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A Facile Synthesis of (E,Z)‐3‐Chloro‐2‐propenamides,
Acids, and Esters from 2,3‐Acetylenic Acids with
Oxalyl Chloride in DMF
Neudo A. Urdaneta a , José Salazar a , Julio C. Herrera a & Simón E. López a
a Departamento de Química, Universidad Simón Bolívar, Apdo. 89000, Sartenejas‐Baruta,
Caracas, 1080‐A, Venezuela
Version of record first published: 16 Aug 2006.
To cite this article: Neudo A. Urdaneta , José Salazar , Julio C. Herrera & Simón E. López (2004): A Facile Synthesis
of (E,Z)‐3‐Chloro‐2‐propenamides, Acids, and Esters from 2,3‐Acetylenic Acids with Oxalyl Chloride in DMF, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 34:4, 657-664
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SYNTHETIC COMMUNICATIONSw
Vol. 34, No. 4, pp. 657–664, 2004
A Facile Synthesis of (E,Z)-3-Chloro-2-
propenamides, Acids, and Esters from
2,3-Acetylenic Acids with Oxalyl
Chloride in DMF
*
Neudo A. Urdaneta, Jose Salazar, Julio C. Herrera,
*
´
´ ´
and Simon E. Lopez
´ ´ ´
Departamento de Quımica, Universidad Simon Bolıvar,
Sartenejas-Baruta, Caracas, Venezuela
ABSTRACT
A simple route is described for the synthesis of E and Z 3-chloro-2-
propenamides (4a-e), esters (3a) and acids (2a-c) by the reaction of
2,3-acetylenic acids with oxalyl chloride in DMF followed by treatment
of the corresponding 3-chloro-2-propenoyl chloride derivative with
amines, alcohol and water.
Key Words: 2,3-Acetylenic acids; 3-Chloro-2-alkenoic acids; Hydro-
chlorination; Oxalyl chloride; DMF.
*
´ ´
Correspondence: Neudo A. Urdaneta and Jose Salazar, Departamento de Quımica,
´ ´
Universidad Simon Bolıvar, Apdo. 89000, Sartenejas-Baruta, Caracas 1080-A,
Venezuela; E-mails: urdanet@usb.ve, jsalazar@usb.ve
657
DOI: 10.1081/SCC-120027713
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

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Urdaneta et al.
Recently, we have demonstrated that 2,3-acetylenic acids react with
thionyl chloride in dimethylformamide to give E and Z 3-chloro-2-alkenoic
acid derivatives.[1] The versatility of this method consists in both the hydro-
chlorination of the acetylenic bond and the in situ generation of the
corresponding 3-chloro-2-propenoyl chloride intermediate, which permits its
reaction with solvent nucleophiles as water and alcohols giving acids and
esters and it has been extended for the preparation of 3-chloro-2-alkenamides.
Due to their high functionality[2–5] (vinylic halogen bond, carbon–carbon
double bond and a carboxylic acid, ester or amide), these compounds have
proved to be valuable and versatile intermediates in the design and construc-
tion of more elaborated and biological active molecules, specially acrylamide
derivatives.[6–9]
In continuation of our investigation exploring and extending the use of
other potential hydrohalogenating agents and other nucleophiles, we reported
herein the results of our studies on the hydrochlorination of 2,3-acetylenic
acids with oxalyl chloride in DMF. Thus, the reaction of 2-propynoic acid
(1a), 3-phenyl-2-propynoic acid (1b) and 2-butynoic acid (1c) with oxalyl
Scheme 1. Conditions (i) DMF 08C and (COCl2); (ii) H2O; (iii) n-pentane and alchol,
6 h r.t., and (iv) 2508C, amine/CH2Cl2 6 h r.t.

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659
Table 1. E,Z-3-Chloro-2-alkenoic acids 2a-c and esters 3a obtained according to
Scheme 1.
Compound
3-Chloro-2-alkenoic acids and esters
Overall yielda
E,Z ratiob
2a
75
Ec
2b
2c
3a
88
80
75
25 : 75
40 : 60
24 : 76
aYield of isolated mixture after work-up.
bCalculated based on the NMR spectral data of the purified mixture.
cOnly E isomer was isolated after work-up.
chloride in DMF, afforded the corresponding E,Z-3-chloro-2-propenoic acids,
esters and amides derivatives, when treating the 3-chloro-2-propenoyl
chloride intermediate either with water (ice), alcohol or amines (Sch. 1).
A variety of 2,3-acetylenic acids were submitted to these reactions and
conditions and the results are summarized in Tables 1 and 2. When the
reaction mixture was treated with ice, alcohol (ethanol) or amines (pyr-
rolidine, piperidine, diethylamine and S (2)-1-phenylethylamine) in dichloro-
methane at 2508C, the corresponding E,Z-3-chloro-2-alkenoic acids (2a-c)
and E,Z-3-chloro-2-alkenoates (3a) (Table 1) and E,Z-3-chloro-alkenamides
(4a-e) (Table 2) were formed respectively in moderated to high yield. The
formation of a Vielsmeier–Haack type (COCl)2–DMF complex[10] may
account for the generation of hydrogen chloride in the hydrochlorination of
the triple bond and the formation of the acid chloride intermediate.[11] In the

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Table 2. E,Z-3-Chloro-2-propenamides 4a-e obtained according to Scheme 1.
Compound
E,Z-3-Chloro-2-propenamides
Overall yielda
E,Z ratiob
4a
75
24 : 76
4b
4c
76
82
10c : 90
Zd
4d
4e
76
70
Zd
30e : 70
aYield of isolated mixture after work-up.
bCalculated based on the NMR spectral data of the purified mixture.
cA 7 : 3 E,Z mixture by 1H NMR as an oil was separated.
dOnly Z isomer was isolated after work-up.
eA 8 : 2 E,Z mixture by NMR as an oil was separated.
reaction of 1a, the predominant product was the E-(2a) isomer, while the
reaction of 1b and 1c gave the Z-isomers as predominant products.
This new methodology avoids the traditional two steps sequence for the
synthesis of 3-alkenoic acid derivatives[12–14] (hydrohalogenation of the
previously prepared carbonyl derivative). The described one pot procedure is
carry out under more gentle conditions, such as lower temperature, short times

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661
and easier work-up when compared with other methods[12,13] and our previous
report.[1]
In conclusion, we have developed a novel and convenient methodology
for the synthesis of 3-chloro-2-alkenoic acid derivatives, via the simple
reaction of 2,3-acetylenic acids with oxalyl chloride in DMF under mild
conditions and in short reaction times. A more extensive search concerning
these results, their mechanistic aspects and some other potential applications
are ongoing in our laboratory.
EXPERIMENTAL
1
IR spectra were recorded on a Excalibur (Biorad) FT-IR. H NMR and
13C NMR were recorded on a Eclipse þ (JEOL) 400 MHz spectrometer using
CDCl3 as solvent. Mass spectra were obtained on a Series II-HP5890 Gas-
Chromatograph (Hewlett Packard) with a HP5971A (Hewlett Packard) Mass
Detector. The high resolution mass spectra were obtained on a JEOL JMS-
AX505WA mass spectrometer. Specific rotation was determined at 208C at
the Hg line (546 nm) on a Perkin-Elmer 341 model polarimeter. Melting
points were taken on a Fisher-Johns apparatus and are uncorrected.
General procedure for the preparation of E,Z-3-chloro-2-alkenoic
acids, esters and amides. To a solution of acetylenic acid 1 (2 mmol) in dry
DMF (1.5 mL) cooled at 08C was slowly added oxalyl chloride (4.1 mmol).
After stirring for 45 min, the reaction mixture was poured on ice and the
resulting aqueous solution was extracted with ethyl ether or dichloromethane.
The organic layer was then washed with water, dried with anhydrous Na2SO4,
filtered and concentrated under vacuum to give a mixture of the corresponding
alkenoic acids (2a-c). For both the esters (3a) and amides (4a-e), the acid
chloride containing reaction mixture was treated in a different way. In the case
of esters (3a), after stirring for 45 min., n-pentane was added (3 mL) and then
ethanol (4 mmol) with additional stirring at room temperature for 6 h. For
the amides (4a-e), 3 mL of dry dichloromethane was added lowering the
temperature to 2508C, followed by slow (drop by drop) addition of the
corresponding amine (4.0 mmol) dissolved in dry dichloromethane (5 mL) to
the reaction mixture with stirring for additional 6 h. The E,Z-ester and amide
mixtures were separated by column chromatography on Silicagel, with
n-hexane and ethyl acetate as eluent, (80 : 20) and (75 : 25) respectively. All
products 2a,[12,13] 2b,[14,15] 2c,[15,16a,16b] 3a[17] and 4a[18] were known except
4b, 4c, 4d and 4e.
(E)-3-Chloropropenoic acid (2a). m.p. 80–818C (Lit.[12] 82–838C).
1H NMR (CDCl3): d 6.26 (d, 1H, J ¼ 13 Hz), 7.52 (d, 1H, J ¼ 13 Hz), 9.24
(bs, 1H). MS m/z (%): Mþ. 106 (90), 89 (100), 71 (60), 61 (50), 45 (30).

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Urdaneta et al.
(Z)-3-Chloro-3-phenyl-2-propenoic acid (2b). m.p. 134–1358C
1
(Lit.[14,15] 1338C). H NMR (CDCl3): d 6.59 (s, 1H), 7.45–7.72 (m, 5H),
10.2 (bs, 1H). MS m/z (%): Mþ. 182 (90), 89 (100), 71 (60), 61 (50), 45 (30).
(E)-3-Chloro-3-phenyl-2-propenoic acid (2b). m.p. 141–1428C
1
(Lit.[14,15] 142–1438C). H NMR (CDCl3): d 6.38 (s, 1H), 7.45–7.98 (m,
5H), 9.95 (bs, 1H). MS m/z (%): Mþ. 182 (100), 165 (20), 137 (15), 102 (40),
77 (20),69 (20), 51 (20).
(Z)-3-Chloro-2-butenoic acid (2c). m.p. 588C (Lit.[15,16a,16b] 598C).
1H NMR (CDCl3): d 2,23 (s, 3H), 6.06 (s, 1H), MS m/z (%): Mþ. 120 (100),
104 (20), 102 (40), 84 (80).
(E)-3-Chloro-2-butenoic acid (2c). m.p. 928C (Lit.[15,16a,16b] 948C).
1H NMR (CDCl3): d 2,58 (s, 3H). 6.10 (s, 1H). MS m/z (%): Mþ. 120 (100),
104 (20), 102 (40), 84 (80).
Ethyl-(Z)-3-chloro-3-phenyl-2-propenoate (3a).[17] A pale yellow oil.
1H NMR (CDCl3): d 1.35 (t, 3H) 4.25 (q, 2H), 6.52 (s, 1H), 7.27–7.75 (m,
5H). 13C NMR (CDCl3): d 14.22, 60.60, 116.45, 127.20, 128.62, 130.71,
137.20, 146.10, 164.13.
Ethyl-(E)-3-chloro-3-phenyl-2-propenoate (3a).[17] A pale yellow oil.
1H NMR (CDCl3): d 1.11 (t, 3H), 4.18 (q, 2H), 6.35 (s, 1H), 7.30–7.45 (m,
5H). 13C NMR (CDCl3): d 13.82, 60.60, 119.95, 127.90, 128.55, 129.92,
136.60, 149.75, 163.7.
(Z)-3-Chloro-3-phenyl-N-pyrrolidyl-2-propenamide (4a).[18] A pale
yellow oil. 1H NMR (CDCl3): d 1.92 (m, 4H), 3.52–3.54 (m, 4H), 6.60 (s, 1H),
7.40–7.60 (m, 5H). 13C NMR (CDCl3): d 24.40, 25.90, 45.52, 46.90, 120.70,
126.75, 128.55, 129.80, 136.90, 138.38, 164.05; HRMS-EI, m/z (Mþ)
235.0770. Calcd. for C13H14ClNO 235.0764.
(E)-3-Chloro-3-phenyl-N-pyrrolidyl-2-propenamide (4a).[18] A pale
yellow oil. 1H NMR (CDCl3): d 1.70–1.72 (m, 4H), 3.10–3.11 (m, 4H), 6.43
(s, 1H), 7.40–7.50 (m, 5H). 13C NMR (CDCl3): d 24.10, 25.70, 45.50, 47.00,
122.90, 128.15, 128.20, 129.80, 136.40, 136.88, 163.85; HRMS-EI, m/z (Mþ)
235.0770. Calcd. for C13H14ClNO 235.0764.
(Z)-3-Chloro-3-phenyl-N-piperidyl-2-propenamide (4b). A pale
yellow oil. IR, neat, (n, cm21): 1630 (C55O), 1556 (C55C). 1H NMR
(CDCl3): d 1.55–1.59 (m, 6H), 3.43–3.44 (m, 2H), 3.59–3.62 (m, 2H),
6.56 (s, 1H), 7.30–7.32 (m, 3H), 7.57–7.59 (m, 2H). 13C NMR (CDCl3):
d 24.60, 25.49, 26.64, 42.41, 47.49, 120.47, 126.59, 128.53, 129.71, 136.38,
136.71 164.28. HRMS-EI m/z(Mþ) 249.0869. Calcd. for C14H16ClNO
249.0920.
(Z)-3-Chloro-3-phenyl-N,N-diethyl-2-propenamide (4c). A white
solid m.p. 39–408C. IR, KBr, (n, cm21): 1632 (C55O), 1560 (C55C).
1H NMR (CDCl3): d 1.19 (t, 6H), 3.48 (q, 4H), 6.0 (s, 1H), 7.33–7.35 (m, 5H).
13C NMR (CDCl3): d 12.90, 14.50, 42.64, 39.26, 120.61, 126.68, 129.75,

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663
136.59, 137.06, 165.23. HRMS-EI m/z (Mþ) 237.0194. Calcd. for
C13H16ClNO 237.0190.
(Z)-3-Chloro-3-phenyl-N-(2)-1-phenylethyl-2-propenamide (4d). A
white solid m.p. 98–1008C. IR, KBr (n, cm21): 1635 (C55O),1568 (C55C).
1H NMR (CDCl3): d 1.39 (d, 6H), 5.0 (q, 1H), 6.91 (s, 1H), 7.36–7.46 (m,
10H), 8.65–8.67 (m, 1H). 13C NMR (CDCl3): d 21.90, 49.27, 121.23, 126.32,
127.06, 127.39, 127.54, 128.67, 128.80, 130.26, 130.90, 137.09, 138.94,
142.89, 163.00 HRMS-EI, m/z (Mþ) 285.0844. Calcd. for C17H16ClNO
285.0847 [a]546 25.0 (c, 1.3 mg/mL, MeOH).
(Z)-3-Chloro-N-pyrrolidyl-2-butenamide (4e). A pale yellow oil IR,
1
neat (n, cm21): 1650 (C55O), 1560 (C55C). H NMR (CDCl3): d 1.74–1.85
(m, 4H), 2.40 (s, 3H), 3.34–3.37 (m, 4H), 6.13 (s, 1H). 13C NMR (CDCl3):
d 23.48, 24.29, 26.07, 28.18, 120.36, 147.09, 163.27. HRMS-EI m/z (Mþ)
173.0770. Calcd. for C8H12ClNO 173.0775.
ACKNOWLEDGMENTS
The authors would like to thank the NMR Laboratory at the Chemistry
´ ´
Department-Universidad Simon Bolıvar (Proyect BID-CONICIT QF-13) and
The National NMR Laboratory.
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Received in the USA August 14, 2003

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