A green and rapid approach for the stereoselective vinylation of phenol, thiol and amine derivatives in water

Article abstract of DOI:10.1039/c1gc15625j

The stereoselective formation of C-O, C-S and C-N bonds by the reaction of phenols, thiols and amines with activated alkynes is described. The reactions are successfully conducted in water with excellent yields at room temperature. The lack of organic sol

Full text of DOI:10.1039/c1gc15625j

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PAPER
A green and rapid approach for the stereoselective vinylation of phenol, thiol
and amine derivatives in water†
Yaghoub Sarrafi,* Marzieh Sadatshahabi, Kamal Alimohammadi and Mahmood Tajbakhsh
Received 30th May 2011, Accepted 20th July 2011
DOI: 10.1039/c1gc15625j
The stereoselective formation of C–O, C–S and C–N bonds by the reaction of phenols, thiols and
amines with activated alkynes is described. The reactions are successfully conducted in water with
excellent yields at room temperature. The lack of organic solvent use in the work-up procedure,
the short reaction time and the environmentally benign mild reaction conditions are advantages of
this method.
condensation of amines with b-dicarbonyl compounds,20 the
Introduction
dehydrohalogenation of aryl 2-haloethyl ethers,21 Michael-type
A basic issue for sustainable growth in the chemical industry
addition–elimination processes,22 allyl ether isomerization,23
is the further development of green chemistry. The concept
amine, phenols or thiol addition to acetylene derivatives under
of green chemistry has been adopted in organic synthesis to
different conditions,24–31 the coupling of vinyl halides with
meet the essential challenges of protecting human health and
amines, phenols or thiols,32 the Wittig reaction33 and the
the environment from chemical hazards.1 The most promising
coupling of various vinyl sources with amines, phenols or thiols
way to attain this objective is undoubtedly to carry out
in conjunction with a metal catalyst.34–37
reactions under aqueous conditions for economical and safety
Although all of these methods are effective, some of them
reasons.2-4 Furthermore, using water as a solvent also offers
have drawbacks, such as harsh reaction conditions,26–28,32d long
many advantages, such as simplicity of reaction conditions, ease
reaction times,24o,32e,34a,36,37 low yields,29,31 the use of expensive
of work-up and product isolation, increasing the selectivity of
catalysts,24a,32e,34a,36,37 tedious work-ups25 and the formation of
a wide variety of organic reactions and accelerating reaction
stereoisomer mixtures.20b,24a,i,l,29,30,32e Thus, there remains a need
rates.2a,5 Recently, water has been employed as a solvent in many
to develop an operationally simple, selective, mild and useful
organic transformations, for example, in the formation of C–S,6
method under green reaction conditions.
C–N7 and C–O8 bonds by conjugated addition reactions.
The vinyl–nitrogen bond is a versatile functional group
capable of partaking in a variety of important reactions,
Results and discussion
including regioselective alkylation and acylation, annulation
cascade and cycloaddition.9 Aryl vinyl ethers and sulfides
are employed as a key synthetic intermediates in the stere-
oselective synthesis of substituted alkenes,10 the generation
of natural product analogs,11 selective herbicides,12 new poly-
meric materials13 and as valuable compounds found in many
biologically-active molecules.14 They are involved in reactions
such as cycloadditions,15 hydroformylations,16 transition metal-
catalyzed carbon–carbon bond formation,17 Michael acceptors18
and enolate equivalents.19
As a part of our program aimed at developing new selective
and environmentally friendly methodologies for the preparation
of organic compounds,38 we report an efficient and green route
for the stereoselective formation of C–O, C–S and C–N bonds
through the reaction of a wide range of substituted phenols,
thiols and amines with dialkyl acetylenedicarboxylates in the
presence of potassium carbonate in water (Scheme 1).
Over the years, several methods have been developed to
synthesize enamines, aryl vinyl ethers and sulfides, such as the
Department of Organic Chemistry, Faculty of Chemistry, University of
Mazandaran, Babolsar, 47416, Islamic Republic of Iran.
E-mail: ysarrafi@umz.ac.ir
† Electronic supplementary information (ESI) available: Detailed exper-
imental procedure, including 1H NMR and 13C NMR spectra for all new
compounds. See DOI: 10.1039/c1gc15625j
Scheme 1 Reaction of phenols, thiols and amines with dialkyl
acetylenedicarboxylates in the presence of potassium carbonate in water
at room temperature.
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Table 1 Stereoselective synthesis of aryl vinyl ethers in water at room
More interesting results were obtained when salicylaldehyde
derivatives were reacted with acetylenedicarboxylate esters un-
der the same reaction conditions (Scheme 2). Salicylaldehyde in
a reaction with DMAD gave exclusively the (Z)-configuration
of O-vinylic salicylaldehyde in high yield. However, when this
reaction was carried out in aprotic solvents such as acetonitrile
or acetone, a mixture of E,Z-isomers of vinyl ether 1 and 4H-
chromen 3 was obtained.
temperature
Entry
R
R¢
Product (Z) yield (%)
1
2
3
4
5
6
7
8
Phenyl
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
Et
Et
Et
Et
Et
Et
Et
t-Bu
Me
Me
1a
1b
1c
1d
1e
1f
1g
1h
1i
98, 99a
97
96
94
95
91
92
90
93
89
92
90
81
83
79
82
4-Chlorophenyl
4-Bromophenyl
3-Nitrophenyl
4-Nitrophenyl
2,6-Dimethylphenyl
2,5-Dimethylphenyl
2,6-Dichlorophenyl
3-Methoxyphenyl
1-Naphthyl
9
10
11
12
13
14
15
16
17
18
19
20
21
22b
23b
24
25b
26b
1j
1k
1l
2-Naphthyl
Phenyl
2-Chlorophenyl
4-Bromophenyl
2,6-Dimethylphenyl
3-Methoxyphenyl
3-Nitrophenyl
2-Naphthyl
Phenyl
2,4-Di-tert-butylphenyl
2-Formyl phenyl
4-Bromo-2-formyl phenyl Me
4-Chloro-2-formyl phenyl Me
2-Formyl phenyl
4-Bromo-2-formyl phenyl Et
4-Chloro-2-formyl phenyl Et
1m
1n
1o
1p
1q
1r
—
—
1s
1t
1u
1v
1w
1x
85
80
No reaction
No reaction
Scheme 2 Selective synthesis of O-vinylic salicylaldehydes.
96
94
93
81
84
83
Et
Similarly, chloro and bromo salicylaldehydes afforded (Z)-
vinyl ethers selectively in excellent yields without the formation
of any (E)-isomer and 4H-chromen (Table 1, entries 21–26).
To the best of our knowledge, this selectivity has not been
observed before, as all the previously reported procedures gave
4H-chromen and E,Z-isomers of the expected vinyl ethers.40
In order to demonstrate the importance of water as a more
superior solvent than organic solvents, a few further experiments
were performed. Salicylaldehyde was treated with DMAD
in MeOH in the presence of K2CO3 at room temperature.
Dimethyl-2-methoxy-butendioate from the attack of methanol
at DMAD as the main product, and a trace amount of the
corresponding vinyl ether and 4H-chromen 3 were formed.
When this reaction was carried out in MeOH/H2O (1 : 1), the
aryl vinyl ether as the major product together with a small
amount of dimethyl-2-methoxy-butendioate and 4H-chromen
3 were obtained. According to these observations, together
with the results obtained in the aprotic solvents mentioned
previously, a possible explanation could be the insolubility
and fast protonation of the carbanion intermediate in water,
which reduces significantly the chance of isomerization and self-
condensation to form compound 3.
Due to the importance of divinyl ethers as interesting pre-
cursors in polymer chemistry, as components of homo- and
copolymers, the reactions of dihydroxybenzenes were investi-
gated. Hydroquinone and resorcinol were reacted with 2 mol of
DMAD or DEAD to afford the expected bis(vinyloxy)benzene
derivatives under optimal conditions (Table 2, entries 1–4).
However, as indicated in Table 2, in the case of pyrocatechol,
only a trace amount of the corresponding adduct was obtained
(Table 2, entries 5 and 6).
a Phenol (100 mmol) was allowed to react with DMAD (100 mmol) in
the presence of K2CO3 in water at room temperature. b NaOH was used
instead of K2CO3.
At the beginning of the present study, we conducted the reac-
tion of phenol derivatives with dimethyl acetylenedicarboxylate
(DMAD) in an aqueous solution of K2CO3 (Table 1, entries
1–11). The reactions were rapid and stereoselectively afforded
the corresponding fumarate aryl vinyl ethers in excellent yields
after only 5–15 min at room temperature. After completion of
the reaction, the crude product was simply collected from the
aqueous medium by filtration or decantation. The structures of
the products were assigned using spectroscopic data, and their
1H NMR spectra clearly indicated the formation of the fumarate
stereoisomer as the sole product based on the vinylic proton
positions in comparison with previously reported values.27,30,31,39
As shown in Table 1, when phenolic substrates with electron-
withdrawing or electron-donating groups were used, the reaction
time and yields were not affected.
To evaluate the scope of this transformation, the reaction
of bulky acetylenic esters or phenols containing a bulky
group on the ortho position was investigated. When diethyl
acetylenedicarboxylate (DEAD) was subjected to the reaction
conditions, slightly lower yields ofarylvinylethers were obtained
(Table 1, entries 12–18). However, in the case of di(tert-butyl)
acetylenedicarboxylate or 2,4-di-tert-butylphenol, which are not
soluble in aqueous media, the reaction did not occur, even after
a long reaction time and a higher temperature (Table 1, entries
19 and 20). Upon repeating the reactions of entries 19 and 20
in acetone/water (1 : 1) to dissolve the starting materials, only
the reaction of entry 19 proceeded to give a mixture of E,Z aryl
vinyl ethers (10 : 90). The lack of formation of product in entry
20 could be due to the steric effect of 2,4-di-tert-butylphenol.
To extend the generality and applicability of this method,
C–S and C–N bond formation via the coupling of mercaptans
and amines with dialkyl acetylenedicarboxylates was examined.
Various aliphatic and aromatic thiols, and secondary amines
generated the desired products under the optimal reaction
conditions in higher yield and purity (Table 3).
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Table 2 Stereoselective synthesis of bis(vinyloxy)benzenes in water at
room temperature
stereoselectivity was obtained under the same conditions. All
the reactions proceeded rapidly (within 10–15 min) to give only
the (Z)-form conjugate addition product. The results of using
1
this mild and simple procedure are shown in Table 4. The H
NMR spectra of the products displayed two doublets with a
coupling constant corresponding to the (Z)-form isomer for the
two olefinic protons, which is in agreement with values reported
in the literature.32j,41
In order to demonstrate the applicability of this method, a
large-scale experiment was run. The reaction of 100 mmol (9.4 g)
phenol with DMAD under the same reaction conditions gave
1a in almost the same yield as on the small scale (99%, Table 1,
entry 1).
Entry
Substrate
R¢
Product
(Z) yield (%)
1
2
3
4
5
6
Hydroquinone
Resorcinol
Hydroquinone
Resorcinol
Pyrocatechol
Pyrocatechol
Me
Me
Et
Et
Me
Et
4a
4b
4c
4d
4e
—
95
92
87
79
6
Conclusions
Trace
In summary, we have developed a stereoselective, mild, single-
step and green procedure for the preparation of aryl vinyl ethers,
aryl vinyl sulfides and enamines through the direct coupling of
various substituted phenols, thiols and amines with activated
alkynes in water at room temperature. This process leads
exclusively to the (Z)-configuration of the vinylation products.
The availability of the starting material, short reaction times,
quantitative yields of products and the fairly mild reaction
conditions without using any volatile organic solvents make this
protocol convenient for industrial applications.
Table 3 Stereoselective synthesis of aryl vinyl sulfides and enamines in
water at room temperature
Entry
Substrate
R¢
Product
(Z) yield (%)
1
2
3
4
5
6
7
8
Thiophenol
Me
Me
Me
Me
Me
Et
Et
Et
Et
Me
Me
Me
Et
Et
Et
2a
2b
2c
2d
2e
2f
2g
2h
2i
2j
2k
2l
2m
2n
2o
97
96
93
97
94
89
87
84
85
97
97
96
90
87
89
4-Methyl thiophenol
2-Naphthylthiol
Cyclohexylthiol
Pentylthiol
Thiophenol
4-Bromo thiophenol
4-Methyl thiophenol
Cyclohexylthiol
Piperidine
N-Methylaniline
Morpholine
Piperidine
N-Methylaniline
Morpholine
Experimental
9
10
11
12
13
14
15
General considerations
Melting points were measured on an Electrothermal 9100
apparatus. Infrared spectra were recorded on a Shimadzu IR-
8300 series FT-IR spectrophotometer. 1H NMR and 13C NMR
spectra were recorded on a Bruker 400-MHz instrument in
CDCl3 solvent with TMS as a standard. Mass spectra were
recorded by a Jeol DX303 HF mass spectrometer. Elemental
analyses were carried out using a Perkin-Elmer CHN 2400
instrument.
Table 4 Reactions of various nucleophiles with methyl- and ethyl-
propiolate
Typical procedure for the synthesis of 1a
Phenol (0.188 g, 2 mmol) was dissolved in aqueous solution
of K2CO3 (0.276 g, 2 mmol) and DMAD (0.284 g, 2 mmol)
was added. The reaction mixture was stirred vigorously at
room temperature. A turbid solution was formed which by
consumption of phenol (monitored by TLC) in 5 min, the
reaction mixture became clear and dimethyl (Z)-2-(phenoxy)-
2-butenedioate 1a existed as solid in water. The product was
isolated by filtration without further purification.
Compounds 1a–f, 1j, 1k, 1s, 1v, 1w and 5h are known
compounds, and were characterized by comparison of
their physical and spectroscopic data with those previously
reported.24n,o,27,30,31,32j,40 The physical properties and spectral data
of the new compounds are reported here.
Entry
Substrate
R¢
Product
(Z) yield (%)
1
2
3
4
5
6
7
8
9
Phenol
Me
Me
Me
Me
Me
Me
Et
Et
Et
Et
5a
5b
5c
5d
5e
5f
93
92
89
94
92
95
89
86
83
83
4-Chlorophenol
2-Formyl phenol
Thiophenol
Cyclohexylthiol
Piperidine
Phenol
5g
5h
5i
Thiophenol
Cyclohexylthiol
Piperidine
10
5j
The reaction of dialkyl acetylenedicarboxylates with primary
amines did not give satisfactory results.
Furthermore, to expand the reaction scope, other activated
alkynes, such as methyl- and ethyl-propiolate, were treated with
phenols, thiols and amines (Table 4). It was found that excellent
Dimethyl (Z)-2-(2,5-dimethylphenoxy)-2-butenedioate (1g).
◦
1
White solid. mp 53–55 C. H NMR (400 MHz, CDCl3): d
2.26 (s, 3H, CH3), 2.33 (s, 3H, CH3), 3.73 (s, 3H, OCH3), 3.75
(s, 3H, OCH3), 6.50 (s, 1H, Ar–H), 6.55 (s, 1H, HC C), 6.80
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(d, 1H, J = 7.6 Hz, Ar–H), 7.08 (d, 1H, J = 7.6 Hz, Ar–H). 13
NMR (100 MHz, CDCl3): d 15.68, 21.02 (2CH3), 51.88, 52.97
C
Diethyl (Z)-2-(2,6-dimethylphenoxy)-2-butenedioate (1o).
Yellow oil. H NMR (400 MHz, CDCl3): d 1.16 (t, 3H, J =
1
(2OCH3), 113.81, 115.09, 124.19, 124.68, 131.00, 136.61, 150.62,
7.2 Hz, CH3), 1.24 (t, 3H, J = 7.2 Hz, CH3), 2.26 (s, 3H, CH3),
2.28 (s, 3H, CH3), 4.05 (q, 2H, J = 7.2 Hz, OCH2), 4.16 (q, 2H,
J = 7.2 Hz, OCH2), 6.08 (s, 1H, HC C), 6.95–7.01 (m, 3H,
Ar–H). 13C NMR (100 MHz, CDCl3): d 13.76, 14.07, 15.89,
16.89 (4CH3), 60.61, 62.16 (2CH2), 105.35, 120.14, 124.99,
128.58, 129.90, 151.79, 152.42 (4C, 4CH), 162.258, 164.18
(2C O, ester). IR (neat, nmax, cm-1): 1727, 1662, 1205, 1131.
Elemental analysis for C16H20O5: Calc. C, 65.74; H, 6.90.
Found: C, 65.60; H, 6.95. EIMS: m/z 292.1 (M+).
154.75 (4CH, 4C), 162.79, 164.13 (2C O, ester). IR (KBr, nmax
,
cm-1): 1732, 1634, 1425, 1210. Elemental analysis for C14H16O5:
Calc. C, 63.63; H, 6.10. Found: C, 63.75; H, 6.23. EIMS: m/z
264.1 (M+).
Dimethyl (Z)-2-(2,6-dichlorophenoxy)-2-butenedioate (1h).
White solid. mp 40–42 ◦C. 1H NMR (400 MHz, CDCl3): d 3.72
(s, 3H, OCH3), 3.77 (s, 3H, OCH3), 6.68 (s, 1H, HC C), 6.76 (d,
1H, J = 8.8 Hz, Ar–H), 7.14 (dd, 1H, J = 7.6 Hz, J = 2.4 Hz, Ar–
H), 7.42 (d, 1H, J = 2.4 Hz, Ar–H). 13C NMR (100 MHz, CDCl3):
d 52.15, 53.27 (2OCH3), 115.89, 116.94, 124.40, 127.61, 128.77,
130.45, 149.01, 151.20 (4C, 4CH), 161.80, 163.40 (2C O, ester).
IR (KBr, nmax, cm-1): 1724, 1655, 1487, 1212, 1100. Elemental
analysis for C14H16O5: Calc. C, 47.24; H, 3.30. Found: C, 47.12;
H, 3.44. EIMS: m/z 303.8 (M+).
Diethyl (Z)-2-(3-methoxyphenoxy)-2-butenedioate (1p). Yel-
low oil. 1H NMR (400 MHz, CDCl3): d 1.19 (t, 3H, J = 7.2 Hz,
CH3), 1.23 (t, 3H, J = 7.2 Hz, CH3), 3.77 (s, 3H, OCH3), 4.19
(2q, 4H, J = 7.2 Hz, 2OCH2), 6.58 (s, 1H, HC C), 6.51–
7.20 (m, 4H, Ar–H). 13C NMR (100 MHz, CDCl3): d 13.87,
14.03, 55.35 (3CH3), 60.99, 62.29 (2CH2), 102.53, 108.09, 109.16,
115.18, 129.95 (5CH), 149.90, 157.72, 160.82 (3C), 162.18,
163.57 (2C O, ester). IR (neat, nmax, cm-1): 1738, 1636, 1220,
1145. Elemental analysis for C15H18O6: Calc. C, 61.22; H, 6.16.
Found: C, 61.13; H, 6.04. EIMS: m/z 294.1 (M+).
Dimethyl (Z)-2-(3-◦Methoxyphenoxy)-2-butenedioate (1i).
White solid. mp 56–57 C. 1H NMR (400 MHz, CDCl3): d 3.73
(s, 3H, OCH3), 3.77 (s, 3H, OCH3), 3.80 (s, 3H, OCH3), 6.61 (s,
1H, HC C), 6.50–7.22 (m, 4H, Ar–H). 13C NMR (100 MHz,
CDCl3): d 52.03, 53.06, 55.37 (3CH3), 102.49, 107.94, 109.21,
115.16, 130.04 (5CH), 149.68, 157.61, 160.87 (3C), 162.64,
163.85 (2C O, ester). IR (KBr, nmax, cm-1): 1747, 1645, 1460,
1223, 1155. Elemental analysis for C13H14O6: Calc. C, 58.64; H,
5.30. Found: C, 58.73; H, 5.19. EIMS: m/z 266 (M+).
Diethyl (Z)-2-(3-nitrophenoxy)-2-butenedioate (1q). Yellow
oil. 1H NMR (400 MHz, CDCl3): d 1.21 (t, 3H, J = 7.2 Hz, CH3),
1.25 (t, 3H, J = 7.2 Hz, CH3), 4.18 (q, 2H, J = 7.2 Hz, OCH2),
4.26 (q, 2H, J = 7.2 Hz, OCH2), 6.80 (s, 1H, HC C), 7.056 (d,
2H, J = 9.2 Hz, Ar–H); 8.24 (d, 2H, J = 9.2 Hz, Ar–H). 13C
NMR (100 MHz, CDCl3): d 13.95, 13.99 (2CH3), 61.36, 62.82
(2CH2), 116.03, 117.83, 120.27, 125.89, 148.33, 161.24 (5CH,
3C), 161.50, 162.82 (2C O, ester). IR (neat, nmax, cm-1): 1758,
1640, 1217, 1155. Elemental analysis for C14H15NO7: Calc. C,
54.37; H, 4.89. Found: C, 54.25; H, 4.97. EIMS: m/z 309 (M+).
1
Diethyl (Z)-2-(phenoxy)-2-butenedioate (1l). Yellow oil. H
NMR (400 MHz, CDCl3): d 0.91 (t, 3H, J = 7.2 Hz, CH3), 1.33 (t,
3H, J = 7.2 Hz, CH3), 3.81 (q, 2H, J = 7.2 Hz, OCH2), 4.27 (q, 2H,
J = 7.2 Hz, OCH2), 6.40 (s, 1H, HC C), 6.31–7.48 (m, 5H, Ar–
H). 13C NMR (100 MHz, CDCl3): d 13.50, 14.26 (2CH3), 60.95,
62.20 (2CH2), 119.46 ( CH), 128.81, 129.04, 132.35, 133.22
(CH, C-Ar), 149.46 ( C), 164.48, 165.19 (2C O, ester). IR
(neat, nmax, cm-1): 1737, 1654, 1221, 1196. Elemental analysis
for C14H16O5: Calc. C, 63.63; H, 6.10. Found: C, 63.75; H, 6.29.
EIMS: m/z 264.1 (M+).
Diethyl (Z)-2-(2-naphtoxy)-2-butenedioate (1r). Yellow oil.
1H NMR (400 MHz, CDCl3): d 1.15 (t, 3H, J = 7.2 Hz, CH3),
1.22 (t, 3H, J = 7.2 Hz, CH3), 4.19 (q, 4H, J = 7.2 Hz, 2OCH2),
6.70 (s, 1H, HC C), 7.23–7.85 (m, 6H, Ar–H). 13C NMR
(100 MHz, CDCl3): d 13.87, 14.05 (2CH3), 61.00, 62.32 (2CH2),
110.88, 115.58, 118.09, 124.72, 126.65, 127.11, 127.80, 129.91,
130.65 (5CH), 130.18, 133.99, 150.02, 154.64 (4C), 162.23,
163.57 (2C O, ester). IR (neat, nmax, cm-1): 1734, 1668, 1265,
1158. Elemental analysis for C18H18O5: Calc. C, 68.78; H, 5.77.
Found: C, 68.70; H, 5.64. EIMS: m/z 314.1 (M+).
Diethyl (Z)-2-(2-chlorophenoxy)-2-butenedioate (1m). Yel-
low oil. 1H NMR (400 MHz, CDCl3): d 1.17 (t, 3H, J = 7.2 Hz,
CH3), 1.20 (t, 3H, J = 7.2 Hz, CH3), 4.17 (q, 2H, J = 7.2 Hz,
OCH2), 4.19 (q, 2H, J = 7.2 Hz, OCH2), 6.65 (s, 1H, HC C),
6.82–7.42 (m, 4H, Ar–H). 13C NMR (100 MHz, CDCl3): d
13.79, 13.94 (2CH3), 61.07, 62.40 (2CH2), 115.64, 116.20, 123.48,
124.09, 127.52, 130.65, 149.46, 152.47 (5CH, 3C), 161.46, 163.28
(2C O, ester). IR (neat, nmax, cm-1): 1750, 1634, 1454, 1211,
1186. Elemental analysis for C14H15ClO5: Calc. C, 56.29; H, 5.06.
Found: C, 56.36; H, 4.95. EIMS: m/z 297.9 (M+).
Dimethyl 2-(4-brom◦o-2-formylphenoxy)-2-butenedioate (1t).
White solid. mp 88–90 C. 1H NMR (400 MHz, CDCl3): d 3.74,
3.81 (2 s, 6H, 2OCH3), 6.76 (d, 1H, J = 8 Hz, Ar–H), 6.79 (s,
1H, HC C), 7.59 (dd, 1H, J = 8 Hz, J = 4 Hz, Ar–H), 8.02 (d,
1H, J = 4 Hz, Ar–H), 10.47 (s, 1H, CHO). 13C NMR (100 MHz,
CDCl3): d 52.31, 53.43 (2CH3), 116.79, 117.32, 117.35, 131.25,
137.96, 148.66, 157.78 (CH, C), 161.80, 163.22 (2C O, ester),
187.56 (CHO). IR (KBr, nmax, cm-1): 2830, 1747, 1720, 1646,
1200, 1141. Elemental analysis for C13H11BrO6: Calc. C, 45.50;
H, 3.23. Found: C, 45.65; H, 3.31. EIMS: m/z 341.9 (M+).
Diethyl (Z)-2-(4-bromophenoxy)-2-butenedioate (1n). Yel-
1
low oil. H NMR (400 MHz, CDCl3): d 1.41 (2t, 6H, J = 7.2,
2CH3), 4.17 (q, 2H, J = 7.2 Hz, OCH2), 4.20 (q, 2H, J = 7.2 Hz,
CH2), 6.83 (s, 1H, HC C), 6.85 (d, 2H, J = 8.8 Hz, Ar–H),
7.39 (d, 2H, J = 8.8 Hz, Ar–H). 13C NMR (100 MHz, CDCl3): d
13.89, 14.02 (2CH3), 61.09, 62.44 (2CH2), 115.80, 116.00, 117.93,
132.48, 149.42, 155.83 (CH, C), 161.81, 163.34 (2C O, ester).
IR (neat, nmax, cm-1): 1744, 1619, 1222, 1169. Elemental analysis
for C14H15BrO5: Calc. C, 56.29; H, 5.06. Found: C, 56.36; H,
4.90. EIMS: m/z 342 (M+).
Dimethyl 2-(4-chloro-2-formylphenoxy)-2-butenedioate (1u).
White solid. mp 96–98 ◦C. 1H NMR (400 MHz, CDCl3): d 3.75,
3.80 (2 s, 6H, 2OCH3), 6.79 (s, 1H, HC C), 6.82 (d, J = 8.8 Hz,
1H, Ar–H), 7.45 (dd, J = 8.8 Hz, J = 2.6 Hz, 1H, Ar–H), 7.88 (d,
J = 2.8 Hz, 1H, Ar–H), 10.48 (s, 1H, CHO). 13C NMR (100 MHz,
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CDCl3): d 52.30, 53.42 (2CH3), 117.00, 117.27, 128.22, 126.64,
135.06, 129.56, 148.75, 157.26 (C, CH), 161.84, 163.24 (2C O,
ester), 187.68 (CHO). IR (KBr, nmax, cm-1): 2843, 1740, 1723,
1627, 1211, 1189. Elemental analysis for C13H11ClO6: Calc. C,
52.28; H, 3.71. Found: C, 52.37; H, 3.62. EIMS: m/z 298 (M+).
3.74 (s, 3H, OCH3), 3.84 (s, 3H, OCH3), 6.30 (s, 1H, HC C). 13C
NMR (100 MHz, CDCl3): d 13.83 (CH3), 22.10, 29.31, 30.79,
32.57 (4CH2), 51.68, 52.97 (2OCH3), 118.57 ( CH), 149.53
(
C), 164.94, 165.62 (2C O, ester). IR (neat, nmax, cm-1): 1755,
1474, 1229, 1117. Elemental analysis for C11H18O4S: Calc. C,
53.64; H, 7.37. Found: C, 53.60; H, 7.49. EIMS: m/z 246 (M+).
Diethyl 2-(4-chloro-2-formylphenoxy)-2-butenedioate (1x).
1
Yellow oil. H NMR (400 MHz, CDCl3): d 1.238 (2t, 6H, J =
Diethyl (Z)-2-(phenylthio)-2-butenedioate (2f). Yellow oil.
1H NMR (400 MHz, CDCl3): d 0.91 (t, 3H, J = 7.2 Hz, CH3),
1.33 (t, 3H, J = 7.2 Hz, CH3), 3.81 (q, 2H, J = 7.2 Hz, OCH2), 4.27
(q, 2H, J = 7.2 Hz, OCH2), 6.40 (s, 1H, HC C), 7.32–7.48 (m,
5H, Ar–H). 13C NMR (100 MHz, CDCl3): d 13.50, 14.26 (2CH3),
60.95, 62.20 (2OCH2), 119.46 ( CH), 128.81, 129.04, 132.35,
133.22 (CH, C-Ar), 149.59 ( C), 164.48, 165.19 (2C O, ester).
IR (neat, nmax, cm-1): 1731, 1429, 1198, 1123. Elemental analysis
for C14H16O4S: Calc. C, 59.98; H, 5.75. Found: C, 59.89; H, 5.65.
EIMS: m/z 280 (M+).
7.2 Hz, 2CH3), 4.21 (q, 2H, J = 7.2 Hz, OCH2), 4.24 (q, 2H,
J = 7.2 Hz, OCH2), 6.78 (s, 1H, HC C), 6.84 (d, 1H, J =
8.8 Hz, Ar–H), 7.46 (dd, 1H, J = 8.8 Hz, 2.8 Hz, Ar–H), 8.88
(d, 1H, J = 2.8 Hz, Ar–H), 10.50 (s, 1H, CHO). 13C NMR
(100 MHz, CDCl3): d 13.92, 14.02 (2CH3), 61.38, 62.80 (2CH2),
117.11 ( CH), 117.55, 126.64, 128.10, 129.45, 135.01, 157.39
(C, CH-Ar), 148.77 ( C), 161.36, 162.91 (2C O, ester), 187.75
(CHO). IR (neat, nmax, cm-1): 2891, 1741, 1719, 1639, 1205,
1176. Elemental analysis for C15H15ClO6: Calc. C, 55.14; H, 4.63.
Found: C, 55.01; H, 4.50. EIMS: m/z 326 (M+).
Diethyl (Z)-2-(4-b◦romophenylthio)-2-butenedioate (2g). Yel-
low solid. mp 64–65 C. 1H NMR (400 MHz, CDCl3): d 0.98 (t,
3H, J = 7.2 Hz, CH3), 1.33 (t, 3H, J = 7.2 Hz, CH3), 3.88 (q, 2H,
J = 7.2 Hz, OCH2), 4.26 (q, 2H, J = 7.2 Hz, OCH2), 6.45 (s, 1H,
HC C), 7.32 (d, 2H, J = 8.4 Hz, Ar–H), 7.46 (d, 2H, J = 8.8 Hz,
Ar–H). 13C NMR (100 MHz, CDCl3): d 13.62, 14.24 (2CH3),
61.10, 62.38 (2OCH2), 120.72 ( CH), 123.24, 131.63 (C-Ar),
132.18, 134.56 (4CH), 148.20 ( C), 164.14, 165.06 (2C O,
ester). IR (KBr, nmax, cm-1): 1741, 1475, 1192, 1115. Elemental
analysis for C14H15BrO4S: Calc. C, 46.81; H, 4.21. Found: C,
46.93; H, 4.30. EIMS: m/z 357.9 (M+).
Dimethyl (Z)-2-(phenylthio)-2-butenedioate (2a). Yellow oil.
1H NMR (400 MHz, CDCl3): d 3.33 (s, 3H, OCH3), 3.79 (s, 3H,
OCH3), 6.37 (s, 1H, HC C), 7.28–7.48 (5H, Ar–H). 13C NMR
(100 MHz, CDCl3): d 51.89, 52.60 (2CH3), 118.69 ( CH),
128.95, 130.51, 133.35, 134.28 (C, CH-Ar), 149.94 ( C), 164.78,
165.53 (2C O, ester). IR (neat, nmax, cm-1): 1745, 1617, 1474,
1229. Elemental analysis for C12H12O4S: Calc. C, 57.13; H, 4.79.
Found: C, 57.26; H, 4.65. EIMS: m/z 252 (M+).
Dimethyl (Z)-2-(4-methylphenylthio)-2-butenedioate (2b).
◦
1
Yellow solid. mp 77–79 C. H NMR (400 MHz, CDCl3): d
2.33 (s, 3H, CH3), 3.34 (s, 3H, OCH3), 3.78 (s, 3H, OCH3),
6.29 (s, 1H, HC C), 7.13 (d, 2H, J = 7.6, Ar–H), 7.36 (d, 2H,
J = 8, Ar–H). 13C NMR (100 MHz, CDCl3): d 21.20, 51.86,
52.54 (3CH3), 117.67 (CH), 128.14, 129.80, 133.64, 139.30 (C,
CH-Ar), 150.79 (C), 164.82, 165.59 (2C O, ester). IR (KBr,
Diethyl (Z)-2-(4-methylphenylthio)-2-butenedioate (2h). Yel-
low oil. 1H NMR (400 MHz, CDCl3): d 0.94 (t, 3H, J = 7.2 Hz,
CH3), 1.33 (t, 3H, J = 7.2 Hz, CH3), 2.34 (s, 3H, CH3), 3.81 (q,
2H, J = 7.2 Hz, OCH2), 4.26 (q, 2H, J = 7.2 Hz, OCH2), 6.32 (s,
1H, HC C), 7.13 (d, 2H, J = 8.4 Hz, Ar–H), 7.35 (d, 2H, J =
8.4 Hz, Ar–H). 13C NMR (100 MHz, CDCl3): d 13.54, 14.26,
21.20 (3CH3), 60.86, 62.11 (2OCH2), 118.38 ( CH), 129.75,
129.04, 133.55, 128.45, 39.17 (CH, C-Ar), 150.48 ( C), 164.50,
165.25 (2C O, ester). IR (neat, nmax, cm-1): 1752, 1646, 1220,
1160. Elemental analysis for C15H18O4S: Calc. C, 61.20; H, 6.16.
Found: C, 61.11; H, 6.08. EIMS: m/z 294 (M+).
n
max, cm-1): 1720, 1654, 1585, 1425, 1190. Elemental analysis for
C13H14O4S: Calc. C, 58.63; H, 5.30. Found: C, 58.51; H, 5.23.
EIMS: m/z 266 (M+).
Dimethyl (Z)-2-(naphtylthio)-2-butenedioate (2c). Pale yel-
◦
1
low solid. mp 60–62 C. H NMR (400 MHz, CDCl3): d 3.28,
3.84 (s, 6H, 2OCH3), 6.47 (s, 1H, HC C), 7.48–7.99 (m, 7H, Ar–
H). 13C NMR (100 MHz, CDCl3): d 52.00, 52.69 (2CH3), 119.41
Diethyl (Z)-2-(cyclohexylthio)-2-butenedioate (2i). Yellow
oil. 1H NMR (400 MHz, CDCl3) d 1.36 (t, 3H, J = 7.2 Hz, CH3),
1.38 (t, 3H, J = 7.2 Hz, CH3), 1.38–2.06 (10H, CH2 cyclohexan),
3.31 (tt, 1H, J = 10.6 Hz, J = 3.6 Hz, CH-Cyclohexan), 4.22
(q, 2H, J = 7.2 Hz, OCH2), 4.32 (q, 2H, J = 7.2 Hz, OCH2),
6.35 (s, 1H, HC C). 13C NMR (100 MHz, CDCl3): d 14.13,
14.17 (2CH3), 25.33, 25.94, 32.76, 44.65 (CH, CH2), 60.65,
62.37 (2OCH3), 120.24 ( CH), 148.27 ( C), 164.83, 165.21
(2C O, ester). IR (neat, nmax, cm-1): 1739, 1661, 1428, 1219,
1153. Elemental analysis for C14H22O4S: Calc. C, 58.71; H, 7.74.
Found: C, 58.59; H, 7.68. EIMS: m/z 286.1 (M+).
(
CH), 126.86, 127.07, 128.72, 129.37, 29.73, 132.77, 132.91,
133.37 (C, CH-Ar), 149.58 ( C), 164.85, 165.57 (2C O, ester).
IR (KBr, nmax, cm-1): 1724, 1650, 1585, 1195. Elemental analysis
for C16H14O4S: Calc. C, 63.56; H, 4.67. Found: C, 63.45; H, 6.75.
EIMS: m/z 302 (M+).
Dimethyl (Z)-2-(cyclohexylthio)-2-butenedioate (2d). Yellow
1
oil. H NMR (400 MHz, CDCl3): d 1.34–1.90 (10H, 5CH2,
cyclohexan), 3.27 (tt, 1H, J = 10.6 Hz, J = 3.6 Hz, CH-
Cyclohexan), 3.76 (s, 3H, OCH3), 3.86 (s, 3H, OCH3), 6.38 (s, 1H,
HC C). 13C NMR (100 MHz, CDCl3): d 25.34, 25.93 (2CH3),
33.80, 44.95, 51.73, 53.06 (CH, CH2), 120.26 ( CH), 148.04
Dimethyl-(Z)-2-(piperidine-1-yl)-2-butenedioate (2j). Pale
(
C), 165.30, 165.55 (2C O, ester). IR (neat, nmax, cm-1): 1740,
◦
1
orange solid. mp 79–81 C. H NMR (400 MHz, CDCl3): d
1.62 (m, 6H, 3CH2), 3.15 (m, 4H, 2NCH2), 3.62 (s, 3H, OCH3),
3.90 (s, 3H, OCH3), 4.72 (s, 1H, HC C). 13C NMR (100 MHz,
CDCl3): d 23.91, 25.08, 48.57 (6CH2), 50.76, 52.78 (2CH3),
84.68 ( CH), 154.55 ( C), 166.35, 168.39 (2C O, ester). IR
(KBr, nmax, cm-1): 1736, 1445, 1173, 1152. Elemental analysis for
1623, 1474, 1210. Elemental analysis for C12H18O4S: Calc. C,
55.79; H, 7.02. Found: C, 55.88; H, 6.91. EIMS: m/z 258 (M+).
Dimethyl (Z)-2-(pentylthio)-2-butenedioate (2e). Yellow oil.
1H NMR (400 MHz, CDCl3): d 0.87 (t, 3H, J = 7.0, CH3), 1.35
(m, 2H, CH2), 1.57 (m, 2H, CH2), 2.81 (t, 2H, J = 7.4, CH2–S),
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C11H17NO4: Calc. C, 58.14; H, 7.54; N, 6.16. Found: C, 58.10;
(4OCH3), 114.74 (2 CH), 117.45 (4CH), 149.99, 152.44 (4C),
162.55, 163.88 (4C O, ester). IR (KBr, nmax, cm-1): 1724, 1503,
1253, 1197. Elemental analysis for C18H18O10: Calc. C, 54.83; H,
4.60. Found: C, 54.95; H, 4.69. EIMS: m/z 394 (M+).
H, 7.60; N, 6.18. EIMS: m/z 227.1 (M+).
Dimethyl-(Z)-2-(phenylmethylamino)-2-butenedioate
(2k).
White solid. mp 72–73 ◦C. 1H NMR (400 MHz, CDCl3): d 3.24
(s, 3H, CH3), 3.66 (s, 3H, OCH3), 3.69 (s, 3H, OCH3), 4.82 (s,
1H, HC C), 7.20–7.40 (m, 5H, Ar–H). 13C NMR (100 MHz,
CDCl3): d 40.83, 50.96, 52.63 (3CH3), 88.14 ( CH), 126.54,
127.40, 129.46 (5CH-Ar), 144.55, 154.20 (2C), 165.34, 167.85
(2C O, ester). IR (KBr, nmax, cm-1): 1749, 1434, 1218, 1118.
Elemental analysis for C13H15NO4: Calc. C, 62.64; H, 6.07; N,
5.62. Found: C, 62.72; H, 6.15; N, 5.71. EIMS: m/z 249.1 (M+).
1,3-Bis(dimethyl (Z)-2-butenedioatoxy)benzene (4b). White
◦
1
solid. mp 70–72 C. H NMR (400 MHz, CDCl3): d 3.72 (s,
6H, 2OCH3), 3.76 (s, 6H, 2OCH3), 6.61 (s, 2H, 2 HC C), 6.59–
7.25 (m, 4H, Ar–H). 13C NMR (100 MHz, CDCl3): d 52.04,
53.07 (4OCH3), 104.95 (2 CH), 111.12, 115.38, 130.31, 157.54
(C, CH-Ar), 149.43 (2 C), 162.41, 163.70 (4C O, ester). IR
(KBr, nmax, cm-1): 1722, 1583, 1255, 1190. Elemental analysis for
C18H18O10: Calc. C, 54.83; H, 4.60. Found: C, 54.75; H, 4. 49.
EIMS: m/z 394 (M+).
Dimethyl-(Z)-2-(morpholino)-2-butenedioate (2l). Pale yel-
◦
1
low solid. mp 50–52 C. H NMR (400 MHz, CDCl3): d 3.12
(t, 4H, J = 4.8 Hz, 2NCH2), 3.63 (s, 3H, OCH3),. 3.72 (t,
4H, J = 4.8 Hz, 2OCH2), 3.90 (s, 3H, OCH3), 4.78 (s, 1H,
HC C). 13C NMR (100 MHz, CDCl3): d, 47.09, 51.02, 53.03,
65.84 (CH2, CH3), 87.13 ( CH), 154.69 ( C), 165.83, 167.83
(2C O, ester). IR (KBr, nmax, cm-1):1745, 1454, 1200, 1146.
Elemental analysis for C10H15NO5: Calc. C, 52.40; H, 6.60; N,
6.11. Found: C, 52.5; H, 6.73; N, 6.16. EIMS: m/z 229.1 (M+).
1,4-Bis(diethyl (Z)-2-butenedioatoxy)benzene (4c). Yellow
oil. 1H NMR (400 MHz, CDCl3): d 1.18 (t, 6H, J = 7.2, 2CH3),
1.23 (t, 6H, J = 7.2, 2CH3), 4.18 (q, 4H, J = 7.2 Hz, 2OCH2),
4.18 (q, 4H, J = 7.2 Hz, 2OCH2), 6.55 (s, 2H, 2 HC C), 6.92
(s, 4H, Ar–H). 13C NMR (100 MHz, CDCl3): d 13.85, 14.04
(4CH3), 60.95, 62.25 (4OCH2), 114.96 (2 CH), 117.39 (4CH-
Ar), 150.13 (2 C), 152.51 (2C-Ar), 162.07, 163.51 (4C O,
ester). IR (neat, nmax, cm-1): 1724, 1658, 1503, 1253, 1197.
Elemental analysis for C18H18O10: Calc. C, 54.83; H, 4.60. Found:
C, 54.92; H, 4.65. EIMS: m/z 450.1 (M+).
Diethyl-(Z)-2-(piperidine-1-yl)-2-butenedioate (2m). Yellow
1
oil. H NMR (400 MHz, CDCl3): d 1.23 (t, 3H, J = 7.2 Hz,
CH3), 1.37 (t, 3H, J = 7.2 Hz, CH3), 1.62 (m, 6H, 3CH2),
3.17 (m, 4H, 2NCH2), 4.09 (q, 2H, J = 7.2 Hz, OCH2), 4.39
(q, 2H, J = 7.2 Hz, OCH2), 4.73 (s, 1H, HC C). 13C NMR
(100 MHz, CDCl3): d 13.93, 14.48 (2CH3), 23.98, 25.08, 48.52
(5CH2), 59.21, 62.02 (2OCH2), 85.18 ( CH), 154.56 ( C),
165.89, 167.82 (2C O, ester). IR (neat, nmax, cm-1): 1734, 1521,
1444, 1152, 1129. Elemental analysis for C13H21NO4: Calc. C,
61.16; H, 8.29; N, 5.49. Found: C, 61.21; H, 8.40; N, 5.58. EIMS:
m/z 255.1 (M+).
1,3-Bis(diethyl (Z)-2-butenedioatoxy)benzene (4d). Yellow
oil. 1H NMR (400 MHz, CDCl3): d 1.18 (t, 6H, J = 7.2, 2CH3),
1.22 (t, 6H, J = 7.2, 2CH3), 4.15 (q, 8H, J = 7.2 Hz, 4OCH2),
6.59 (s, 2H, 2 HC C), 6.60–7.25 (m, 4H, Ar–H). 13C NMR
(100 MHz, CDCl3) d 13.85, 14.00 (4CH3), 61.09, 62.31 (4OCH2),
105.00, 110.93, 115.46, 130.08, 149.53, 157.90 (C, CH)), 161.70,
163.32 (4C O, ester). IR (neat, nmax, cm-1): 1722, 1640, 1585,
1253, 1190. Elemental analysis for C18H18O10: Calc. C, 54.83; H,
4.60. Found: C, 54.85; H, 4.62. EIMS: m/z 450.1 (M+).
Diethyl-(Z)-2-(phenylmethylamino)-2-butenedioate
(2n).
◦
1
White solid. mp 66–68 C. H NMR (400 MHz, CDCl3): d
1.09 (t, 3H, J = 7.2 Hz, CH3), 1.24 (t, 3H, J = 7.2 Hz, CH3),
3.23 (s, 3H, CH3), 4.01 (2q, 4H, J = 7.2 Hz, 2OCH2), 4.81 (s,
1H, HC C), 7.21–7.38 (m, 5H, Ar–H). 13C NMR (100 MHz,
CDCl3): d 13.62, 14.39, 40.83 (3CH3), 59.47, 61.75 (2OCH2),
88.50 ( CH), 126.82, 127.38, 129.36 (5CH-Ar), 144.65, 154.16
(2C), 164.75, 167.31 (2C O, ester). IR (KBr, nmax, cm-1): 1740,
1453, 1201, 1171. Elemental analysis for C15H19NO4: Calc. C,
64.07; H, 6.91; N, 5.05. Found: C, 64.00; H, 6.83; N, 5.11.
EIMS: m/z 277.1 (M+).
(Z)-Methyl 3-phenoxyacrylate (5a). Colorless oil. 1H NMR
(400 MHz, CDCl3): d 3.79 (s, 3H, OCH3), 5.18 (d, 2H, J = 6.8 Hz,
HC C), 6.90 (d, 2H, J = 7.2 Hz, HC C), 7.11–7.40 (m, 5H,
Ar–H). 13C NMR (100 MHz, CDCl3): d 51.86 (CH3), 100.11,
115.36, 117.64, 124.71, 129.53, 129.85, 154.15, 157.16 (CH, C),
164.83 (C O, ester). IR (KBr, nmax, cm-1): 1729, 1630, 1450,
1212, 1154. Elemental analysis for C10H10O3: Calc. C, 67.41; H,
5.66. Found: C, 67.25; H, 5.56. EIMS: m/z 178.1 (M+).
(Z)-Methyl 3-(4-chlorophenoxy)acrylate (5b). Colorless oil.
1H NMR (400 MHz, CDCl3): d 3.78 (s, 3H, OCH3), 5.23 (d,
2H, J = 6.8 Hz, HC C), 6.85 (d, 2H, J = 7.2 Hz, HC C),
7.03 (d, 2H, J = 9.2 Hz, Ar–H), 7.16 (d, 2H, J = 8.8 Hz, Ar–
H). 13C NMR (100 MHz, CDCl3): d 51.58 (CH3), 99.94, 116.74,
118.94, 129.37, 129.90, 154.24, 154.75, 155.46 (CH, C), 165.76
(C O, ester). IR (KBr, nmax, cm-1): 1731, 1652, 1423, 1244,
1121. Elemental analysis for C10H9ClO3: Calc. C, 56.49; H, 4.27.
Found: C, 56.38; H, 4.15. EIMS: m/z 212.6 (M+).
Diethyl-(Z)-2-(morpholino)-2-butenedioate (2o). Yellow oil.
1H NMR (400 MHz, CDCl3): d 1.21 (t, 3H, J = 7.2 Hz, CH3),
1.35 (t, 3H, J = 7.2 Hz, CH3), 3.12 (t, 4H, J = 4.8 Hz, 2NCH2),
3.72 (t, 4H, J = 4.8 Hz, 2OCH2), 4.09 (q, 2H, J = 7.2 Hz,
CH2), 4.36 (q, 2H, J = 7.2 Hz, CH2), 4.77 (s, 1H, HC C). 13
C
NMR (100 MHz, CDCl3): d 13.90, 14.39 (2CH3), 47.04, 59.52,
62.23, 65.86 (4CH2), 87.67 ( CH), 154.69 ( C), 165.36, 167.21
(2C O, ester). IR (neat, nmax, cm-1): 1738, 1445, 1155, 1163.
Elemental analysis for C12H16NO5: Calc. C, 56.02; H, 7.44; N,
5.44. Found: C, 56.14; H, 7.5; N, 5.58. EIMS: m/z 243.1 (M+).
(Z)-Methyl 3-(2-formylphenoxy)acrylate (5c). White solid.
◦
1
mp 82–85 C. H NMR (400 MHz, CDCl3): d 3.79 (s, 3H,
OCH3), 5.34 (d, 2H, J = 6.8 Hz, HC C), 7.01 (d, 2H, J =
6.8 Hz, HC C), 7.14–7.96 (m, 4H, Ar–H), 10.58 (s, 1H, CHO).
13C NMR (100 MHz, CDCl3): d 51.45 (CH3), 101.82, 116.33,
124.86, 126.32, 128.60, 135.93, 151.99, 158.65 (CH, C), 164.70
(C O, ester), 188.83 (CHO). IR (KBr, nmax, cm-1): 2824, 1739,
1,4-Bis(dimethyl ◦(Z)-2-butenedioatoxy)benzene (4a). White
solid. mp 142–144 C. 1H NMR (400 MHz, CDCl3): d 3.73 (s,
6H, 2OCH3), 3.75 (s, 6H, 2OCH3), 6.56 (s, 2H, 2 HC C), 6.92
(s, 4H, Ar–H). 13C NMR (100 MHz, CDCl3): d 52.02, 53.04
2856 | Green Chem., 2011, 13, 2851–2858
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1720, 1644, 12251, 1161. Elemental analysis for C11H10O4: Calc.
C, 64.07; H, 4.89. Found: C, 64.19; H, 5.01. EIMS: m/z 206.1
(M+).
H, 9.35; N, 7.64. Found: C, 65.47; H, 9.28; N, 7.60. EIMS: m/z
183.2 (M+).
Di-tert-butyl 2-(phenoxy)-2-butenedioate. Colorless oil.
Mixture of Z:E isomer = 90 : 10; 1H NMR (400 MHz, CDCl3):
d 1.34 (s, 9H, 3CH3), 1.42 (s, 9H, 3CH3), 1.46 (s, 9H, 3CH3),
1.53 (s, 9H, 3CH3), 5.14 (s, 1H, HC C), 6.43 (s, 1H, HC C),
6.95–7.42 (m, Ar–H). 13C NMR (100 MHz, CDCl3): d 27.63,
27.99, 81.64, 83.22, 101.81, 116.02, 116.21, 120.75, 123.01,
125.71, 129.44, 129.91, 150.15, 156.86, 161.34, 163.15. IR (KBr,
(Z)-Methyl 3-(phenylthio)acrylate (5d). Colorless oil. 1H
NMR (400 MHz, CDCl3): d 3.79 (s, 3H, OCH3), 5.93 (d, 2H,
J = 10 Hz, HC C), 7.29 (d, 2H, J = 10.4 Hz, HC C), 7.34–
7.51 (m, 5H, Ar–H). 13C NMR (100 MHz, CDCl3): d 51.46
(CH3), 112.19, 128.29, 129.39, 131.12, 136.04, 150.16 (CH, C),
166.96 (C O, ester). IR (KBr, nmax, cm-1): 1734, 1638, 1457,
1206, 1116. Elemental analysis for C10H10O2S: Calc. C, 61.83;
H, 5.19. Found: C, 61.77; H, 5.27. EIMS: m/z 194.2 (M+).
n
max, cm-1): 1751, 1632, 1445, 1225, 1129. Elemental analysis
for C18H24O5: Calc. C, 67.48; H, 7.55. Found: C, 67.59; H, 7.61.
EIMS: m/z 320.3 (M+).
(Z)-Methyl 3-(cyclohexylthio)acrylate (5e). Colorless oil. 1H
NMR (400 MHz, CDCl3): d 1.26–2.03 (m, 10H, CH2), 2.83
(tt, 1H, J = 10.8 Hz, J = 4 Hz, CH), 3.72 (s, 3H, OCH3),
5.83 (d, 2H, J = 10.4 Hz, HC C), 7.18 (d, 2H, J = 10.4 Hz,
HC C). 13C NMR (100 MHz, CDCl3): d 25.37, 25.82, 33.55,
47.56(CH, CH2), 51.18(OCH3), 112.12, 148.73(2 CH), 167.11
(C O, ester). IR (KBr, nmax, cm-1): 1731, 1652, 1465, 1222,
1119. Elemental analysis for C10H16O2S: Calc. C, 59.96; H, 8.05.
Found: C, 60.06; H, 8.18. EIMS: m/z 200.3 (M+).
Acknowledgements
We are grateful for the financial support of the University of
Mazandaran, Islamic Republic of Iran.
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