly available 2-oxo-N-substituted propanamides.

Full text of DOI:10.1134/S1070428007080052

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 8, pp. 1124−1129. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © N.A. Nedolya, N.I. Shlyakhtina, 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43, No. 8, pp. 1134−1138.
Reactions of Heterocumulenes with Organometallic Reagents:
XII*. Reaction of Metallated Vinyl Ethers with Isocyanates:
Ingenious Synthesis of Pyruvic Acid Amides
N. A. Nedolya and N. I. Shlyakhtina
Faworsky Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
Irkutsk, 664033 Russia
e-mail: nina@irioch.irk.ru
Received September 28, 2006
Abstract—Acid hydrolysis of 2-alkoxy-N-substituted acrylamides easily obtained by reacting α-metallated vinyl
ethers with isocyanates proceeded regiospecifically leading to the formation in a high yield of virtually undescribed
and difficultly available 2-oxo-N-substituted propanamides.
DOI: 10.1134/S1070428007080052
Vinyl ethers find versatile applications [2], in
particular, in the synthesis of carbonyl compounds,
including industrially important acetaldehyde, oxy-
aldehydes, 19-norsteroids (promising substances for the
hormonal therapy) etc., due to the high ability of the
vinyloxy group to undergo protolytic [3, 4]. The acid
hydrolysis of the α-metallated vinyl ethers with electro-
philes readily provides more complex and functionalized
keto-systems which mostly are unavailable by other
procedures [5].
acid hydrolysis conditions. The double carbon-carbon
bond in vinyl ethers and acrylamides is known to possess
qualitatively different chemical character: electrophilic
reactions are characteristic of vinyl ethers and nucleo-
philic reactions, of acrylamides. Moreover, the structure
of compounds I and II alongside the vinyl group contains
a rival reaction center, amide function, and this fact can
complicate the reaction (lead to the formation of products
mixtures), or totally direct it to another pathway, for the
amides are also prone to the hydrolytic cleavage, not only
in basic but also in acidic media [9]. At the same time a
successful performance of regioselective protolytic
cleavage of compounds I and II at the vinyloxy group
opens the way to previously unknown derivatives of
pyruvic (2-oxopropanoic) acid that takes a fairly
significant part in various biochemical processes [10].
Involving into the reaction with α-metallated vinyl
ethers {alkoxyethane carbanions easily generated in situ
by treatment with the Lochmann–Schlosser base (n-
BuLi–t-BuOK, THF–hexane, –100...–40°C [6])}
accessible aliphatic and aromatic isocyanates that we
have recently performed [7] ensures a simple and
convenient route to a new family of previously unknown
and difficultly available N-mono- I and N,N-di- II
substituted acrylamides, promising monomers, synthons,
and building blocks for the fine organic synthesis,
including a synthesis of ingenious keto-systems.
We report here on the investigation of the behavior
under acid hydrolysis conditions of certain representa-
tives of α-substituted acrylic acid amides which we have
formerly synthesized [7]. The study resulted in
demonstrating the retention of the principal properties
of vinyl ethers by 2-methoxy-N-propyl- (I) and 2-alkoxy-
N-alkyl-N-methyl- (II) acrylamides, although the
presence of the amide fragment in their structure might
significantly affect as already mentioned the reactivity
of the vinyloxy group. The compounds sufficiently
readily underwent a protolytic cleavage giving in high
yields previously unknown and inaccessible 2-oxo-N-
However, inasmuch as 2-alkoxy-N-alkyl- I and 2-alk-
oxy-N,N-dialkyl- II acrylamides [7] are, on the one hand,
α-substituted vinyl ethers and on the other hand, amides
of α-substituted acrylic acid, i.e., typical representatives
of captodative alkenes [8], it is fairly difficult to predict
a priori their reactivity, in particular, their behavior under
* For Communication XI, see [1 ].
1124

REACTIONS OF HETEROCUMULENES WITH ORGANOMETALLIC REAGENTS: XII
1125
OR R'
N
O
R'
N
H+
H2O
H2O
H
Me
Me
H
(1) BuLi_t-BuOK
OR
OR R'
O
I
O
III
(2) R'N=C=O
N
H
_
M+
OR R'
N
O
R'
N
O
H+
Me H2O
MeI
Vа, Vb
VI
Me
O
O
IIа, IIb
IVа, IVb
M = K, Li; I, III, R = Me, R' = n-Pr; II, IV, R = Me, R' = n-Pr (a); R = Et, R' = i-Pr (b); V, R = Me (a), Et (b).
propyl- (III) and 2-oxo-N-alkyl-N-methyl- (IV)
propanamides (pyruvic acid amides).
ammonium chloride or by N-alkylation with methyl
iodide of adduct VI) under conditions comprehensively
described in [7]. Hydrolysis of compounds I and II was
performed in a mixed water-organic (dioxane, methanol)
solvent in the presence of hydrochloric acid taken not in
a commonly used catalytic quantity [2–4], but in a super-
The synthesis of acrylamides I and II was carried
out by reaction of α-metallated methyl and ethyl vinyl
ethers (V) with propyl and isopropyl isocyanates
(followed by mild hydrolysis with water solution of
Preparation conditions for 2-oxo-N-alkyl- III and 2-oxo-N,N-dialkyl- IV propanamides by acid-catalyzed hydrolysis of acrylamides
I, II, and VII (2 ml of water, 2 ml of dioxane, 1.4 mmol of acrylamide)
Temperature,
°C
Time,
min
Amount of HCl, Conversion of compounds
Reaction
product no.
III
R'
Run no. Reagent no.
XR
ga (mmol)b
0.20 (1.8)
0.50 (4.5)
I and II, %c
1
2
Ia
Ia
OMe n-Pr
OMe n-Pr
OMe n-Pr
OMe n-Pr
OMe n-Pr
OMe n-Pr
OMe n-Pr
OMe n-Pr
OMe n-Pr
OEt i-Pr
OEt i-Pr
SEt n-Pr
SEt n-Pr
SEt n-Pr
~20
~20
10
10
~0
~0
III
3
Ia
III
30–40
~20
30
0.30 (2.7)
0.20 (1.8)
0.20 (1.8)
0.20 (1.8)
0.25 (2.3)
0.25 (2.3)
0.41 (11.3)
0.25 (2.3)
0.41 (11.3)
0.26 (2.4)
0.50 (4.5)
0.50 (4.5)
~100
~0
4
IIa
IIa
IIa
IIa
IIa
IIaf
IIb
IIbh
VII
VII
VII
IVa
IVa
IVa
IVa
IVa
IVa
IVb
IVb
IVa
IVa
IVa
10
5
30–40
30–40
30–40
30–40
40–45
30–40
45
40
~90
6
135
60
~100
~100
~94
~100g
~100
~100i
~0
7
8d
9e
10d
11e
12d
13d
14d
60
60
60
60
30–40
30–40
30–40
180
60
~70
~75j
120
a 33% water solution of HCl.
b Calculated on dry HCl.
c Estimated from the integral intensity of vinyl protons signals in the 1H NMR spectra.
d In methanol (2 ml).
e In 10 ml of MeOH.
f 7.0 mmol.
g Preparative yield of compound IVa 75%.
h 6.0 mmol.
i Preparative yield of compound IVb 78%.
j Reaction product is obviously impure: many foreign signals in the 1H NMR spectrum.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 8 2007

NEDOLYA, SHLYAKHTINA
1126
stoichiometric amount (1.3–3.2 mmol of HCl per 1 mmol
of substrate), for it had been shown before [11] that the
amide moiety efficiently bound the acid catalyst. The
investigated reaction conditions and the results obtained
are presented in the table.
For comparison, the thioanalog of compound IIa,
N-methyl-N-propyl-2-(ethylsulfanyl)acrylamide (VII)
[H2C=C(SEt)C(=O)N(Me)Pr] prepared analogously from
the carbanion of (ethysulfanyl)ethene and propyl-
isocyanate [7] in reaction under study proved to be as
expected considerably more passive than 2-alkoxy-
acrylamides I and II. Under comparable hydrolysis
conditions (see the table, cf. run no. 12 and runs nos. 8
and 10) compound VII showed high stability against
The reaction progress was monitored by IR [7, 12,
1
13] and H NMR [7, 13, 14] spectra of the reaction
mixtures. The intensity of absorption bands ν(C=C)
1580–1630 cm–1 and signals at 4.40 d and 5.36 d ppm
(CH2=) were followed in the spectra of compound I or
signals at 4.21–4.30 d and 4.36–4.46 d ppm (CH2=) in
the spectra of compounds IIa and IIb, 3.62–3.64 s ppm
(OMe) or 1.29 t and 3.77 q ppm (OEt) of alkoxyethene
fragment (up till their total disappearance), and
simultaneously was observed the appearance of very
strong carbonyl absorption bands at 1700 cm–1 (MeC=O)
1
hydrolysis and was recovered intact (by the H NMR
data). Even prolonging the reaction to 3 h (instead of
40–60 min for compound II) at HCl concentration 1.7
mmol per 1 mmol of substrate (see the table, run no. 12)
did not initiated the hydrolysis. Only the raising the HCl
concentration to 3.2 mmol per 1 mmol of substrate,
namely, nearly twofold, resulted in formation of
compound IVa in ~70% yield (see the table, run no. 13).
However the attempt to raise the conversion of 2-(ethyl-
sulfanyl)acrylamide (VII) by increasing the reaction time
from 1 to 2 h keeping the same other parameters of
reaction from the run no. 13 provided only a target
product contaminated with impurities (see the table, run
no. 14).
1
and singlets in the H NMR spectra [2.37–2.46 ppm
(Me)] belonging to the acyl group. The absorption band
at 1630 cm–1 in the IR spectra of the reaction products
corresponds to NC=O vibrations. In the 13C NMR spec-
trum the acyl carbonyl signal appeared at 194–198 ppm,
whereas the amide carbonyl signal was observed at 166–
167 ppm. The carbonyl signals of the initial amides I
and II are located in the same region, at 162 and 166
ppm respectively. The lack of vinyl carbon signals [86–
89 (CH2=), 154–157 ppm (C=)] in the 13C NMR spectra
of the reaction products is an additional proof of the
protolytic cleavage at the vinyloxy group in acrylamides
I and II.
The electron-donor properties of sulfur atom in vinyl
sulfides are known to be less pronounced than those of
oxygen atom in the alkoxyethenes (different estimates
[4, 16, 17] consider the p,π-conjugation in a vinylsulfanyl
group to be 2–3 times weaker than in a vinyloxy group).
Therefore the π-electron density excessive with respect
to ethylene or 3-chloro-1-propene [18] on the β-carbon
atom subjected to the electrophile attack in alkyl vinyl
sulfides is ~3 times lower (0.06–0.10 of an electron
charge) than in the oxygen analogs (0.20–0.25) [16, 17].
The stabilization of the intermediate carbocation by the
unshared electron pairs of sulfur is also less efficient.
Consequently the α,β-unsaturated sulfides are less active
in reactions of electrophilic addition than the correspond-
ing ethers[4, 16, 19]. In particular, the hydrolysis of vinyl
sulfides occurs usually 100–1000 times slower than the
hydrolysis of the structurally similar vinyl ethers [4, 19,
20].
As seen from the table, compounds I and II are
sufficiently easily (from the preparative viewpoint)
converted into 2-oxo-N-alkyl- (III) and 2-oxo-N,N-
dialkyl- (IV) propanamides: by short (0.5–1 h) heating
of water-dioxane or water-methanol solutions at
relatively not high (30–45°C) temperature in the presence
of hydrochloric acid. At the same time the reaction did
not proceed at room temperature even at the 3.2 molar
excess of HCl (see the table, runs nos. 1, 2, 4); these
findings showed that compared to the unsubstituted alkyl
vinyl ethers whose lower representatives underwent total
hydrolytic cleavage in water solutions of low acidity and
even neutral [3] the reactivity of alkoxyethenes I and II
containing in the α-position an amide moiety was sharply
reduced in the electrophilic addition reactions at the
vinyloxy group [15]. The rate of the reaction under study
grows naturally with the hydrochloric acid concentration
(see the table, runs nos. 6 and 7). The data available did
not reveal any significant effect on the reaction rate of
the substituent at the nitrogen atom.
However a more well-grounded conclusion on the
reactivity of 2-(alkylsulfanyl)acrylamides with respect
to electrophilic reagents requires additional careful
research. At the same time since the hydrolysis of
2-(ethylsulfanyl)acrylamide (VII) gives 2-oxo-N-propyl-
propanamide (IVa) that is easily obtained from
2-methoxyacrylamide (IIa) (see the table) we consider
in the framework of this study to be unnecessary the
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 8 2007

REACTIONS OF HETEROCUMULENES WITH ORGANOMETALLIC REAGENTS: XII
1127
optimization of the conditions for protolytic cleavage of
compound VII.
N-Methyl-2-oxo-N-propylpropanamide (IVa). To
a solution of 1.10 g (7.0 mmol) of compound IIa in
10 ml of methanol was added a solution of 1.25 g
(11.30 mmol) of 33% HCl in 10 ml of water, and the
mixture was stirred for 1 h at 40–45°C. The reaction
mixture was treated with water solution of KOH. The
reaction product was extracted into ethyl ether, the extract
was dried with K2CO3, and the solvents were removed
under reduced pressure to obtain a residue of 0.75 g
(75%) of compound IVa, after distillation in a vacuum
yield was 0.63 g (~63%), bp 61–64°C (0.5–1 mm Hg),
nD18 1.4590. IR spectrum, cm–1: 580, 750, 890, 980, 1010,
1100, 1190, 1220, 1270, 1310, 1350, 1380, 1400, 1460,
1490, 1630, 1700, 2870, 2920, 2950. 1H NMR spectrum,
δ, ppm: 3.33 m, 3.21 m (2H, NCH2), 2.96 s, 2.93 s (3H,
NMe), 2.39 s (3H, MeC=O), 1.61 m (2H, β-CH2), 0.90 t,
0.84 t (3H, Me, J 7.4 Hz). 13C NMR spectrum, δ, ppm:
198.23, 194.21 (MeC=O), 166.68, 166.09 (NC=O),
50.92, 48.39, 44.68, 44.07, 42.55 (NCH2), 34.60, 31.92,
30.83, 29.32 (NMe), 28.09, 27.88, 27.43, 27.20
(MeC=O), 21.12, 20.76, 19.56 (β-CH2), 10.72, 10.46
(Me). Found, %: C 58.89; H 9.21; N 9.66. C7H13NO2.
Calculated, %: C 58.72; H 9.15; N 9.78.
2-Oxo-N-propyl- (III) and 2-oxo-N,N-dialkyl- (IV)
propanamides are weakly colored fluids, practically
odorless. Like the initial alkoxyacrylamides II, com-
pounds IV exist as isomers mixtures: alongside the
characterisic for amides cis-trans isomerism [9] caused
by hindered rotation around the partially sp2-hybridized
amide bond C(=O)–N also a different reciprocal orienta-
tion of the key fragments of the molecule may be
manifested, namely, of acyl and amide groups with
respect to the C–C bond [Me(O=)C–C(=O)N]. This fact
1
clearly appears in their H and 13C NMR spectra: all
signals are split (but MeC=O) in the proton spectrum.
The IR spectra of compounds IVa and IVb contain
characteristic absorption bands of C=O stretching
vibrations at 1630 and 1700 cm–1 belonging respectively
to amide and acyl moieties. The absorption of C=C bond
commonly observed in the region 1580–1630 cm–1 is
lacking.
Thus we demonstrated that carbanions generated from
available vinyl ethers can be used in reactions with
heterocumulenes, in particular, with isocyanates, as
efficient synthons of acyl anions providing a possibility
to obtain new families and classes of oxocompounds.
N-Isopropyl-N-methyl-2-oxopropanamide (IVb).
To a solution of 1.03 g (6.0 mmol) of compound IIb
in 10 ml of methanol was added a solution of 1.25 g
(11.30 mmol) of 33% HCl in 10 ml of water, and the
mixture was stirred for 1 h at ~45°C. The reaction mixture
was treated with water solution of KOH. The reaction
product was extracted into ethyl ether, the extract was
dried with K2CO3, and the solvents were removed under
reduced pressure to obtain a residue of 0.67 g (~78%)
of compound IVb, after distillation in a vacuum yield
was 0.60 g (~71%), bp 53–55°C (0.5–1 mm Hg), nD18
1.4515. IR spectrum, cm–1: 580, 700, 750, 880, 910, 980,
1010, 1100, 1170, 1200, 1260, 1340, 1370, 1390, 1400,
EXPERIMENTAL
IR spectra were recorded on a spectrophotometer
Specord 75IR from thin films. NMR spectra were
registered on a spectrometer Bruker DPX-400 (operating
frequency 400 and 100 MHz for 1H and 13C respectively)
from ~5–10% solutions of samples in CDCl3 at room
temperature, internal reference HMDS.
Compounds I and II were prepared in 66–76% yield
as described in [7].
1
1460, 1630, 1700, 2920, 2970. H NMR spectrum, δ,
2-Oxo-N-propylpropanamide (III). To a solution of
0.20 g (1.40 mmol) of compound I in 2 ml of dioxane
was added a solution of 0.30 g (2.71 mmol) of 33% HCl
in 2 ml of water, and the mixture was stirred for 0.5 h at
30–40°C. The reaction product was extracted into hexane
and ethyl ether, the extract was dried with K2CO3, and
the solvents were removed under reduced pressure to
obtain a residue of 0.18 g (~100%) of compound III.
1H NMR spectrum, δ, ppm: 7.25 br.s (1H, NH), 3.23 m
(2H, NCH2), 2.46 s (3H, MeC=O), 1.55 m (2H, β-CH2),
0.93 t (3H, Me). Found, %: C 55.65; H 8.70; N 10.55.
C6H11NO2. Calculated, %: C 55.80; H 8.58; N 10.84.
ppm: 4.59 m, 3.77 m (1H, NCH), 2.70 s, 2.69 s (3H,
NMe), 2.27 s (3H, MeC=O), 1.10 d, 1.04 d (6H, Me2C,
J 6.7 Hz). 13C NMR spectrum, δ, ppm: 198.95, 198.91
(MeC=O), 167.16, 166.38 (C=O), 48.74, 44.22 (NCH),
28.23, 28.18, 27.69, 27.40 (NMe), 24.94, 22.52, 22.20
(MeC=O), 20.27, 18.83 (Me2C). Found, %: C 59.01;
H 9.05; N 9.82. C7H13NO2. Calculated, %: C 58.72;
H 9.15; N 9.78.
The study was carried out under a financial support
of the Russian Foundation for Basic Research (grants
nos. 05-03-32578 and 01-03-32698).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 8 2007

NEDOLYA, SHLYAKHTINA
vol. 35, p. 235; Nedolya, N.A., Brandsma, L., Zinov’e-
1128
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