Alkylation of dimethyl 1,3-acetonedicarboxylate

Article abstract of DOI:10.1081/SCC-120023437

A reliable, reproducible, general, and detailed procedure for the alkylation of dimethyl-1,3-acetonedicarboxylate are is described.

Full text of DOI:10.1081/SCC-120023437

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Alkylation of Dimethyl 1,3-Acetonedicarboxylate
Adrián Covarrubias-Zúñiga a , Laura San Germán-Sanchez a & José G. Avila-Zárraga b
a Instituto de Química , Universidad Nacional Autónoma de México, Ciudad Universitaria ,
Coyoacán, México
b Facultad de Química , Universidad Nacional Autónoma de México, Ciudad Universitaria ,
Coyoacán, México
Published online: 17 Aug 2006.
To cite this article: Adrián Covarrubias-Zúñiga , Laura San Germán-Sanchez & José G. Avila-Zárraga (2003) Alkylation of
Dimethyl 1,3-Acetonedicarboxylate, Synthetic Communications: An International Journal for Rapid Communication of
Synthetic Organic Chemistry, 33:18, 3165-3172, DOI: 10.1081/SCC-120023437
To link to this article: http://dx.doi.org/10.1081/SCC-120023437
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SYNTHETIC COMMUNICATIONSÕ
Vol. 33, No. 18, pp. 3165–3172, 2003
Alkylation of Dimethyl 1,3-Acetonedicarboxylate
1
Adrian Covarrubias-Zuniga,1, Laura San German-Sanchez,
*
and Jose G. Avila-Zarraga2
2
1Instituto de Quımica, and Facultad de Quımica,
Universidad Nacional Autonoma de Mexico,
Ciudad Universitaria, Coyoacan, Mexico
ABSTRACT
A reliable, reproducible, general, and detailed procedure for the
alkylation of dimethyl-1,3-acetonedicarboxylate is described.
Key Words:
*Correspondence: Adrian Covarrubias-Zuniga, Instituto de Quımica, Universidad
Nacional Autonoma de Mexico, Circuito Exterior, Ciudad Universitaria,
Coyoacan 04510, Mexico; E-mail: adriancz@servidor.unam.mx.
3165
DOI: 10.1081/SCC-120023437
Copyright & 2003 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
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3166
Covarrubias-Zuniga, San German-Sanchez, and Avila-Zarraga
Our synthetic requirements led us to prepare a series of dimethyl-2-
alkyl-1,3-acetonedicarboxylates I (R: Me, iPr, allyl, and n-hexyl).
O
I a: R= Me
I b: R= iPr
R
CO2Me
I c: R= allyl
I d: R= n-hexyl
CO2Me
I
Since we had experience of alkylating dimethyl 1,3-acetonedicarbox-
ylate II with geranyl chloride, using NaH as base in dry THF,[1] we
decided to extend these reaction conditions to MeI, iPrBr, allyl bromide,
and hexyl iodide. The reaction times with MeI and hexyl iodide were long
(ꢀ48 h) and the yield was moderate (42% and 38% respectively). With
allyl bromide the desired monoalkylated product (55% yield) was
obtained, together with 2,4-dialkylated product (22.6% yield) and start-
ing material (13.8%). A mixture of O- and C-alkylated products was
obtained with isopropyl bromide. The synthesis of compound Ic had
been reported elsewhere[2] with similar results to ours: sodium ethoxyde
was used as base. In view of these results we decided to develop the three
step sequence shown in Sch. 1.
The methyl enol ether III was easily prepared from II with trimethyl
orthoformiate in dry MeOH and catalytic amounts of p-TsOH in 95%
yield. III was alkylated with NaH in dry DMF and the corresponding
alkyl halide with excellent yield; finally the hydrolysis of the methyl enol
ethers IV was accomplished with a mixture of HCO2H and hexane,[3] in
good yield. The overall yields are comparable with the method reported
by Muramoto[4] where Mg(OMe)2 or Mg(OEt)2 were used as base.
Noritada et al.[5] used these conditions with a 71% yield, but the purity
of the product after distillation was only 83% (GLC). The purity of the
products obtained by our method turned out to be high. Two additional
examples were considered to test our method: (a) with benzyl chloride
OMe
OMe
1)NaH/DMF
2)RX
(MeO) CH
3
CO2Me
CO2Me
HCO H
2
II
I
HCL (g)
MeOH
CO2Me
R
CO2Me
hexane
III
X= Br, I or OTs
IV
Scheme 1.

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Dimethyl 1,3-Acetonedicarboxylate
3167
and (b) with 1,2-dibromobutane. In the latter case, the !,!0-dihalide
compound may be employed for generating intramolecular ring closures
using doubly activated methylenes[6] or open chain compounds by inter-
molecular attack[8] the alkylation reaction with BnCl resulted with a 85 %
yield; when 1,2-dibromoethane was used, the apparently less favored
monoalkylated product IVf was obtained in 62% yield. Ring closure
products were also detected (15% yield) with the (E)-isomer being the
major product (10% yield) and 5% with the (Z)-isomer. The stereochem-
1
istry was assigned by H NMR (see Sch. 2 and Table 1) and by X-ray
analysis of compound Ivb.[8] In compound V the signal at 3.90 ppm
greatly differs from the other signals assigned to the methyl groups
hydrogen atoms. This shift difference lead us to propose the stereochem-
istry (Z) i nV.
OMe
OMe
IVa: R= Me
IVb: R= iPr
IVc: R= allyl
IVd: R= n-hexyl
IVe: R= benzyl
IVf: R= CH CH Br
IVg: R= H
Me OC
2
CO2Me
CO2Me
R
CO2Me
V
OMe
IV
2
2
CO2Me
IVh
CO Me
2
Scheme 2.
Table 1. 1 HNMR ꢀ ppm chemical shifts (CDCl3, 300 MHz).
Singulet signals of
vinylic protons
Singulet signals for both –CO2Me
and –MeO groups
Compound
IVa
IVb
5.10
5.17
5.16
5.15
5.03
5.20
5.20
5.14
3.66
3.66
3.64
3.65
3.60
3.67
3.68
3.65
3.68
3.68
3.68
3.67
3.62
3.69
3.69
3.67
3.69
3.70
3.69
3.69
3.66
3.71
3.71
3.69
IVc
IVd
IVe
IVf
IVg
Average of signals
from IVa–g
IVh
V
5.20
5.10
3.668
3.67
3.672
3.74
3.675
3.90

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3168
Covarrubias-Zuniga, San German-Sanchez, and Avila-Zarraga
In summary the method reported herein is a reliable, reproducible,
advantageous, and general alkylating route for dialkyl-1,3-acetonedicar-
boxylates.
EXPERIMENTALSECTION
Melting points are uncorrected. Thin-layer chromatography was per-
1
formed on silica gel 60 F254 and visualized by UV irradation. H NMR
spectra were recorded either at 200 or 300 MHz; while 13C NMR spectra
were run at 75 MHz in CDCl3 solution. Mass spectra were measured at
70 eV (EI). Elemental analyses were performed by Galbrait Laboratories,
Inc.; column chromatography purifications were carried out using gel
(70–230 mesh).
E-Methyl-4-carbomethoxy-3-methoxy-2-butenoate III
A mixture of 50 g of 1,3-dimethyl acetonedicarboxylate (0.28 mol,
42 mL, 97%), 400 mL of dry methanol, 18.8 g (0.177 mol) of trimethyl
orthoformiate and 0.1 g of p-TsOH was refluxed 40 h. The mixture was
poured over 0.5 of Na2CO3 in 300 mL of water and extracted with ethyl
acetate (3 Â 100 mL). The combined organic phase was dried over anhyd.
Na2SO4 and concentrated. The residue was purified by column chro-
matography (750 g of silica gel) and methyl-4-carbomethoxy-3-methoxy-
2-butenoate III (49.8 g, 95% yield) was eluted using 5% ethyl acetate in
hexane. IR (neat) 1142, 1119, 1633, 1712, 1745, and 2953 cmÀ1. 1H NMR
ꢀ ppm 3.68 (s, 3H), 3.69 (s, 3H), 3.71 (s, 3H), 3.84 (s, 2H), 5.20 (s, 1H).
13C NMR ꢀ ppm 38.10, 50.98, 52.06, 55.90, 92.95, 167.66, 168.05, 169.45.
MS (EI) 188 (Mþ, 24), 157 (100), 156 (46), 125 (55). Anal. calcd. for
C8H12O5: C, 51.06%; H, 6.38. Found: C, 51.10; H, 6.36.
General Procedure for the Alkylation of the Compound III
To 0.234 g (5.85 mmol) of NaH (60%) in dry DMF (12 mL) was
added dropwise 846 mg (4.5 mmol) of methyl-4-carbomethoxy-3-meth-
oxy-2-butenoate, alkyl halide was added (9.9 mmol) and the mixture
was stirred for 36 h at 45ꢁC. The mixture was poured in 60 mL of
water and extracted with ethyl acetate (4 Â 20 mL). The organic phase
was washed with H2O (2 Â 10 mL), dried over Na2SO4 and concentrated.
The residue was subjected to column chromatography (eluant ethyl

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Dimethyl 1,3-Acetonedicarboxylate
3169
acetate:hexane 4:96, 30 g of silica gel) affording methyl-4-carbomethoxy-
4-alkyl-3-methoxy-2-butenoate IVa–f.
E-Methyl- 4- carbomethoxy- 4-methyl-3- methoxy-2- butenoate IVa.
.
Yield: 78%. IR (neat) 1147, 1630, 1711, 1744 cmÀ1 1H NMR ꢀ ppm
1.35 (d, 3H, J ¼ 7.1 Hz), 3.66 (s, 3H), 3.68 (s, 3H), 3.69 (s, 3H), 4.96 (q,
1H, J ¼ 7.1 Hz), 5.10 (s, 1H). 13C NMR ꢀ ppm 14.25, 40.95, 50.96, 52.07,
55.90, 91.26, 167.58, 172.40, 172.95. MS (EI) m/z (relative intensity) 202
(Mþ, 22), 170 (84), 142 (100), 127 (40), 111 (51). Anal. calcd. for
C9H14O2: C, 53.46; H, 6.93. Found: C, 53.66; H, 6.90.
E-Methyl-4-carbomethoxy-4-isopropyl-3-methoxy-2-butenoate IVb.
Yield: 79.7%. m.p. 40–41ꢁC. IR (KBr) 1153, 1198, 1633, 1709, 1739,
2956 cmÀ1
.
1H NMR ꢀ ppm 0.86 (d, 3H, J ¼ 6.9 Hz), 1.02 (d, 3H,
J ¼ 6.9 Hz), 2.25–2.45 (m, 1H), 3.66 (s, 3H), 3.68 (s, 3H), 3.70 (s, 3H),
4.79 (d, 1H, J ¼ 9.6 Hz), 5.17 (s, 1H). 13C NMR ꢀ ppm 19.60, 21.25, 28.12,
50.94, 51.87, 52.31, 55.75, 93.05, 167.62, 170.80, 171.37. MS (EI) m/z
(relative intensity) 230 (Mþ, 16), 198 (55), 183 (74), 128 (100). Anal.
calcd. for C11H17O5: C, 57.64; H, 7.42. Found: C, 57.72; H, 7.45.
E-Methyl-4-carbomethoxy-4-allyl-3-methoxy-2-butenoate IVc. Yield:
80%. IR (neat) 1146, 1630, 1711, 1743, 2952 cmÀ1 1H NMR ꢀ ppm
.
2.40–2.56 (m, 1H), 2.64–2.76 (m, 1H), 3.64 (s, 3H), 3.68 (s, 3H), 3.69
(s, 3H), 4.96–5.10 (m, 3H), 5.16 (s, 1H), 5.68–5.83 (m, 1H). 13C NMR
ꢀ ppm 33.26, 45.81, 50.95, 52.06, 55.78, 92.68, 116.68, 134.88, 167.52,
170.87, 171.27. MS (EI) m/z (relative intensity) 228 (Mþ, 24), 213 (85),
197 (89), 164 (59), 137 (89), 109 (100). Anal. calcd. for C11H16O5: C,
57.89; H, 7.01. Found: C, 58.02; H, 6.94.
E-Methyl-4-carbomethoxy-4-hexyl-3-methoxy-2-butenoate IVd. Yield:
1
76%. IR (neat) 1146, 1197, 1631, 1715,1744, 2859 cmÀ1. H NMR ꢀ ppm
0.88 (t, 3H, J ¼ 6.9 Hz), 1.15–1.35 (m, 8H), 1.65–2.05 (m, 2H), 3.65 (s, 3H),
3.67 (s, 3H), 3.69 (s, 3H), 4.93 (dd, 1H, J ¼ 6.38 Hz, and J ¼ 6.26 Hz).
13C NMR ꢀ ppm 14.01, 22.54, 29.01, 31.57, 31.58, 46.03, 50.97, 52.02,
55.83, 90.92, 92.44, 167.64, 171.73, 171.98. MS (EI) m/z (relative intensity)
272 (Mþ, 13), 169 (100), 156 (98), 128 (68), 241 (48). Anal. calcd. for
C14H24O5: C, 61.69; H, 8.81. Found: C, 61.71; H, 8.79.
E-Methyl-4-carbomethoxy-4-benzyl-3-methoxy-2-butenoate IVe.
Yield: 85.2%. IR (neat) 1144, 1437, 1630, 1710, 1742, 2951 cmÀ1
.
1H NMR ꢀ ppm 2.99 (dd, 1H, Jgem ¼ 13.8 Hz, Jxa ¼ 7.2 Hz, Hx), 3.28 (dd,
1H, Jgem ¼ 13.8 Hz, Jba ¼ 7.5 Hz, Hb), 3.60 (s, 3H), 3.62 (s, 3H), 3.66 (s,
3H), 5.03 (s, 1H), 5.30 and 5.31 (dd, 1H, Jax ¼ 7.2, Jab ¼ 7.5 Hz, Ha), 7.22
(bs, 5H). 13C NMR ꢀ ppm 35.22, 47.59, 50.92, 52.13, 55.76, 92.79, 126.21,
128.06, 129.05, 138.53, 167.33, 170.56, 171.20. MS (EI) m/z (relative
intensity) 278 (Mþ, 32), 246 (50), 219 (34), 187 (71), 91 (100). Anal.
calcd. for C15H18O5: C, 6.74; H, 6.47. Found: C, 64.82; H, 6.50.

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3170
Covarrubias-Zuniga, San German-Sanchez, and Avila-Zarraga
E-Methyl-4-carbomethoxy-4-(2-bromoethane)-3-methoxy-2-butenoate
IVf. Yield: 62%. IR (neat) 1150, 1195, 1632, 1712, 1743, 2951 cmÀ1
.
1H NMR ꢀ ppm 2.20–2.34 (m, 1H, Hx), 2.47–2.60 (m, 1H, Hb),
3.35–3.48 (m, 2H), 3.67 (s, 3H), 3.69 (s, 3H), 3.71 (s, 3H), 5.11 (t, 1H,
J ¼ 6.6 Hz). 13C NMR ꢀ ppm 30.11, 32.38, 45.22, 51.14, 52.28, 55.93, 93.27,
167.31, 169.93, 170.78. MS (EI) m/z (relative intensity) 296 (Mþ þ 2, 14),
294 (Mþ, 15), 264 (Mþ þ 2-MeOH, 85), 262 (Mþ, -MeOH, 78), 183 (100).
Anal. calcd. for C10H15O5Br: C, 40.69; H, 5.08. Found: C, 40.62; H, 5.06.
E-Methyl-4-carbomethoxy-4-ethylen-3-methoxy-2-butenoate IVh.
1
Yield: 10.25%. IR (neat) 1157, 1313, 1619, 1728, 2952 cmÀ1. H NMR
ꢀ ppm 1.20 (q, 2H, J ¼ 4.5 Hz), 1.57 (q, 2H, J ¼ 4.5 Hz), 3.668 (s, 3H),
3.672 (s, 3H), 3.675 (s, 3H), 5.20 (s, 1H). 13C NMR ꢀ ppm 17.03, 27.99,
38.11, 50.89, 52.29, 56.16, 94.04, 166.90, 170.89, 172.54. MS (EI) m/z
(relative intensity) 214 (Mþ, 31), 199 (68), 183 (92), 155 (100). Anal.
calcd. for C10H14O5: C, 56.07; H, 6.54. Found: C, 56.14; H, 6.60.
Z-Methyl-4-carbomethoxy-4-ethylen-3-methoxy-2-butenoate V. Yield:
1
5%. IR (neat) 1165, 1298, 1635, 1722, 2953 cmÀ1. H NMR ꢀ ppm 1.23
(q, 2H, J ¼ 4.5 Hz), 1.58 (q, 2H, J ¼ 4.5 Hz), 3.67 (s, 3H), 3.74 (s, 3H),
3.90 (s, 3H), 5.10 (s, 1H).
General Procedure for the Preparation of the
Compounds Ia–e
Methyl-4-carbomethoxy-4-alkyl-3-methoxy-2-butenoate (22 mmol),
HCO2H (10 mL, 88%, ꢀ0.23 mol), and hexane (10 mL) were stirred to
40ꢁC for 36 h. The mixture reaction was poured portionwise into an
Erlen-Meyer flask (250 mL) containing Na2CO3 (11 g, 0.1 mol) and
H2O (35 mL) with stirring and extracted with ether (3 Â 15 mL). The
organic layer was separated, washed with water (3 Â 5 mL), dried
(Na2SO4) filtered, and concentrated. The residue was purified by
column chromatography (eluant ethyl acetate:hexane, 5:95, 80 g of
silica gel) affording 1,3-dimethyl-4-alkyl-acetonedicarboxylate.
Dimethyl 2-methyl-1,3-acetonedicarboxylate Ia. Yield: 86%. IR (neat)
1210, 1252, 1720, 1746, 2956 cmÀ1 1H NMR ꢀ ppm 1.38 (d, 3H,
.
J ¼ 7.2 Hz), 3.63 (AB system, 2H, J ¼ 15.9 Hz), 3.741 (s, 3H), 3.736 (q,
J ¼ 7.2 Hz) 3.748 (s, 3H). 13C NMR ꢀ ppm 12.47, 47.60, 51.32, 52.36,
89.70, 167.18, 170.25, 197.93. MS (EI) m/z (relative intensity) 188 (Mþ,
12), 157 (87), 115 (80), 101 (99), 88 (100). Anal. calcd. for C8H12O5: C,
51.06; H, 6.38. Found: C, 51.18; H, 6.33.
Dimethyl 2-isopropyl-1,3-acetonedicarboxylate Ib. Yield: 85%. IR
1
(neat) 1154, 1200, 1329, 1439, 1628, 1718, 1746, 2962 cmÀ1. H NMR

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Dimethyl 1,3-Acetonedicarboxylate
3171
ꢀ ppm 0.95 (d, 3H, J ¼ 6.7 Hz), 0.98 (d, 3H, J ¼ 6.7 Hz), 2.15–2.25 (m,
1H), 3.36 (d, 1H, J ¼ 9.3 Hz), 3.50 and 3.67 (AB system, 2H, J ¼ 16 Hz),
3.73 (s, 6H). 13C NMR 20.25, 28.92, 48.01, 52.36, 66.45, 91.12, 93.10,
167.03, 169.09, 197.40. MS (EI) m/z (relative intensity) 216 (Mþ, 3),
185 (25), 174 (25), 142 (38), 116 (26), 101 (100), 69 (38). Anal. calcd.
for C10H16O5: C, 55.55; H, 7.40. Found: C, 55.57; H, 7.37.
Dimethyl 2-allyl-1-3-acetonedicarboxylate Ic. Yield: 83%. With iden-
tical properties of the same reported compound.[2]
Dimethyl 2-hexyl-1,3-acetonedicarboxylate Id. Yield: 85%. IR (neat)
1660, 1747, 2859 cmÀ1. 1H NMR ꢀ ppm 0.87 (t, 3H, J ¼ 6.9 Hz), 1.10–1.18
(m, 8H), 1.63–1.91 (m, 2H), 3.57–3.66 (m, 3H), 3.73 (s, 6H).
13C NMR ꢀ ppm 13.88, 22.40, 27.14, 28.04, 28.86, 31.37, 47.76, 52.29,
58.76, 90.43, 167.07, 169.75, 197.53. MS (EI) m/z (relative intensity)
272 (Mþ, 13), 169 (100), 156 (98), 128 (68), 241 (48). Anal. calcd. for
C14H24O5: C, 60.46; H, 8.52. Found: C, 60.49; H, 8.50.
Dimethyl 2-benzyl-1,3-acetonedicarboxylate. Yield: 90%. IR (neat)
1
1244, 1328, 1438, 1720, 1744, 2955 cmÀ1. H NMR (d, 2H, 7.5 Hz), 3.51
(AB system, 2H, J ¼ 16 Hz) 3.65 (s, 3H), 3.69 (s, 3H), 4.00 (t, 1H,
J ¼ 7.5 Hz), 7.10–7.40 (m, 5H). 13C NMR ꢀ ppm 33.85, 48.62, 91.12,
52.35, 52.58, 126.77, 128.57, 128.81, 137.73, 166.71, 168.82, 196.69. MS
(EI) m/z (relative intensity) 264 (Mþ, 8), 232 (24), 163 (89), 131 (100), 91
(73). Anal. calcd. for C14H16O5: C, 63.63; H, 6.06. Found: C, 63.64;
H, 6.04.
ACKNOWLEDGMENTS
This research was supported by a Grant-in Aid for Scientific
Research No. 27610-E from CONACYT, Mexico. The authors thank
Professor J. Muchowskiand Dr. N. Zu niga for helpful discussions,
We thank Messrs. R. Gavino, R. Patino, L. Velasco, and F. J. Perez
for running the spectra.
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2. Arsian, Tuncer.; Benner, Steven A. J. Org. Chem. 1993, 58, 2260.
3. Barbot, F.; Miginiac, P. Synthesis 1983, 651. We substituted hexane
for pentane.

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3172
Covarrubias-Zuniga, San German-Sanchez, and Avila-Zarraga
4. (a) Muramoto, Y.; Oishi, K.; Ichimoto, I.; Ueda, H. Nippon
Nogeikagaku Kaishi 1973, 46, 201; (b) Muramoto, Y.; Oishi, I.;
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6. Zefirov, N.S.; Kuznetsova, T.S.; Kozhushkov, S.I.; Surmina, C.S.;
Rashchupkina, Z.A. J. Org. Chem. USSR 1983, 19, 474.
7. March, J.; Smith, M.B. March’s Advanzed Organic Chemistry, 5th
Ed.; John Wiley & Sons, Inc., 2001; 548–549.
8. Covarrubias-Zuniga, A.; Arias-Salas, D.; Zuniga-Villarreal Noe;
Toscano, R.A. Analytical Sciences 2001, 17, 1.
Received in the USA December 18, 2002