A tandem Finkelstein-rearrangement-elimination reaction: a straightforward synthetic route to allyl esters

Article abstract of DOI:10.1016/j.tet.2009.04.042

Allyl esters can be obtained by a Finkelstein-rearrangement-elimination reaction of 2-chloro-1-(chloromethyl)ethyl esters induced by NaI. Sodium iodide can be used below equivalence using a reductive agent as sodium thiosulfate. High yields are obtained with most of the diverse esters studied. The method described avoids the use of allyl alcohol as a reagent. 2-Chloro-1-(chloromethyl)ethyl esters are prepared from glycerol, the main by-product of biodiesel industry. The effectiveness of iodine as reagent to hydrolyze allyl esters is also confirmed.

Full text of DOI:10.1016/j.tet.2009.04.042

Tetrahedron 65 (2009) 4866–4870
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
A tandem Finkelstein-rearrangement–elimination reaction: a straightforward
synthetic route to allyl esters
a
a
a
a
a,b
`
´
´
`
Jordi Eras , Marc Escriba , Gemma Villorbina , Mireia Oromı-Farrus , Merce Balcells
,
Ramon Canela a
,b,
*
a Department of Chemistry, Lleida University, 25198 Lleida, Spain
b Centre UdL-IRTA, Lleida University, Rovira Roure 191, 25198 Lleida, Spain
a r t i c l e i n f o
a b s t r a c t
Article history:
Allyl esters can be obtained by a Finkelstein-rearrangement–elimination reaction of 2-chloro-1-
(chloromethyl)ethyl esters induced by NaI. Sodium iodide can be used below equivalence using a re-
ductive agent as sodium thiosulfate. High yields are obtained with most of the diverse esters studied. The
method described avoids the use of allyl alcohol as a reagent. 2-Chloro-1-(chloromethyl)ethyl esters are
prepared from glycerol, the main by-product of biodiesel industry. The effectiveness of iodine as reagent
to hydrolyze allyl esters is also confirmed.
Received 22 December 2008
Received in revised form 4 April 2009
Accepted 9 April 2009
Available online 17 April 2009
Dedicated on the occasion of Professor Josep
Font’s retirement
Ó 2009 Elsevier Ltd. All rights reserved.
Keywords:
Allylic compounds
Elimination
Esters
Nucleophilic substitution
Rearrangement
1. Introduction
While trying to induce desymmetrisztion in the 2-chloro-1-
(chloromethyl)ethyl esters, we found that NaI was able to induce
Agricultural raw materials have become a matter of interest in
the 21st century in the search for new sources of chemicals to help
sustainable development. Oils and fats of vegetable and animal
origin make up the greatest proportion of the current consumption
of renewable raw materials in the chemical industry because they
offer a large number of possibilities for application.1 Recently, the
industrial interest in vegetable oils has increased because they
constitute the raw material for the biodiesel industry. One of the
by-products of this industry is glycerol, which already has many
applications.2 However, the expected increase in biodiesel pro-
duction is stimulating research to find new industrial applications
for glycerol.3 Glycerol can be easily transformed into several 2-
chloro-1-(chloromethyl)ethyl esters directly4–6 or through its
transformation to different derivatives as 4-hydroxymethyl-2,2-
dimethyl-1,3-dioxolane (solketal) and a subsequent one-pot ester-
ification–chlorination.7 These esters are putative precursors of
2-chloro-1-(iodomethyl)ethyl esters (3a–j in Scheme 1), which are
versatile starting materials with a chiral center.
the formation of the corresponding allyl esters starting from 1a.8
Herein we report different parameters having an effect on the allyl
esters formation by the Finkelstein-rearrangement–elimination
reaction of 2-chloro-1-(chloromethyl)ethyl esters induced by NaI.
To the best of our knowledge, this type of combined reaction in the
presence of NaI is unprecedented.
O
O
O
R
O R
+I2+2NaCl
2a-j
1a-j
Cl Cl
NaI
NaI
O
I
R
Cl-
O
R
O
O
Cl
I
5a-j
3a-j
R
I-
O
O
Cl
6a-j
* Corresponding author. Tel.: þ34 973 702840; fax: þ34 973 238264.
E-mail address: canela@quimica.udl.cat (R. Canela).
Scheme 1. Proposed mechanism for allyl ester formation (R¼entries a–j, Table 1).
0040-4020/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2009.04.042

J. Eras et al. / Tetrahedron 65 (2009) 4866–4870
4867
2. Results and discussion
O
O
O
I
O
O
R
R
O
R
NaI
First, we studied the treatment of 1a with NaI (2.0 equiv) in ac-
etone at 80 ꢀC for 48 h. Ester 2a was obtained in moderate yield.
Nevertheless, considering that allyl esters have manyapplications in
such wide-ranging fields as cosmetics,9 flavorings,10 resins,11 energy
storage,12 olefin metathesis,13 and precursors in allylation re-
actions14–16 a set of experiments were carried out trying to improve
the yield of this new reaction.
Butanone
Cl
Cl
Cl
1a
2a
3a
100
When the same reaction was carried out at 115 ꢀC using buta-
none as solvent, the yield increased up to 93%.
80
60
40
20
0
2a
To study the scope of this reaction, the same process was studied
with several alkyl and aryl acids (Table 1). Yields varied from 61%
(entry h) to 98% (entry d). Finally, the process was scaled up to 30
times using 2-chloro-1-(chloromethyl)ethyl esters 1a and 1j. The
yields were 91% and 82% of purified allyl esters 2a and 2j,
respectively.
Our approach differs from most of the methods described so far
in that the use of allyl alcohol, undesired residue on some allylic
ester preparations,17 is avoided. These methods use catalysts such
as hydrogen chloride,18,19 sulfuric acid,20,21 and titanium sulfate,22
or enzymes such as lipases.23 Allyl acetate can also be prepared by
acetoxylation of propylene18 and pyrolysis of 1,3-diacetoxy-
propane24 and 1,2-diacetoxypropane.25
3a
1a
0
10
20
time, h
30
40
To study some aspects of the mechanism of this transformation,
two different approaches were followed. First, the progress of the
reaction between 1a and sodium iodide in butanone at 115 ꢀC was
studied for 48 h. Besides the starting compound 1a and the final
allyl palmitate (2a), the formation of about 48% 2-chloro-1-(iodo-
methyl)ethyl palmitate (3a) as an intermediate compound was
observed (chromatographic peak at tR¼34.7 min presenting ions
[M]þ: 458; [MꢁCl]þ: 423; [MꢁI]þ: 331; [MꢁC3H5ICl]þ: 255; and
[C3H5ICl]þ: 203) after 6 h of reaction (see Supplementary data).
Figure 1 shows the progress of the reaction. Whereas the
starting ester 1a had almost disappeared after 6 h, 3a reached its
maximum concentration between 3 and 6 h, and then a gradual
decline was observed. Allyl palmitate (2a) and a dark color, con-
sidered to be due to free iodine, appeared as the reaction time in-
creased. A dynamic NMR experiment carried out for 28 h using
CD3COCD3 (see Supplementary data) only permitted the detection
of the compounds indicated in Figure 1.
Figure 1. Evolution of the starting material (1a), the final product (2a), and an in-
termediate (3a) in presence of NaI at 115 ꢀC (R¼CH3(CH2)14).
and 1:4 molar ratios, the reaction progressed to 2a without
detecting the formation of 4a.
Based on these results, the mechanism of the present reaction is
proposed as shown in Scheme 1. Substitution of chlorine by iodine
forms the compounds 3a–j. Nucleophilic attack of the sp2 oxygen
present in the carboxylic group could form the 1,3-dioxolane cat-
ions 5a–j and 6a–j, similar to the intermediates proposed by several
authors.4,26 Intermediates 6a–j could be transformed to 5a–j by
a new chlorine–iodine exchange. Compounds 5a–j could also be
formed from 2-iodo-1-(iodomethyl)ethyl esters (not shown in
Scheme 1). However, these esters were not detected in the NMR
experiment indicated above. Finally, 5a–j could be transformed into
the stable 2a–j through the corresponding ring opening. This last
step is very similar to that proposed by several authors for some
dehalogenation reactions occurring in polar solvents. Barluenga
et al.27 proposed the formation of an allyl alcohol through an
Second, the same reaction was studied using different ratios of
1a to NaI. Figure 2 shows that when amounts of NaI are used under
equivalence, the reaction is not complete and the formation of
small amounts of 4a is observed. When 1:1 molar ratio was used,
only 4a was recovered after 48 h of reaction. When using the 1:2
O
O
R
O
R
O
I2
NaI
O
R
OH
Butanone
Butanone
Table 1
Cl Cl
1a
2-Chloro-1-(chloromethyl)ethyl ester (1a–j) dechlorination with sodium iodide in
2a
4a
butanone
O
O
Butanone
R
R
2NaI
O
100
80
60
40
20
0
O
Cl
Cl
2a
4a
2a-j
1a-j
1a
Entry (1)
R
Isolate yield (%) 2
a
b
c
d
e
f
g
h
i
CH3(CH2)14
CH3(CH2)8
(CH3)3C
C6H5–CH]CH
C6H5
o-Cl–C6H4
p-NO2–C6H4
o-HO–C6H4
1-Naphthyl
2-Naphthyl
93
91
84
98
97
81
96
61
96
83
1/0.1
1/0.25
1/0.5
1/1
1a/NaI ratio
1/2
1/4
Figure 2. Effect of 1a/NaI ratio in the products obtained from the transformation of 1a
after 48 h of reaction at 115 ꢀC (R¼CH3(CH2)14).
j

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J. Eras et al. / Tetrahedron 65 (2009) 4866–4870
iodide-induced
b
-elimination of an epiiodohydrin. Similar iodide-
confirms that iodide anion should be present in the rate-de-
termining step of this reaction. An increase of the amount of so-
dium thiosulfate does not cause an increase of the reaction rate nor
the yield (results not shown). These results could be explained
considering the low solubility of sodium thiosulfate in butanone.
induced b-elimination mechanism was proposed for the sodium
iodide dehalogenation of vic-bromochlorides and vic-dichlorides.28
Moreover, ionic mechanisms were proposed for some abnormal
Finkelstein reactions29 and the decomposition of ethylene diiodide
in polar solvents.30 Compounds 2a–j could also be formed from 6a–
j through the corresponding ring opening (not shown in Scheme 1).
In this case ClI will be formed.
3. Summary
When NaI was not in molar excess, the amount of iodide anion
was not sufficient to bring the reaction to full completion. More-
over, the presence of some free iodine could cause the hydrolysis of
a certain amount of 2a.
2-Chloro-1-(chloromethyl)ethyl alkyl or aryl esters prepared
from glycerol can be transformed to the corresponding allyl ester
when 2 equiv of NaI is used. Shorter reaction times yield note-
worthy amounts (almost 50%) of 2-chloro-1-(iodomethyl)ethyl
esters, a potentially valuable compound to be obtained. Using less
NaI leads to the formation of carboxylic acid unless a reducing
agent like sodium thiosulfate is present in the reaction media. In
this case, the reaction can be carried out to completion using
0.5 mmol (0.25 equiv) of NaI during 48 h. Iodine in butanone is
a suitable reagent to hydrolyze some allyl esters.
Taksande et al.31 have recently described iodine as a useful
catalyst for hydrolyzing allyl esters in DMSO. As the amount of NaI
increases, the amount of 4a can also increase, as can the iodine
present. This could explain why only 4a is obtained when the 1:1
1a/NaI molar ratio was used. An extra increase in NaI could help the
formation of Iꢁ3 , which could stop the hydrolysis.
To confirm this hypothesis, 2a was heated in the presence of
different amounts of I2/NaI mixture for 24 h. Figure 3 shows that
when NaI was not present compound 2a was fully hydrolyzed. This
confirms that iodine is a suitable reagent for the hydrolysis of allyl
esters even in butanone.31 When the NaI amount increased, hy-
drolysis decreased. Finally, from an I2/NaI ratio of 70:30 onward 2a
was not hydrolyzed.
Considering these results a final set of experiments was planned
using esters 1a and 1j again. They consisted on the introduction of
sodium thiosulfate as an I2 reducing agent in the reaction media.
Using this approach, we tried to maintain the I2 concentration
below that, which causes allyl esters hydrolysis while trying to
diminish the amount of NaI, an expensive reagent. Moreover, iodide
anion should always be present to catalyze the rearrangement–
elimination reaction.
Table 2 shows that reaction can be carried out using amounts of
NaI below the equivalence. Thus, 89% crude yield of 2a is reached
after 48 h using 0.5 mol of this salt. Yields are poorest for 2j.
However, 94% crude yield of 2j could be obtained using 1 mmol NaI,
half of the stochiometric equivalents needed. This confirms that
iodine concentration is maintained below the amount needed to
cause the hydrolysis of allyl esters. No free acid was detected in any
of these experiments. Nevertheless, the reaction time needed to
reach similar yields depends on the amount of initial NaI used. This
The application of this methodology to the synthesis of chiral
halohydrin esters to be used as building blocks is under study, as is
the utilization of butanone/iodine mixture as hydrolyzing system
for other allyl esters. Both studies will be reported in due course.
4. Experimental section
4.1. Material and methods
1H NMR (400 MHz) and 13C NMR (100 MHz) spectra were
recorded on a VARIAN 400 spectrometer. All chemical shifts are
reported in delta units (d), parts per million (ppm) relative to the
singlet at 7.26 ppm of CDCl3 for 1H and centre line of a triplet at
77.00 ppm for 13C NMR. The following abbreviations are used; s:
singlet, d: doublet, t: triplet, q: quartet, quin: quintet, m: multiplet.
GC-FID analyses wereperformed inan AgilentTechnologies 6890N
equipped with a DB5-MS column (J&W) (30 mꢂ0.25 mꢂ0.25 mm)
m
and He as carrier gas. The following chromatographic conditions were
used:constantflow2 mL/min, splitinjectionratio20:1at300 ꢀC. Oven
started at 50 ꢀC for 5 min, temperature was increased at 5 ꢀC/min to
110 ꢀC, then increased at 10 ꢀC/min until final temperature of 260 ꢀC
for 15 min. Tridecane from Aldrich was used as internal standard to
carry out GC quantification.
GC–MSanalyseswereperformedinanAgilentTechnologies6890N
equipped with a DB5-MS column (J&W) (30 mꢂ0.25 mꢂ0.25 mm)
m
coupled to an Agilent Technologies 5973 Network detector and He as
Table 2
2-Chloro-1-(chloromethyl)ethyl ester (1a–j) dechlorination with sodium iodide/
sodium thiosulfate in butanone
120
100
2
80
60
40
Entry (1)
NaI (equiv)
Crude yield (%) 2
24 h
48 h
a
a
a
a
a
j
j
j
j
j
0.50
0.38
0.25
0.13
0.05
0.50
0.38
0.25
0.13
0.05
98
95
72
43
12
87
52
40
18
6
99
98
89
66
18
94
71
50
38
11
20
4
0
I2/NaI
Figure 3. Evolution of the hydrolysis of 2a in presence of different relative amounts of
I2 and NaI. The reaction was carried out at 110 ꢀC for 24 h (R¼CH3(CH2)14).

J. Eras et al. / Tetrahedron 65 (2009) 4866–4870
4869
carrier gas. The following chromatographic conditions were used:
4.7. Study of the evolution of 1,3-dichloro-2-propyl palmitate
constant flow 2 mL/min, split injection ratio 20:1 at 280 ꢀC. Oven
started at 50 ꢀC for 5 min, temperature was increased at 5 ꢀC/min to
110 ꢀC, then increased at 10 ꢀC/min until final temperature of 260 ꢀC
for 15 min.
IR spectra were recorded on a Magna IR 560 NicoleT FTIR
spectrophotometer in the range 4000–600 cmꢁ1 with KBr pellets
or with diamond HATR from SpectraTech as specified. Spectra are
reported in reciprocal centimeters (cmꢁ1).
(1a), 1-chloro-3-iodo-2-propyl palmitate (3a), and allyl
palmitate using dynamic 1H NMR spectra
In a screw cap NMR tube were added 2-chloro-1-(chloro-
methyl)ethyl palmitate (1a) (25,5 mg, 0.07 mmol), sodium iodide
(42 mg, 0.28 mmol), and 1.5 mL acetone-d6. The mixture was in-
troduced in NMR spectrometer at 80 ꢀC for 30 h recording one
spectrum every 2 h until the end of the experiment.
High-resolution mass spectral (HRMS) data were obtained by
direct infusion on LC-TOF-MS Waters LCT Premier XE using ESI or
APCI or on Waters GCT Premier using EI as specified.
4.8. Reaction progress study (Fig. 1 main text)
2-Chloro-1-(chloromethyl)ethyl palmitate (1a, 366 mg; 1 mmol)
and sodium iodide (600 mg, 4 mmol) in dried butanone (1.5 mL)
were heated at 115 ꢀC in a reaction vial. Samples were collected in
triplicate at 2, 4, 8, 16, 24, 48 h and analyzed by GC and GC–MS in
duplicate.
4.2. General procedure for the preparation of 2-chloro-1-
(chloromethyl)ethyl esters (2a–j)
A carboxylic acid (1 mmol), glycerol (184 mg, 2 mmol), and
CTMS (540 mg, 5 mmol) were added to a reaction vial fitted with
a PTFE-lined cap. The mixture was heated at 80 ꢀC for 48 h. After
cooling, an organic solvent was added, and the mixture was washed
three times with water. The organic layer was dried over anhydrous
MgSO4, and the solvent was evaporated under vacuum. The crude
product was purified by crystallization, distillation, or SiO2 column
chromatography. Spectroscopic data are in accordance with the
literature.6,7
4.9. Influence of sodium iodide ratio (Fig. 2 main text)
2-Chloro-1-(chloromethyl)ethyl palmitate5 (1a, 366 mg;1 mmol),
dried butanone (1.5 mL) and the amounts of sodium iodide as in-
dicated in the following table:
NaI (mg)
1a/NaI molar ratio
15
37.5
75
150
300
600
1:0.1
1:0.25
1:0.5
1:1
1:2
1:4
4.3. General procedure for the preparation of allyl esters
(2a–j)
A solution of 2-chloro-1-(chloromethyl)ethyl ester (0.5 mmol)
and sodium iodide (300 mg, 2 mmol) in dried butanone (1 mL) was
heated for 48 h at 115 ꢀC in a reaction vial. After cooling, tert-butyl
methyl ether was added; the mixture was washed with saturated
solution of Na2S2O3 and water. The upper layer was recovered and
dried over anhydrous MgSO4. The solvent was evaporated under
vacuum to give the allyl derivate. The crude was purified by SiO2
column chromatography to give the corresponding allyl ester.
were heated at 115 ꢀC for 48 h in a reaction vial. Samples were col-
lected and analyzed by GC and GC–MS in duplicate.
4.10. Stability in front NaI/I2 ratio (Fig. 3 main text)
Allyl palmitate (2a, 50 mg; 0,17 mmol) was heated in presence
of different I2,NaI molar ratios (100:0; 95:5; 90:10; 80:20; 75:25;
70:30; 65:35; 55:45; 50:50; 25:75; 0:100) for 24 h at 110 ꢀC in
a reaction vial. The samples were collected and analyzed by GC–MS
in duplicate.
4.4. General procedure for the preparation of allyl esters
using Na2S2O3 (2a–j)
A solution of 2-chloro-1-(chloromethyl)ethyl ester (0.5 mmol),
sodium iodide (150–15 mg, 1–0.1 mmol) and (158 mg, 1 mmol) in
dried butanone (1 mL) was heated for 24–48 h at 115 ꢀC in a re-
action vial. After cooling, tert-butyl methyl ether was added; the
mixture was washed with water. The upper layer was recovered
and dried over anhydrous MgSO4. The solvent was evaporated
under vacuum to give the allyl derivate. The crude was analyzed by
GC to determine the yield of the corresponding allyl ester.
4.11. Analytical data
4.11.1. Allyl palmitate (2a)
CAS: 43211-62-7: 1H NMR (CDCl3)
d: 5.92 (m, 1H, CH2–
CH]CH2), 5.31 (dq, Jtrans¼17.2 Hz, Jgem¼1.6 Hz, 1H, CH]CH2), 5.23
(dq, Jcis¼10.2 Hz, Jgem¼1.2 Hz, 1H, CH]CH2), 4.57 (dt, J1¼5.5 Hz,
J2¼1.5 Hz, 2H, CH2–CH]CH2), 2.33 (t, J¼7 Hz, 2H, CH2( )(C]O)), 1.63
a
4.5. Scaled up preparation of allyl palmitate (2a)
(quin, J¼7.5 Hz, 2H, CH2( )(C]O)), 1.25 (m, 24H, CH2), 0.88 (t, J¼7 Hz,
b
3H, CH3). 13C NMR (CDCl3)
d: 173.7 (C]O), 132.6 (CH]), 118.3
Prepared following the general procedure in a 125 mL reaction
vial fitted with PFE-lined cap. A solution of 2-chloro-1-(chloro-
methyl)ethyl palmitate 3a (6.6 g, 18 mmol) and sodium iodide
(10 g, 67 mmol) in dried butanone (25 mL) yielded the allyl pal-
mitate 12a (4.9 g, 91%).
(]CH2), 65.1 (O–CH2), 34.5 (CH2( )(C]O)), 32.2 (CH2–CH2–CH3),
a
29.9, 29.8, 29.7, 29.6, 29.5, 29.4 (CH2), 25.2 (CH2( )(C]O)), 22.9 (CH2–
b
CH3), 14.3 (CH3). GC–MS m/z: 296 [M]þ, 267 [MꢁC2H3]þ, 253
[MꢁC3H5]þ, 239 [MꢁOC3H5]þ. IR ATR nmax: 3075, 2924, 2853, 1740,
1592, 1437, 1245, 1115, 1051, 747 cmꢁ1
.
4.6. Scaled up preparation of allyl 2-naphthoate (2j)
4.11.2. Allyl caprate (2b)
CAS: 57856-81-2: 1H NMR (CDCl3)
d: 5.91 (m, 1H, CH2–
Prepared as described above. A solution of 2-chloro-1-(chloro-
methyl)ethyl naphthoate 3j (7.1 g, 27 mmol) and sodium iodide
(16.2 g, 108 mmol) in dried butanone (30 mL) yielded the allyl 2-
naphthoate (12j) (4.3 g, 82%).
CH]CH2), 5.26 (m, 2H, CH]CH2), 4.56 (dd, J1¼5.6 Hz, J2¼1.2 Hz,
2H, CH2–CH]CH2), 2.33 (t, J¼8 Hz, 2H, CH2( )(C]O)), 1.62 (m, 2H,
a
CH2( )(C]O)), 1.25 (m, 12H, CH2), 0.87 (t, J¼6.8 Hz, 3H, CH3). 13C NMR
b
(CDCl3) d: 173.7 (C]O), 132.5 (CH]), 118.2 (]CH2), 65.1 (O–CH2),

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J. Eras et al. / Tetrahedron 65 (2009) 4866–4870
34.5 (CH2( )(C]O)), 32.1 (CH2–CH2–CH3), 29.6, 29.5, 29.4 (CH2), 25.2
evidenced by the presence of a characteristic quintuplet at 4.93 and
a multiplet at 3.42 ppm of the O–CH and CH2–I groups, respectively.
a
(CH2( )(C]O)), 22.9 (CH2–CH3), 14.3 (CH3). GC–MS m/z: 212 [M]þ, 183
b
[MꢁC2H3]þ, 169 [MꢁC3H5]þ, 155 [MꢁOC3H5]þ. IR KBr film nmax
:
3074, 2924, 2854, 1737, 1460, 1159, 989, 723 cmꢁ1
.
Acknowledgements
4.11.3. Allyl pivaloate (2c)
CAS: 15784-26-6. Spectroscopic data are in accordance with the
literature.32
This work was supported in part by a Grant-in-Aid for the Sec-
´
´
´
´
retarıa de Estado de Polıtica Cientıfica y Tecnologica of the Spanish
Ministry of Education and Culture (Contract grant number:
CTQ2006-07451/PPQ). The authors are grateful to the Comissionat
4.11.4. Allyl cinnamate (2d)
´
per a Universitats i Recerca del Departament d’Innovacio, Uni-
CAS: 1866-31-5. Spectroscopic data are in accordance with the
versitats i Empresa de la Generalitat de Catalunya and to the Eu-
literature.33
`
ropean Social Fund (ESF) for the FI grant of Marc Escriba Gelonch.
4.11.5. Allyl benzoate (2e)
Supplementary data
CAS: 583-04-0. Spectroscopic data are in accordance with the
literature.34
Supplementary data associated with this article can be found in
the online version, at doi:10.1016/j.tet.2009.04.042.
4.11.6. Allyl 2-chlorobenzoate (2f)
CAS: 15721-27-4. Spectroscopic data are in accordance with the
literature.34
References and notes
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Ru¨sch, K.; Scha¨fer, H. J.; Manfred, P. S. Angew. Chem., Int. Ed. 2000, 39,
2206–2223.
2. (a) Zhou, C. H. C.; Beltramini, J. N.; Fana, Y.-X.; Lu, G. Q. M. Chem. Soc. Rev. 2008,
37, 527–549; (b) Zheng, Y.; Chen, X.; Shen, Y. Chem. Rev. 2008, 108, 5253–5277;
(c) Pagliaro, M.; Ciriminna, R.; Kimura, H.; Rossi, M.; Della Pina, C. Angew. Chem.,
Int. Ed. 2007, 46, 4434–4440.
3. Je´roˆme, F.; Pouilloux, Y.; Barrault, J. ChemSusChem 2008, 1, 586–615.
4. Eras, J.; Balcells, M.; Canela, R. Afinidad 2007, 64, 203–206.
5. Schrec, D. J.; Kruper, W. J., Jr.; Varjian, R. D.; Jones, M. E.; Campbell, R. M.;
Kearns, K.; Hook, B. D.; Briggs, J. R.; Hippler, J. G. (Dow Global Technologies Inc.,
USA). WO Patent 2006020234, 2006.
4.11.7. Allyl 4-nitrobenzoate (2g)
CAS: 15757-80-7: 1H NMR (CDCl3)
d: 8.28 (m, 4H, CHar), 6.05
(m, 1H, CH2–CH]CH2), 5.43 (dq, Jtrans¼17.2 Hz, Jgem¼1.6 Hz, 1H,
CH]CH2), 5.34 (dq, Jcis¼10 Hz, Jgem¼1.2 Hz, 1H, CH]CH2), 4.87
(dt, J1¼6 Hz, J2¼1.6 Hz, 2H, CH2–CH]CH2). 13C NMR (CDCl3)
d:
164.6 (C]O), 150.8 (CHar–NO2), 135.8 (CH]), 131.7, 131.1, 131.0,
123.9, 123.8 (CHar),119.4 (]CH2), 66.7 (O–CH2). GC–MS m/z:
207 [M]þ, 150 [MꢁCO2C3H5]þ, 134 [MꢁNO2C2H3]þ, 120
[MꢁNO2C3H5]þ, 104 [MꢁCO2C3H5]þ, 76 [MꢁC2H2CO2C3H5]þ. IR
KBr film nmax: 3112, 3080, 2962, 1727, 1528, 1351, 1260, 1099,
6. Villorbina, G.; Toma`s, A.; Escriba´, M.; Oromı´-Farru´ s, M.; Eras, J.; Balcells, M.;
Canela, R. Tetrahedron Lett. 2009, 50, 2828–2830.
1016, 872, 799, 719 cmꢁ1
.
7. Eras, J.; Mendez, J. J.; Balcells, M.; Canela, R. J. Org. Chem. 2002, 67, 8631–8634.
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8. Eras-Joli, J.; Canela-Garayoa, R.; Balcells-Fluvia`, M.; Villorbina-Noguera, G; Es-
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criba-Gelonch, M. (Universitat de Lleida). SP P200601993 2006.
4.11.8. Allyl salicylate (2h)
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CAS: 10484-09-0. Spectroscopic data are in accordance with the
literature.35
4.11.9. Allyl 1-naphthoate (2i)
CAS: 53548-26-8. Spectroscopic data are in accordance with the
14. Nowicki, A.; Keldenich, J.; Agbossou-Niedercorn, F. Eur. J. Org. Chem. 2007,
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15. Mariampillai, B.; Herse, C.; Lautens, M. Org. Lett. 2005, 7, 4745–4747.
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4.11.10. Allyl 2-naphthoate (2j)
CAS: 53409-01-1: 1H NMR (CDCl3)
d: 8.64 (s, 1H, CHar), 8.08 (dd,
J1¼8.4 Hz, J2¼1.2 Hz, 1H, CHar), 7.96 (d, J¼8 Hz, 1H, CHar), 7.89 (d,
J¼8.8 Hz, 2H, 2CHar), 7.57 (m, 2H, 2CHar), 6.10 (m, 1H, CH2–
CH]CH2), 5.46 (dq, Jtrans¼16.8 Hz, Jgem¼1.6 Hz, 1H, CH]CH2), 5.34
(dq, Jcis¼10.4 Hz, Jgem¼1.2 Hz, 1H, CH]CH2), 4.89 (dt, J1¼5.6 Hz,
J2¼1.2 Hz, 2H, CH2–CH]CH2). 13C NMR (CDCl3)
d: 166.6 (C]O),
135.8,132.7 (CHar),132.5 (CH]CH2),131.4,129.6,128.5,128.4, 128.0,
127.6, 126.8, 125.4 (CHar), 118.6 (CH]CH2), 65.9 (O–CH2). GC–MS
m/z: 212 [M]þ, 155 [MꢁOC3H5]þ, 127 [MꢁCO2C3H5]þ. IR ATR nmax
:
3060, 3022, 2942, 1719, 1631, 1469, 1355, 1281, 1227, 1196, 1130,
1093, 980, 778, 762 cmꢁ1
.
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4.12. Determination of 2-chloro-1-(iodomethyl)ethyl
palmitate (3a)
During the GC–MS analysis of the samples obtained in the re-
action of 1a with NaI, a chromatographic peak at tR¼34.7 min was
detected. Its MS presented characteristic ions of 3a ([M]þ: 458;
[MꢁCl]þ: 423; [MꢁI]þ: 331; [MꢁC3H5ICl]þ: 255; and [C3H5ICl]þ:
203). To confirm the presence of this intermediate compound,
these samples were analyzed by 1H NMR. The formation of 3a was