Green and Sustainable Chemistry, 2011, 1, 132-148
doi:10.4236/gsc.2011.14022 Published Online November 2011 (http://www.SciRP.org/journal/gsc)
Poly Ethylene Glycols as Efficient Media for the Synthesis
of β-Nitro Styrenes from α, β-Unsaturated Carboxylic
Acids and Metal Nitrates under Conventional and
Non-Conventional Conditions
Kamatala Chinna Rajanna1, Kola Ramesh2, Soma Ramgopal1, Som ann agari Shylaja2,
Pochampally Giridhar Reddy2, Pondichery Kuppuswamy Saiprakash1
1Department of Chemistry, Osmania University, Hyderabad, India
2Department of Chemistry, CBIT, Gandipet, Hyderabad, India
Received August 18, 2011; revised October 14, 2011; accepted October 26, 2011
Abstract
Poly ethylene glycols (PEG-200, 400, 600, 4000 and 6000) supported reactions were conducted with certain
α, β-unsaturated acids in presence of metal nitrates under solvent free (solid state) and mineral acid free con-
ditions. The reactants were ground in a mortar with a pestle for about 30 minutes. The aromatic acids under-
went nitro decarboxylation and afforded β-nitro styrene derivatives in very good yield while α, β-unsaturated
aliphatic carboxylic acids gave corresponding nitro derivatives. Addition of PEG accelerated rate of the reac-
tion enormously. Reaction times substantially decreased from several hours to few minutes followed by
highly significant increase in the product yield. Among the several PEGs PEG-300 has been found to be
much more effective than other PEGs.
Keywords: Poly Ethylene Glycols (PEG), Rate Accelerations, α, β-Unsaturated Acids, Metal Nitrates,
Solvent Free (Solid State), β-Nitro Styrene Derivatives, α, β-Unsaturated Aliphatic Acids,
Nitro Derivatives
1. Introduction
The use of non volatile solvents is an essential ingredient
in a large number of organic synthesis protocols, which
may be toxic, hazardous and also cause environmental
pollution. Therefore the use of environmentally safe and
non-toxic solvents and more specifically removal of or-
ganic solvents in chemical synthesis are important in the
drive towards benign chemical technologies. Solvent-free
organic reactions make synthesis simpler, save energy,
and prevent solvent wastes, hazards, and toxicity. The
development of solvent-free organic synthetic methods
has thus become an important and popular research area.
Reports on solvent-free reactions between solids, gases
and solids, solids and liquid, between liquids, and on
solid inorganic supports have become increasingly fre-
quent in recent years. A mortar and pestle is a tool used
to crush, grind, and mix solid substances. Solvent less
preparation of organic compounds in the solid state and
via microwave irradiation has been the subject of interest
for the past one decade which has the advantage of being
eco-friendly, easy to handle, employ shorter reaction times
and solvent less conditions. Reactions performed under
solvent-free conditions have gained much attention be-
cause of their enhanced selectivity, mild reaction con-
ditions and associated ease of manipulation. The recent
reviews and publications [1-6] in this field prove the
importance of solvent free organic synthesis and high-
lights that, this process is not only simple but also satis-
fies both economical and environmental demands by
replacing the toxic solvents. Since more than a decade
our group is also actively working on exploiting the use
of a variety of eco friendly materials such as metal ions
and surfactants as catalysts and non-conventional energy
sources (such as microwave and ultra sound) to assist
organic transformations such as Vilsmeier-Haack [7-9],
Hunsdiecker [10] and nitration reactions [11-13]. The
classical Hunsdiecker-Borodin reaction [14,15] is an im-

133 K. C. RAJANNA ET AL.
portant halo decarboxylation reaction, which is used for
the synthesis of β-halo styrenes from α, β-unsaturated
Cinnamic acid. This reaction has been modified by seve-
ral workers with a view to overcome the toxicity factors
arising from the use of molecular bromine and metal salt
catalysts [16-25]. The use of solid acid catalysis has been
found potentially more attractive because of the ease of
removal and recycling of the catalyst and the possibility
that the solid might influence the selectivity. In one of
the recent reports Das and coworkers [26] reported that
nitro styrenes can be achieved from α, β-unsaturated
carboxylic acids using nitric acid (3 equiv) and catalytic
amount of AIBN (2 mol%) in acetonitrile medium. In
another report Rao et al. [27] enlightened the use of ceric
ammonium nitrate (CAN) in nitro Hunsdiecker-Borodin
reactions. Recently we have concentrated on developing
new methodologies using non-conventional energy sou-
rces and eco-friendly materials as catalysts in organic
transformations, and reported a methodology in metal
ion mediated nitration of organic compounds in presence
of small amount of HNO3 under solvent free (solid state)
conditions [28]. Polyethylene glycol (PEG-400) is a bio-
logically acceptable inexpensive polymer and an eco-
friendly reagent [29], which is widely used in many or-
ganic reactions for conversion of oxiranes to thiiranes
[30], asymmetric aldol reactions [31], cross-coupling rea-
ctions [18], Baylis-Hillman reaction [32,33] and ring o-
pening of epoxides [34]. Encouraged by these results, we
want to explore, the use of Polyethylene glycols (PEGs)
as efficient catalyst in this study. We have studied PEG
triggered Hunsdiecker-Borodin reactions for the synthe-
sis of β-nitro styrenes from α, β-unsaturated carboxylic
acids under conventional and non-conventional (solvent
free mortar-pestle and microwave) conditions.
2. Experimental Details
Cinnamic acid, metal nitrates, nitric acid and polyethyle-
ne glycols were obtained from SD Fine Chemicals or
Loba. Substituted Cinnamic acid were prepared by Per-
kins reaction as cited in literature [35].
2.1. General Procedure for PEG Mediated
Synthesis of β-Nitro Styrenes in MeCN
Medium
In a typical solid state synthesis, Cinnamic acid (0.01
mol), PEG (0.02 mmol) and metal nitrate (0.12 mmol)
are placed in a clean two necked R. B. flask and stirred
for certain time. Ground with a pestle for about 30 to 60
minutes until the mixture is homogeneous and particles
are no longer getting smaller. Progress of the reaction is
periodically monitored by TLC. After completion, the
reaction mixture is treated with 2% sodium carbonate
solution, followed by the addition dichloro methane
(DCM) or dichloro ethane (DCE). The organic layer
was separated, dried over Na2SO4 and the solvent is
recollected by distillation using Rotavapor. The resul-
tant compound is further purified with column chroma-
togram-phy using ethyl acetate: hexane (3:7) as eluent
to get pure product. Hexane and ethyl acetate are also
separated using Rotavapor according to standard pro-
cedures [35-37].
2.2. General Procedure for the Synthesis of
β-Nitro Styrenes in Acetonitrile Medium
under Continuously Stirred Conditions
In a typical synthesis, Cinnamic acid (0.01 mol), PEG
(0.02 mmol) and metal nitrate (0.12 mmol) are placed in
a clean mortar and ground with a pestle for about 30 to
60 minutes until the mixture is homogeneous, the parti-
cles are no longer getting smaller. Progress of the reac-
tion is periodically monitored by TLC. After completion,
the reaction mixture is treated with 2% sodium bicarbo-
nate solution, followed by the addition dichloro methane
(DCM) or dichloro ethane (DCE). The organic layer was
further treated in a similar manner discussed in the ear-
lier section to get pure product.
2.3. General Procedure for the Synthesis of
β-Nitro Styrenes under Microwave
Irradiated Conditions
Cinnamic acid (0.01 mol), PEG (0.02 mmol) and metal
nitrate (0.12 mmol) were dissolved in minimum amount
of MeCN, and mixed with silica gel (10 g) and the mix-
ture was transfered into a test tube and subjected to mi-
crowave irradiation (BPL make, BMO 700T, 650 W,
power 80%) for a specified period. Reaction was moni-
tored by TLC (hexane-ethyl acetate, 7:3). After comple-
tion of the reaction, products are isolated as discussed in
the above section.
2.4. General Procedure for the Synthesis of
β-Nitro Styrenes under Solvent-Free
Conditions
A mortar was charged with Cinnamic acid (0.01 mol),
PEG (0.02 mmol) and metal nitrate (0.12 mmol). The
mixture was ground at room temperature with a pestle
until TLC showed complete disappearance of the starting
material. After completion, the reaction mixture is trea-
ted with 2% sodium bicarbonate solution, followed by
addition of dichloro methane (DCM) or dichloro ethane

K. C. RAJANNA ET AL.
134
(DCE). The organic layer was further treated in a similar
manner discussed in the earlier section to get pure product.
3. Results and Discussion
The α, β-unsaturated aromatic carboxylic acids such as
Cinnamic acid afforded β-nitro styrenes when they are
taken along with PEG in presence of metal nitrates in a
mortar and ground with a pestle for about half a hour.
The reactions afforded good yield of products with high
regio selectivity. The yields of major products are com-
piled in Tables 1-3. The products were characterized by
Table 1. NMR and Mass Sp ectral data for selected reaction produ cts.
Spectral data
Entry Substrate Product m/z 1HNMR
1 CA β–Nitro Styrene 149 δ 6.4 (d 1H, β-CH), δ 7.3 - 7.65 (m 5H, Ar-H) δ 7.8(d 1H, α-CH)
2 4-ClCA 4-Chloro β–Nitro Styrene 184 δ 6.6 (d 1H, β-CH) δ 7.2 (d 2H, Ar-H) δ 7.6 (d 2H, Ar-H) δ 8.3 (d 1H, α-CH)
3 4-OMeCA 4-Methoxy β–Nitro Styrene 179 δ 3.8 (s 3H, OCH3) δ 6.4 (d 1H, β-CH) δ 7.32 - 7.7 (m 4H, Ar-H) δ 7.9 (d 1H, α-CH)
4 4-MeCA 4-Methyl β–Nitro Styrene 163 δ 3.0 (s 3H, CH3) δ 6.6 (d 1H, , β-CH) δ 7.4 - 7.7 (m 4H, Ar-H δ 7.9 (d 1H, α-CH)
5 4-NO2CA 4-Nitro β–Nitro Styrene 194 δ 6.6 (d 1H, β-CH) δ 7.4 (d 2H, Ar-H) δ 7.8 (d 2H, Ar-H) δ8.2 (s 1H, α-CH)
6 4-OHCA 4-Hydroxy β–Nitro Styrene 165 δ 6.5 (d 1H, β-CH) δ 7.3 (d 2H, Ar-H) δ 7.8 (d 2H, Ar-H) δ 8.1 (d 1H, α-CH)
δ 10.5 (s 1H, Ar-OH)
7 AA 1–Nitro Ethene 73 δ 5.92 (d 1H, β-CH) δ 6.6 (d 1H, trans β-CH) δ 7.25 (q 1H, α-CH)
8 CRA 1–Nitro Propene 87 δ 2.12 (d 3H, CH3) δ 7.0 (d 1H, α-CH) δ 7.15 (m 1H, β-CH )
9 3-PhCRA 3- Phenyl 1–Nitro Propene 163 δ 3.3 (d 2H, CH2) δ 7.23 - 7.33 (m 5H, Ar-H) δ 8.2 (d 1H, α-C-H)
10 2-ClCA 2-Chloro β–Nitro Styrene 183 δ 6.6 (d 1H, β-CH) δ 7.3 - 7.7 (m 4H, Ar-H) δ 8.2 (d 1H, α- C-H)
11 2-MeCA 2-Methyl β–Nitro Styrene 163 δ 2.9 (s 3H, CH3) δ 6.7 (d 1H, β-CH) δ 7.1 - 7.8 (m 4H, Ar-H) δ 8.2 (d 1H, α-CH)
Table 2. Effect of different PEGs on nitro Hunsdiecker reactions (Solution phase) with Cinnamic acid.
PEG-200 PEG-300 PEG-400 PEG-600 PEG-4000 PEG-6000
S.No Metal
Nitrate RT
(hrs) Yield (%) RT (hrs) Yield (%) RT (hrs) Yield (%) RT (hrs) Yield (%) RT (hrs) Yield (%) RT (hrs) Yield (%)
1 Ni(NO3)2 1.75 75 1.75 88 1.75 85 1.75 80 2.75 85 2.75 81
2 Zn(NO3)2 1.75 80 1.75 85 1.75 86 1.75 85 2.75 87 2.75 86
3 ZrO(NO3)2 1.75 75 1.75 85 1.75 88 1.75 87 2.75 82 2.75 82
4 Cd(NO3)2 1.75 80 1.75 85 1.75 84 1.75 86 2.75 84 2.75 84
5 Hg(NO3)2 1.75 80 1.75 85 1.75 82 1.75 85 2.75 78 2.75 70
6 Mg(NO3)2 1.75 85 1.75 90 1.75 87 1.75 88 2.75 85 2.75 86
7 Sr(NO3)2 1.75 88 1.75 90 1.75 92 1.75 94 2.75 88 2.75 90
8 Al(NO3)2 1.75 83 1.75 89 1.75 85 1.75 86 2.75 83 2.75 83
9 UO2(NO3)2 1.75 88 1.75 90 1.75 90 1.75 91 2.75 88 2.75 89
10 Th(NO3)2 1.75 88 1.75 88 1.75 86 1.75 90 2.75 85 2.75 90
11 AgNO3 1.75 70 1.75 80 1.75 80 1.75 86 2.75 78 2.75 80
12 NH4(NO3)2 1.75 75 1.75 80 1.75 80 1.75 78 2.75 75 2.75 75
13 Ca(NO3)2 1.75 80 1.75 85 1.75 84 1.75 86 2.75 84 2.75 84

135 K. C. RAJANNA ET AL.
Table 3. Effect of different PEGs on (Solvent free-Mortar Pestle) nitro Hunsdiecker reactions with Cinnamic acid.
PEG-200 PEG-300 PEG-400 PEG-600 PEG-4000 PEG-6000
S. No Metal
Nitrate RT
(hrs) Yield (%) RT (hrs) Yield (%)
RT
(hrs) Yield (%)
RT
(hrs) Yield (%) RT (hrs) Yield (%) RT (hrs) Yield (%)
1 Ni(NO3)2 30 80 30 90 30 83 30 85 60 75 60 78
2 ZrO(NO3)2 30 85 30 88 30 86 30 88 60 80 60 76
3 Cd(NO3)2 30 82 30 85 30 85 30 87 60 85 60 75
4 Ca(NO3)2 30 81 30 86 30 84 30 86 60 78 60 80
5 Hg(NO3)2 30 79 30 89 30 85 30 84 60 78 60 75
6 Mg(NO3)2 30 90 30 95 30 90 30 90 60 85 60 86
7 Sr(NO3)2 30 85 30 92 30 90 30 94 60 88 60 90
8 Al(NO3)2 30 90 30 90 30 87 30 89 60 83 60 83
9 Th(NO3)2 30 88 30 90 30 90 30 91 60 88 60 89
10 UO2(NO3)2 30 85 30 90 30 88 30 90 60 85 60 90
11 Ag NO3 30 70 30 80 30 75 30 78 60 75 60 80
12 NH4(NO3)2 30 75 30 85 30 80 30 80 60 75 60 75
13 Zn(NO3)2 30 72 30 83 30 80 30 78 60 78 60 84
IR, 1H-NMR, Mass spectra and physical data with authen-
tic samples and found to agree well with earlier reports
[26-28]. Here we used simple mortar and pestle for grind-
ing purpose to complete the reaction [28]. Grinding, mill-
ing, shearing, scratching and polishing provide mechanical
impact for mechanical breakage of intramolecular bonds by
external force and must be differentiated from molecular
solid-state chemistry. Further, it appears clearly that in
mortar pestle reactions mechanical energy is converted to
thermal energy which is utilized to break intramolecular
chemical bonds to causing chemical change [38].
3.1. Effect of Structure on Reactivity
To check the generality of the reaction an array of sub-
stituted Cinnamic acid and metal nitrates are used under
varied reaction conditions, as shown in Schemes 1 and 2.
In order to have a closer look into the effect of structural
variation on nitro decarboxylation the study has been
taken up extensively the following variable (in solution
phase and under solvent-free) conditions:
Scheme 1. Decarboxylative nitration of α, β-unsaturated acid
under Microwave irradiation. Metal Nitrate = Mg(NO3)2,
Sr(NO3)2, Al(NO3)3, Ca(NO3)2, Ni(NO3)2, Cd(NO3)2, Zn(NO3)2,
Hg(NO3)2, AgNO3, ZrO(NO3)2, UO2(NO3)2, Th (NO3)2, NH4NO3;
PEG = PEG-200, 300, 400, 600, 4000 and 6000.
Scheme 2. Decarboxylative nitration of α, β-unsaturated acid
under Solvent-free conditions (Grinding). Metal Nitrate =
Mg(NO3)2, Sr(NO3)2, Al(NO3)3, Ca(NO3)2, Ni(NO3)2, Cd(NO3)2,
Zn(NO3)2, Hg(NO3)2, AgNO3, ZrO(NO 3)2, UO2(NO3)2, Th(N O3)2,
NH4NO3; PEG = PEG-200, 300, 400, 600, 4000 and 6000.
1) Different α, β-unsaturated aromatic and aliphatic
carboxylic acids.
2) Different metal nitrates belonging to s-block, p-block,
d-block and f-block (Mg(NO3)2, Sr(NO3)2, Al(NO3)3,
Ca(NO3)2, Ni(NO3)2, Cd(NO3)2, Zn(NO3)2, Hg(NO3)2,
AgNO3, ZrO(NO3)2, UO2(NO3)2, Th(NO3)2 , NH4NO3.
3) Different Poly ethylene glycols (PEG-200, 300, 400,
600, 4000 and 6000).
Data presented in Tables 2-4 and Tables 5-22 of elec-
tronic supplementary data) indicate the reaction times
and yield of reaction products under different conditions,
which revealed that the reaction is sensitive to the struc-
tural variation of Cinnamic acid, PEGs and also the na-
ture of metal nitrate. Reaction rates accelerated with the
introduction of electron donating groups and retarded
with electron withdrawing groups. In order to have clari-
ty, kinetic data for Cinnamic acid conversion are sepa-
rately shown in Tables 5-7 and Figures 1 and 2. Figure
1 depicts that addition of PEG gradually decreases the
reaction times (RT) gradually with an increase in the mo-
lecular weight of PEG. Among the several PEGs,

K. C. RAJANNA ET AL.
136
Table 4. Effect of different PEGs on microwave irradiated nitro Hunsdiecker reactions with Cinnamic acid.
PEG-200 PEG-300 PEG-400 PEG-600 PEG-4000 PEG-6000
S. No Metal
Nitrate RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs) Yield (%)
RT
(hrs) Yield (%) RT (hrs) Yield (%) RT (hrs) Yield (%)
1 Ni(NO3)2 180 70 90 86 90 82 90 84 180 80 180 82
2 Zn(NO3)2 180 77 90 89 90 84 90 85 180 82 180 80
3 ZrO(NO3)2 180 77 90 86 90 83 90 84 180 85 180 84
4 Cd(NO3)2 180 78 90 84 90 85 90 85 180 80 180 82
5 Hg(NO3)2 180 74 90 82 90 82 90 80 180 78 180 82
6 Mg(NO3)2 180 82 90 88 90 85 90 86 180 80 180 85
7 Sr(NO3)2 180 83 90 90 90 88 90 86 180 82 180 84
8 Al(NO3)2 180 80 90 86 90 82 90 84 180 82 180 84
9 UO2(NO3)2 180 84 90 86 90 85 90 90 180 85 180 86
10 Th(NO3)2 180 83 90 90 90 88 90 86 180 85 180 86
11 AgNO3 180 62 90 76 90 70 90 74 180 78 180 80
12 NH4(NO3)2 180 75 90 80 90 80 90 80 180 80 180 80
13 Ca(NO3)2 180 78 90 82 90 80 90 82 180 76 180 78
Table 5. Nitro decarboxylation of Cinnamic acid in presence of PEG-200 and metal nitrates under Solution phase.
Entry 1a 1b 1c 1d 1e 1f 1g 1h 1i 1j 1k
Substrate CA 4-ClCA 4-OMeCA 4-MeCA4-NO2CA4-OHCAAACRA 3-PhCRA 2-ClCA2-MeCA
Ni(NO3)2 Zn(NO3)2 ZrO(NO3)2 Cd(NO3)2 Hg(NO3)2Mg(NO3)2Sr(NO3)2Al(NO3)3UO2(NO3)2 Th (NO3)2 AgNO3NH4NO3
Entry RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
1a 1.75 70 1.75 75 1.75 72 1.75 71 1.75 69 1.7585 1.75 88 1.75 83 1.7588 1.75 88 1.75 601.7575
1b 2.00 66 2.00 69 2.00 68 2.00 62 2.00672.00 78 2.00 822.00 852.00 902.00 88 2.00 622.0077
1c 1.50 74 1.50 82 1.50 76 1.50 76 1.50 80 1.5087 1.50 88 1.50 85 1.5088 1.50 89 1.50 651.5070
1d 1.50 78 1.50 75 1.50 76 1.50 70 1.50771.50 83 1.50 861.50 851.50 841.50 83 1.50 621.5068
1e 2.00 64 2.00 62 2.00 70 2.00 62 2.00 75 2.0078 2.00 81 2.00 78 2.0080 2.00 80 2.00 602.0066
1f 1.50 85 1.50 80 1.50 88 1.50 78 1.50761.50 77 1.50 851.5087 1.50861.50 90 1.50 601.5068
1g 1.50 66 1.50 62 1.50 65 1.50 64 1.50611.50 76 1.5073 1.5080 1.5080 1.50 80 1.50 631.5068
1h 2.00 67 2.00 69 2.00 68 2.00 68 2.00682.00 78 2.00 772.00 782.00 762.00 78 2.00 642.0069
1i 1.50 62 1.50 64 1.50 64 1.50 65 1.50 661.5079 1.50 821.50 771.50 741.50 80 1.50 641.5061
1j 2.00 66 2.00 62 2.00 61 2.00 64 2.00 652.0068 2.00 732.00 692.00 662.00 66 2.00 602.0070
1k 1.50 74 1.50 71 1.50 74 1.50 71 1.50711.50 74 1.50 741.50 741.50 701.50 74 1.50 671.5075

137 K. C. RAJANNA ET AL.
Table 6. Nitro decarboxylation of Cinnamic acid in presence of PEG-300 and metal nitrates under Solution phase.
Entry 1a 1b 1c 1d 1e 1f 1g 1h 1i 1j 1k
Substrate CA 4-ClCA 4-OMeCA 4-MeCA4-NO2CA4-OHCAAACRA 3-PhCRA 2-ClCA2-MeCA
Ni(NO3)2 Zn(NO3)2 ZrO(NO3)2 Cd(NO3)2 Hg(NO3)2Mg(NO3)2Sr(NO3)2Al(NO3)3UO2(NO3)2 Th (NO3)2 AgNO3NH4NO3
Entry RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
1a 1.75 71 1.75 75 1.75 83 1.75 72 1.75 701.75 851.75 901.75 851.75 88 1.75 87 1.75 63 1.7574
1b 2.00 68 2.00 70 2.00 70 2.00 75 2.00 682.00782.00842.0087 2.00902.00 89 2.00 642.0078
1c 1.50 75 1.50 83 1.50 76 1.50 78 1.50 811.50 861.50 901.50 871.50 88 1.50 92 1.50 68 1.5072
1d 1.50 80 1.50 76 1.50 76 1.50 72 1.50 78 1.50851.50881.5087 1.50841.50 85 1.50 651.5067
1e 2.00 67 2.00 84 2.00 71 2.00 65 2.00 762.00 802.00 822.00 78 2.0080 2.00 82 2.00 63 2.0068
1f 1.50 87 1.50 82 1.50 88 1.50 79 1.50 77 1.5088 1.5087 1.5087 1.50861.50 92 1.50 631.5070
1g 1.50 68 1.50 65 1.50 67 1.50 66 1.5063 1.50761.50751.5082 1.50821.50 82 1.50 661.5070
1h 2.00 70 2.00 72 2.00 70 2.00 70 2.0070 2.00802.00782.0080 2.00782.00 80 2.00 672.0071
1i 1.50 65 1.50 66 1.50 66 1.50 67 1.5068 1.5080 1.50831.5078 1.5075 1.50 82 1.50 67 1.5063
1j 2.00 71 2.00 64 2.00 63 2.00 66 2.0067 2.0070 2.00732.0070 2.00682.00 68 2.00 622.0072
1k 1.50 78 1.50 72 1.50 77 1.50 72 1.5072 1.50771.50781.5078 1.50721.50 78 1.50 681.5077
Table 7. Nitro decarboxylation of Cinnamic acid in presence of PEG-400 and metal nitrates under Solution phase.
Entry 1a 1b 1c 1d 1e 1f 1g 1h 1i 1j 1k
Substrate CA 4-ClCA 4-OMeCA 4-MeCA4-NO2CA4-OHCAAACRA 3-PhCRA 2-ClCA2-MeCA
Ni(NO3)2 Zn(NO3)2 ZrO(NO3)2 Cd(NO3)2 Hg(NO3)2Mg(NO3)2Sr(NO3)2Al(NO3)3UO2(NO3)2 Th (NO3)2 AgNO3NH4NO3
Entry RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
1a 1.75 73 1.75 76 1.75 75 1.75 74 1.7572 1.75871.75 92 1.7587 1.75901.75 88 1.75 651.7576
1b 2.00 70 2.00 72 2.00 72 2.00 68 2.00 70 2.00802.00 882.00 89 2.00 92 2.00 91 2.00 67 2.0080
1c 1.50 77 1.50 85 1.50 78 1.50 82 1.5084 1.50881.5091 1.5089 1.50901.50 93 1.50 70 1.5074
1d 1.50 83 1.50 78 1.50 79 1.50 76 1.50 80 1.50871.50 881.50 89 1.50 86 1.50 88 1.50 67 1.5070
1e 2.00 69 2.00 66 2.00 74 2.00 68 2.0079 2.00832.00 84 2.0080 2.00822.00 84 2.00 642.0070
1f 1.50 88 1.50 85 1.50 91 1.50 83 1.50 80 1.50901.50 911.50 89 1.50 88 1.50 94 1.50 64 1.5072
1g 1.50 70 1.50 68 1.50 69 1.50 70 1.50651.50 78 1.5078 1.5084 1.50851.50 85 1.50 67 1.5072
1h 2.00 73 2.00 75 2.00 73 2.00 74 2.00 74 2.00732.00 802.00 82 2.00 81 2.00 82 2.00 69 2.0073
1i 1.50 67 1.50 69 1.50 68 1.50 70 1.5072 1.50831.50 85 1.5080 1.50781.50 84 1.50 691.5065
1j 2.00 74 2.00 67 2.00 75 2.00 68 2.0071 2.00732.00 75 2.0072 2.00692.00 70 2.00 632.0074
1k 1.50 80 1.50 74 1.50 78 1.50 74 1.50 76 1.50781.50 781.50 80 1.50 74 1.50 78 1.50 70 1.5079

K. C. RAJANNA ET AL.
138
Table 8. Nitro decarboxylation of Cinnamic acid in presence of PEG-600 and metal nitrates under Solution phase.
Entry 1a 1b 1c 1d 1e 1f 1g 1h 1i 1j 1k
Substrate CA 4-ClCA 4-OMeCA 4-MeCA4-NO2CA4-OHCAAACRA 3-PhCRA 2-ClCA2-MeCA
Ni(NO3)2 Zn(NO3)2 ZrO(NO3)2 Cd(NO3)2 Hg(NO3)2Mg(NO3)2Sr(NO3)2Al(NO3)3UO2(NO3)2 Th (NO3)2 AgNO3NH4NO3
Entry RT Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(hrs) (%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
1a 1.75 75 1.75 78 1.75 77 1.75 76 1.7574 1.75 891.7594 1.7589 1.75911.75 90 1.75 66 1.7578
1b 2.00 72 2.00 75 2.00 76 2.00 70 2.00 72 2.00832.00 90 2.00 92 2.00 93 2.00 93 2.00 68 2.0082
1c 1.50 78 1.50 88 1.50 81 1.50 84 1.5087 1.50 911.5093 1.5092 1.50911.50 96 1.50 71 1.50 76
1d 1.50 85 1.50 80 1.50 82 1.50 79 1.50 84 1.50891.50 901.50 92 1.50 87 1.50 91 1.50 68 1.5071
1e 2.00 72 2.00 69 2.00 76 2.00 70 2.0083 2.00872.00 87 2.0082 2.00832.00 87 2.00 662.0071
1f 1.50 90 1.50 88 1.50 93 1.50 86 1.50 84 1.50931.50 931.50 92 1.50 89 1.50 96 1.50 66 1.5074
1g 1.50 73 1.50 71 1.50 72 1.50 72 1.50 68 1.50801.50 811.50 88 1.50 86 1.50 88 1.50 69 1.5075
1h 2.00 75 2.00 78 2.00 75 2.00 77 2.00 77 2.00872.00 832.00 86 2.00 82 2.00 86 2.00 70 2.0074
1i 1.50 69 1.50 73 1.50 71 1.50 73 1.50 751.50 87 1.50871.50 881.50 791.50 87 1.50 71 1.5067
1j 2.00 77 2.00 71 2.00 69 2.00 71 2.0074 2.00772.00 78 2.0080 2.00722.00 73 2.00 652.0076
1k 1.50 84 1.50 79 1.50 80 1.50 77 1.50 80 1.50801.50 811.50 82 1.50 77 1.50 81 1.50 73 1.5070
Table 9. Nitro decarboxylation of Cinnamic acid in presence of PEG-4000 and metal nitrates under Solution phase.
Entry 1a 1b 1c 1d 1e 1f 1g 1h 1i 1j 1k
Substrate CA 4-ClCA 4-OMeCA 4-MeCA4-NO2CA4-OHCAAACRA 3-PhCRA 2-ClCA2-MeCA
Ni(NO3)2 Zn(NO3)2 ZrO(NO3)2 Cd(NO3)2 Hg(NO3)2Mg(NO3)2Sr(NO3)2Al(NO3)3UO2(NO3)2 Th (NO3)2 AgNO3NH4NO3
Entry RT Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(hrs) (%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
1a 2.75 70 2.75 75 2.75 72 2.75 71 2.75692.75 85 2.7588 2.75832.75 88 2.75 8 2.75 60 2.7575
1b 3.00 66 3.00 70 3.00 68 3.00 62 3.0067 3.00783.0082 3.0085 3.00903.00 88 3.00 62 3.0077
1c 2.50 74 2.50 73 2.50 76 2.50 76 2.50802.50 87 2.5088 2.50852.50 88 2.50 89 2.50 65 2.5070
1d 2.50 78 2.50 74 2.50 76 2.50 70 2.5077 2.50832.5086 2.5085 2.50842.50 83 2.50 62 2.5068
1e 3.00 84 3.00 62 3.00 70 3.00 62 3.00753.00 78 3.0081 3.00783.00 80 3.00 80 3.00 60 3.0066
1f 2.50 85 2.50 60 2.50 88 2.50 78 2.5076 2.50872.50 85 2.50 87 2.5086 2.50 90 2.50 60 2.50 68
1g 2.50 66 2.50 63 2.50 65 2.50 64 2.5061 2.50 762.50 73 2.5080 2.50802.50 80 2.50 63 2.5068
1h 3.00 67 3.00 69 3.00 68 3.00 68 3.0068 3.00783.0077 3.0078 3.00763.00 78 3.00 64 3.0069
1i 2.50 62 2.50 64 2.50 64 2.50 65 2.50662.50 79 2.5082 2.50772.50 74 2.50 80 2.50 64 2.5061
1j 3.00 66 3.00 62 3.00 61 3.00 64 3.00653.00 68 3.0073 3.0069 3.00 663.00 66 3.00 60 3.0070
1k 2.50 74 2.50 71 2.50 74 2.50 71 2.5071 2.50742.5074 2.5074 2.50702.50 74 2.50 67 2.5075

139 K. C. RAJANNA ET AL.
Table 10. Nitro decarboxylation of Cinnamic acid in presence of PEG-6000 and metal nitrates under Solution phase.
Entry 1a 1b 1c 1d 1e 1f 1g 1h 1i 1j 1k
Substrate CA 4-ClCA 4-OMeCA 4-MeCA4-NO2CA4-OHCAAACRA 3-PhCRA 2-ClCA2-MeCA
Ni(NO3)2 Zn(NO3)2 ZrO(NO3)2 Cd(NO3)2 Hg(NO3)2Mg(NO3)2Sr(NO3)2Al(NO3)3UO2(NO3)2 Th (NO3)2 AgNO3NH4NO3
Entry RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
RT
(hrs)
Yield
(%)
1a 2.75 71 2.75 76 2.75 72 2.75 72 2.75 50 2.7586 2.7590 2.7583 2.7589 2.75 90 2.75 602.7575
1b 3.00 67 3.00 70 3.00 68 3.00 66 3.00 683.00 80 3.0084 3.0085 3.0091 3.00 90 3.00 623.0077
1c 2.50 75 2.50 73 2.50 76 2.50 78 2.50 80 2.50 89 2.50 90 2.50 85 2.50 81 2.50 81 2.50 65 2.5070
1d 2.50 79 2.50 75 2.50 77 2.50 72 2.50 782.50 85 2.5088 2.5085 2.5085 2.50 84 2.50 622.5088
1e 3.00 65 3.00 63 3.00 71 3.00 63 3.00 76 3.0080 3.0083 3.0078 3.0081 3.00 82 3.00 603.0066
1f 2.50 85 2.50 81 2.50 89 2.50 75 2.50 772.50 892.50 872.50 872.50 88 2.50 92 2.50 60 2.50 68
1g 2.50 66 2.50 64 2.50 86 2.50 65 2.50 632.50 78 2.5075 2.50 80 2.5082 2.50 84 2.50 632.5068
1h 3.00 67 3.00 69 3.00 69 3.00 69 3.00 703.00 80 3.0079 3.0078 3.0078 3.00 80 3.00 643.0069
1i 2.50 62 2.50 65 2.50 65 2.50 67 2.50 682.50 81 2.5083 2.5077 2.5076 2.50 82 2.50 642.5061
1j 3.00 66 3.00 63 3.00 62 3.00 66 3.00 663.00 70 3.0073 3.0069 3.0068 3.00 68 3.00 603.0070
1k 2.50 74 2.50 72 2.50 76 2.50 63 2.50 732.50 76 2.5074 2.5074 2.5072 2.50 76 2.50 672.5075
Table 11. Nitro decarboxylation of Cinnamic acid in presence of PEG-200 and metal nitrates under Solvent free conditions.
Entry 1a 1b 1c 1d 1e 1f 1g 1h 1i 1j 1k
Substrate CA 4-ClCA 4-OMeCA 4-MeCA4-NO2CA4-OHCAAACRA 3-PhCRA 2-ClCA2-MeCA
Ni(NO3)2 Zn(NO3)2 ZrO(NO3)2 Cd(NO3)2 Hg(NO3)2Mg(NO3)2Sr(NO3)2Al(NO3)3UO2(NO3)2 Th (NO3)2 AgNO3NH4NO3
Entry RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
1a 45 80 45 82 45 81 45 81 45 7845 85 45 86 45 83 4587 45 87 45 60 45 75
1b 60 76 60 75 60 72 60 77 60 7660 78 608060 85 6087 60 88 60 646074
1c 30 78 30 81 30 84 30 83 30 8230 86 30 84 30 84 3088 30 87 30 66 30 70
1d 30 80 30 78 30 84 30 82 30 8030 83 308230 85 3082 30 84 30 653068
1e 60 74 60 72 60 78 60 77 60 7860 79 60 78 60 78 6075 60 80 60 64 60 66
1f 30 88 30 84 30 90 30 90 30 8630 883085 30 87 30 8830 85 30 653068
1g 30 76 30 68 30 75 30 76 30 6930 76307030 81308030 80 30 663068
1h 60 74 60 70 60 78 60 83 60 7860 78 607560 80 6078 60 76 60 676070
1i 30 72 30 70 30 76 30 78 30 75 3079 30 80 30 78 30 7630 78 30 68 30 64
1j 60 78 60 68 60 68 60 76 60 76 6068 60 70 60 70 60 6560 66 60 66 60 72
1k 30 82 30 81 30 88 30 87 30 8430 76 307530 76 3073 30 76 30 783068

K. C. RAJANNA ET AL.
140
Table 12. Nitro decarboxylation of Cinnamic acid in presence of PEG-300 and metal nitrates under Solvent free conditions.
Entry 1a 1b 1c 1d 1e 1f 1g 1h 1i 1j 1k
Substrate CA 4-ClCA 4-OMeCA 4-MeCA4-NO2CA4-OHCAAACRA 3-PhCRA 2-ClCA2-MeCA
Ni(NO3)2 Zn(NO3)2 ZrO(NO3)2 Cd(NO3)2 Hg(NO3)2Mg(NO3)2Sr(NO3)2Al(NO3)3UO2(NO3)2 Th (NO3)2 AgNO3NH4NO3
Entry RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
1a 45 90 45 88 45 85 45 86 45 80 45 88 45 88 45 86 45 90 45 90 45 75 45 85
1b 60 86 60 80 60 76 60 80 60 7860 8360 8260 88 6088 60 88 60 74 6084
1c 30 88 30 86 30 88 30 88 30 84 30 87 30 85 30 86 30 88 30 86 30 78 30 80
1d 30 86 30 83 30 88 30 86 30 8230 8530 8430 88 3082 30 85 30 76 3078
1e 60 76 60 76 60 82 60 80 60 80 60 80 60 80 60 82 60 76 60 80 60 75 60 75
1f 30 92 30 90 30 90 30 90 30 88 30 8830 8630 90 30 8830 86 30 763078
1g 30 80 30 72 30 78 30 78 30 7130 7830 7230 84 3082 30 82 30 78 3076
1h 60 78 60 75 60 82 60 86 60 8060 7860 7660 84 6080 60 78 60 78 6078
1i 30 76 30 75 30 80 30 82 30 78 30 80 30 82 30 82 30 78 30 82 30 76 30 75
1j 60 82 60 72 60 72 60 76 60 78 60 70 60 72 60 77 60 70 60 65 60 76 60 76
1k 30 86 30 86 30 90 30 88 30 8630 7830 7630 80 3076 30 80 30 80 3080
Table 13. Nitro decarboxylation of Cinnamic acid in presence of PEG-400 and metal nitrates under Solvent free conditions.
Entry 1a 1b 1c 1d 1e 1f 1g 1h 1i 1j 1k
Substrate CA 4-ClCA 4-OMeCA 4-MeCA4-NO2CA4-OHCAAACRA 3-PhCRA 2-ClCA2-MeCA
Ni(NO3)2 Zn(NO3)2 ZrO(NO3)2 Cd(NO3)2 Hg(NO3)2Mg(NO3)2Sr(NO3)2Al(NO3)3UO2(NO3)2 Th (NO3)2 AgNO3NH4NO3
Entry RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
1a 45 84 45 85 45 82 45 84 45 85 45 86 45 90 45 84 45 90 45 88 45 70 45 80
1b 60 82 60 77 60 73 60 78 60 7860 8160 8060 86 6086 60 86 60 70 6080
1c 30 84 30 83 30 85 30 86 30 82 30 85 30 82 30 83 30 85 30 85 30 74 30 75
1d 30 82 30 80 30 84 30 84 30 8030 8230 8030 85 3080 30 82 30 72 3072
1e 60 72 60 73 60 80 60 78 60 82 60 78 60 82 60 80 60 72 60 78 60 70 60 70
1f 30 88 30 87 30 86 30 86 30 88 30 8630 8530 90 30 8630 83 30 723073
1g 30 76 30 70 30 75 30 76 30 7030 7630 7030 82 3080 30 80 30 73 3071
1h 60 75 60 72 60 80 60 84 60 8060 7560 7460 80 6078 60 76 60 74 6073
1i 30 72 30 72 30 78 30 80 30 78 30 78 30 80 30 80 30 76 30 80 30 72 30 70
1j 60 78 60 68 60 78 60 74 60 78 60 68 60 70 60 74 60 68 60 62 60 72 60 74
1k 30 82 30 82 30 88 30 85 30 8630 7630 7530 76 3074 30 78 30 76 3075

141 K. C. RAJANNA ET AL.
Table 14. Nitro decarboxylation of Cinnamic acid in presence of PEG-600 and metal nitrates under Solvent free conditions.
Entry 1a 1b 1c 1d 1e 1f 1g 1h 1i 1j 1k
Substrate CA 4-ClCA 4-OMeCA 4-MeCA4-NO2CA4-OHCAAACRA 3-PhCRA 2-ClCA2-MeCA
Ni(NO3)2 Zn(NO3)2 ZrO(NO3)2 Cd(NO3)2 Hg(NO3)2Mg(NO3)2Sr(NO3)2Al(NO3)3UO2(NO3)2 Th (NO3)2 AgNO3NH4NO3
Entry RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
1a 45 85 45 86 45 84 45 84 45 80 45 88 45 88 45 85 45 90 45 88 45 74 45 82
1b 60 83 60 78 60 74 60 78 60 7360 8260 7860 86 6084 60 85 60 72 6082
1c 30 85 30 84 30 84 30 84 30 78 30 84 30 80 30 84 30 86 30 84 30 75 30 76
1d 30 83 30 80 30 85 30 82 30 7530 8230 7830 86 3080 30 82 30 72 3074
1e 60 73 60 74 60 82 60 78 60 78 60 78 60 80 60 80 60 74 60 78 60 70 60 72
1f 30 88 30 86 30 86 30 86 30 85 30 8630 8230 90 30 8630 84 30 753075
1g 30 77 30 72 30 76 30 76 30 6830 7730 7030 82 3080 30 80 30 73 3072
1h 60 76 60 74 60 82 60 84 60 7560 7660 7260 82 6078 60 76 60 74 6073
1i 30 73 30 74 30 80 30 80 30 76 30 78 30 80 30 80 30 74 30 80 30 72 30 70
1j 60 78 60 68 60 78 60 76 60 76 60 70 60 72 60 75 60 68 60 64 60 74 60 74
1k 30 82 30 82 30 88 30 86 30 8430 7830 7430 76 3075 30 78 30 80 3076
Table 15. Nitro decarboxylation of Cinnamic acid in presence of PEG-4000 and metal nitrates under Solvent free conditions.
Entry 1a 1b 1c 1d 1e 1f 1g 1h 1i 1j 1k
Substrate CA 4-ClCA 4-OMeCA 4-MeCA4-NO2CA4-OHCAAACRA 3-PhCRA 2-ClCA2-MeCA
Ni(NO3)2 Zn(NO3)2 ZrO(NO3)2 Cd(NO3)2 Hg(NO3)2Mg(NO3)2Sr(NO3)2Al(NO3)3UO2(NO3)2 Th (NO3)2 AgNO3NH4NO3
Entry RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
1a 90 82 90 84 90 85 90 80 9078 90 82 90 84 90 83 90 86 90 85 90 75 9078
1b 120 81 120 76 120 74 120 74 1207112078 120 74 12084 120 80 120 82 120 73120 78
1c 60 82 60 82 60 83 60 80 6076 60 78 60 76 60 82 60 82 60 80 60 76 6072
1d 60 81 60 80 60 84 60 80 60 7560 7660756082607660 80 60 73 60 70
1e 120 70 120 72 120 82 120 74 120 76 120 70 120 76 120 78 120 70 120 72 120 71 120 68
1f 60 86 60 85 60 86 60 84 60 82608060796088 608260 80 60 76 6072
1g 60 74 60 70 60 75 60 76 60 686071606560 80607660 78 60 74 6070
1h 120 75 120 72 120 80 120 80 1207212070 120 78 12080 120 74 120 75 120 75120 71
1i 60 71 60 72 60 80 60 78 60 75 60 68 60 78 60 7860 70 60 78 60 73 60 70
1j 120 76 120 68 120 78 120 72 1207612065 120 68 12072 120 65 120 62 120 75120 75
1k 60 80 60 80 60 86 60 84 60 8260 7060706072607260 75 60 80 60 77

K. C. RAJANNA ET AL.
142
Table 16. Nitro decarboxylation of Cinnamic acid in presence of PEG-6000 and metal nitrates under Solvent free conditions.
Entry 1a 1b 1c 1d 1e 1f 1g 1h 1i 1j 1k
Substrate CA 4-ClCA 4-OMeCA 4-MeCA4-NO2CA4-OHCAAACRA 3-PhCRA 2-ClCA2-MeCA
Ni(NO3)2 Zn(NO3)2 ZrO(NO3)2 Cd(NO3)2 Hg(NO3)2Mg(NO3)2Sr(NO3)2Al(NO3)3UO2(NO3)2 Th (NO3)2 AgNO3NH4NO3
Entry RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
RT
(min)
Yield
(%)
1a 90 78 90 80 90 82 90 80 90 78 90 86 90 85 90 84 90 86 90 86 90 80 90 78
1b 120 77 120 72 120 71 120 74 120 7212080 120 74120 8412080 120 83 120 7812076
1c 60 78 60 80 60 80 60 82 60 76 60 80 60 76 60 82 60 82 60 82 60 78 60 74
1d 60 78 60 78 60 82 60 82 6074 60 78 6076 6080 6076 60 80 60 7660 72
1e 120 68 120 70 120 80 120 75 120 76 120 72 120 78 120 76 120 72 120 74 120 76 120 68
1f 60 85 60 82 60 83 60 84 6082 6082 60 8060 886082 60 81 60 78 6074
1g 60 72 60 68 60 72 60 75 6068 6075 60 66 608260 7660 78 60 75 6072
1h 120 72 120 70 120 78 120 80 120 7412072 120 78120 8212075 120 76 120 7612072
1i 60 68 60 70 60 78 60 78 60 76 60 70 60 80 60 78 60 72 60 78 60 76 60 74
1j 120 73 120 65 120 80 120 74 120 76 12068120 68120 74 12066120 64 120 7812076
1k 60 80 60 78 60 85 60 82 6082 60 72 6072 6076 6074 60 76 60 8060 78
Table 17. Nitro decarboxylation of Cinnamic acid in presence of PEG-200 and metal nitrates under microwave conditions.
Entry 1a 1b 1c 1d 1e 1f 1g 1h 1i 1j 1k
Substrate CA 4-ClCA 4-OMeCA 4-MeCA4-NO2CA4-OHCAAACRA 3-PhCRA 2-ClCA2-MeCA
Ni(NO3)2 Zn(NO3)2 ZrO(NO3)2 Cd(NO3)2 Hg(NO3)2Mg(NO3)2Sr(NO3)2Al(NO3)3UO2(NO3)2 Th (NO3)2 AgNO3NH4NO3
Entry RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
1a 180 70 180 77 180 77 180 78 180 74 180 82 18083 180 80 180 84 180 83 180 62 180 75
1b 180 66 180 70 180 68 180 73 180 72 180 7518077 180 82 180 84180 85 180 64 18074
1c 180 88 180 66 180 80 180 79 180 78 180 82 18081 180 81 180 85 180 82 180 66 180 70
1d 180 70 180 73 180 80 180 78 180 76 180 8018079 180 82 180 78180 81 180 65 18068
1e 180 64 180 67 180 74 180 73 180 74 180 75 18075 180 75 180 72 180 78 180 64 180 66
1f 120 78 120 80 120 86 120 85 120 82120 85 120 82 120 84120 85 120 82 120 6612070
1g 180 66 180 63 180 71 180 73 180 65180 73 180 66 180 78180 78 180 77 180 6618068
1h 200 64 200 65 200 74 200 80 200 74 200 7520072 200 78 200 75200 73 200 68 20070
1i 180 62 180 65 180 72 180 74 180 72180 76 180 76 180 75180 73 180 75 180 6818065
1j 240 68 240 63 240 64 240 72 240 72240 65 240 67 240 67240 64 240 64 240 6524072
1k 200 72 200 68 200 84 200 82 200 80 200 7320072 200 73 200 70200 75 200 78 20070

143 K. C. RAJANNA ET AL.
Table 18. Nitro decarboxylation of Cinnamic acid in presence of PEG-300 and metal nitrates under microwave conditions.
Entry 1a 1b 1c 1d 1e 1f 1g 1h 1i 1j 1k
Substrate CA 4-ClCA 4-OMeCA 4-MeCA4-NO2CA4-OHCAAACRA 3-PhCRA 2-ClCA2-MeCA
Ni(NO3)2 Zn(NO3)2 ZrO(NO3)2 Cd(NO3)2 Hg(NO3)2Mg(NO3)2Sr(NO3)2Al(NO3)3UO2(NO3)2 Th (NO3)2 AgNO3NH4NO3
Entry RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
1a 90 86 90 89 90 86 90 84 90 82 90 88 90 90 90 86 90 86 90 90 90 76 90 80
1b 120 82 120 80 120 76 120 80 120 78 120 84120 84 120 88 120 85 120 86 120 7412082
1c 90 84 90 85 90 86 90 86 90 82 90 85 90 82 90 86 90 86 90 84 90 78 90 78
1d 60 82 60 84 60 88 60 86 6080 608660 856086 60 80 60 82 60 75 6076
1e 90 72 90 76 90 84 90 82 90 82 90 80 90 80 90 84 90 78 90 78 90 75 90 72
1f 60 90 60 90 60 90 60 90 6088608660 856090 60 8860 86 60 78 6076
1g 120 78 120 74 120 78 120 78 120 70 120 78120 72 120 84 120 80 120 80 120 7612074
1h 120 76 120 75 120 80 120 86 120 80 120 76120 75 120 80 120 78 120 76 120 7812075
1i 120 76 120 75 120 80 120 80 120 78 120 8012082 120 82 120 76 120 80 120 7612072
1j 180 82 180 70 180 72 180 76 180 76 180 7218074 180 76 180 72 180 68 180 7618070
1k 120 86 120 85 120 86 120 88 120 85 120 78120 78 120 78 120 78 120 80 120 8012076
Table 19. Nitro decarboxylation of Cinnamic acid in presence of PEG-400 and metal nitrates under microwave conditions.
Entry 1a 1b 1c 1d 1e 1f 1g 1h 1i 1j 1k
Substrate CA 4-ClCA 4-OMeCA 4-MeCA4-NO2CA4-OHCAAACRA 3-PhCRA 2-ClCA2-MeCA
Ni(NO3)2 Zn(NO3)2 ZrO(NO3)2 Cd(NO3)2 Hg(NO3)2Mg(NO3)2Sr(NO3)2Al(NO3)3UO2(NO3)2 Th (NO3)2 AgNO3NH4NO3
Entry RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
1a 90 82 90 84 90 83 90 85 90 82 90 85 90 88 90 82 90 85 90 88 90 70 90 80
1b 120 80 120 76 120 72 120 78 120 78120 82 120781208412082120 85 120 70 12082
1c 90 82 90 82 90 84 90 85 90 80 90 84 90 80 90 81 90 81 90 84 90 74 90 75
1d 60 80 60 80 60 82 60 84 60826081 6078 6083 607660 80 60 726074
1e 90 70 90 72 90 78 90 78 90 78 90 76 90 80 90 78 90 68 90 78 90 70 90 70
1f 60 88 60 86 60 85 60 86 60 88 6084 60 84 608860 8460 84 60 74 6076
1g 120 74 120 68 120 74 120 75 120 70120 78 120701208012076120 80 120 73 12071
1h 120 72 120 70 120 78 120 82 120 82120 76 120741207812075120 75 120 74 12073
1i 120 70 120 70 120 76 120 80 120 7812078 120801208012072120 80 120 72 12070
1j 180 76 180 66 180 75 180 75 180 7618068 180701807218066180 64 180 70 18072
1k 120 80 120 80 120 84 120 84 120 85120 78 120761207412075120 78 120 76 12076

K. C. RAJANNA ET AL.
144
Table 20. Nitro decarboxylation of Cinnamic acid in presence of PEG-600 and metal nitrates under microwave conditions.
Entry 1a 1b 1c 1d 1e 1f 1g 1h 1i 1j 1k
Substrate CA 4-ClCA 4-OMeCA 4-MeCA4-NO2CA4-OHCAAACRA 3-PhCRA 2-ClCA2-MeCA
Ni(NO3)2 Zn(NO3)2 ZrO(NO3)2 Cd(NO3)2 Hg(NO3)2Mg(NO3)2Sr(NO3)2Al(NO3)3UO2(NO3)2 Th (NO3)2 AgNO3NH4NO3
Entry RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
1a 90 84 90 85 90 84 90 85 90 80 90 86 90 86 90 84 90 90 90 86 90 74 90 80
1b 120 82 120 76 120 75 120 78 120 72 12080 120 76 12085 120 82 120 83 120 7612082
1c 90 83 90 82 90 84 90 82 90 78 90 82 90 78 90 82 90 84 90 82 90 75 90 78
1d 60 82 60 79 60 86 60 80 60 7460 78 60 766084 60 80 60 80 60 7260 76
1e 90 74 90 72 90 80 90 78 90 78 90 76 90 78 90 80 90 74 90 76 90 70 90 72
1f 60 88 60 85 60 86 60 86 60 8460 83 60 806090 60 85 60 84 60 7660 78
1g 120 76 120 70 120 78 120 76 120 68 120 76120 68 12080 120 80 120 78 120 7312072
1h 120 75 120 72 120 82 120 82 120 75 12075 120 70 12082 120 78 120 75 120 7512073
1i 120 74 120 72 120 80 120 80 120 76120 76 120 78120 78 12075 120 78 120 72120 70
1j 180 76 180 66 180 76 180 75 180 78180 72 180 70180 74 18068 180 66 180 74180 78
1k 120 80 120 80 120 86 120 84 120 82 12076 120 76 12075 120 76 120 78 120 8012080
Table 21. Nitro decarboxylation of Cinnamic acid in presence of PEG-4000 and metal nitrates under microwave conditions.
Entry 1a 1b 1c 1d 1e 1f 1g 1h 1i 1j 1k
Substrate CA 4-ClCA 4-OMeCA 4-MeCA4-NO2CA4-OHCAAACRA 3-PhCRA 2-ClCA2-MeCA
Ni(NO3)2 Zn(NO3)2 ZrO(NO3)2 Cd(NO3)2 Hg(NO3)2Mg(NO3)2Sr(NO3)2Al(NO3)3UO2(NO3)2 Th (NO3)2 AgNO3NH4NO3
Entry RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
1a 180 80 180 82 180 85 180 80 180 78 180 80 180 82 180 82 180 85 180 85 180 78 180 80
1b 180 78 180 74 180 74 180 74 1807218076 180 72 18082 180 80 180 80 180 74180 78
1c 180 80 180 80 180 80 180 79 180 76 180 78 180 74 180 80 180 82 180 82 180 75 180 75
1d 120 78 120 78 120 82 120 81 1207512075 120 72 12079 120 76 120 78 120 72120 70
1e 180 72 180 70 180 80 180 74 180 76 180 70 180 75 180 78 180 70 180 74 180 70 180 68
1f 120 85 120 86 120 82 120 85 120 80 120 80 120 78120 86120 82120 80 120 78120 74
1g 180 72 180 68 180 72 180 75 1806818069 180 65 18078 180 76 180 78 180 74180 70
1h 220 74 220 70 220 78 220 80 2207222070 220 76 22080 220 74 220 75 220 75220 71
1i 180 72 180 72 180 80 180 78 1807518068 180 78 18078 180 70 180 78 180 74180 70
1j 240 74 240 70 240 76 240 74 2407024066 240 68 24075 240 68 240 68 240 75240 76
1k 220 80 220 80 220 82 220 82 2208022070 220 74 22076 220 74 220 76 220 80220 78

K. C. RAJANNA ET AL.
145
Table 22. Nitro decarboxylation of Cinnamic acid in presence of PEG-6000 and metal nitrates under microwave conditions.
Entry 1a 1b 1c 1d 1e 1f 1g 1h 1i 1j 1k
Substrate CA 4-ClCA 4-OMeCA 4-MeCA4-NO2CA4-OHCAAACRA 3-PhCRA 2-ClCA2-MeCA
Ni(NO3)2 Zn(NO3)2 ZrO(NO3)2 Cd(NO3)2 Hg(NO3)2Mg(NO3)2Sr(NO3)2Al (NO3)3UO2(NO3)2 Th (NO3)2 AgNO3NH4NO3
Entry RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
RT
(sec)
Yield
(%)
1a 180 82 180 80 180 84 180 82 180 82 180 85 180 84 180 84180 86 180 86 180 80 180 80
1b 180 77 180 76 180 73 180 72 180 74 18082 180 73 18084 180 81 180 84 180 7518076
1c 180 80 180 82 180 82 180 80 180 78 180 80 180 75 180 80180 84 180 82 180 78 180 78
1d 120 78 120 78 120 80 120 80 120 7612078 120 76120 78 120 76120 80 120 76120 72
1e 180 68 180 72 180 78 180 76 180 75 180 74 180 78 180 75180 74 180 75 180 74 180 68
1f 120 85 120 84 120 85 120 86 120 82 12085 120 80 12088 120 84 120 82 120 7812080
1g 180 72 180 68 180 70 180 75 180 70 18076 180 68 18080 180 76 180 78 180 7518072
1h 220 72 220 70 220 78 220 80 220 74 22074 220 78 22082 220 75 220 76 220 7622074
1i 180 68 180 72 180 78 180 78 180 75180 70 180 80180 78 18074 180 78 180 76 180 76
1j 240 73 240 68 240 80 240 76 240 78240 72 240 70240 75 24068 240 68 240 78240 76
1k 220 82 220 82 220 83 220 80 220 80 22075 220 76 22080 220 78 220 80 220 8022078
Figure 2. Effect of different Metal nitrates on RT versus
Yield (%) in presence of PEG-300.
Figure 1. Effect of different Poly ethylene glycols (PEG) on
RT versus Yield (%) in presence of Nickel Nitrate.
PEG-300 has been found to be much more effective than
other PEGs. The catalytic activity was found to be in the
increasing order: PEG-300 > PEG-400 > PEG-600 >
PEG-200. The plot of RT versus PEG type indicated that
reaction time decreases with an increase in molecular
weight of PEG as could be seen from the data presented
in Figure 1.
A comparative data profile given in Figure 2 clearly
shows remarkable rate enhancements in presence of a
variety of metal nitrates.
However, the metal nitrates belonging to s and p
-blocks such as Mg(NO3)2, Sr(NO3)2, Al(NO3)3, found
to be much more reactive than other metal nitrates,
which could be attributed to their hardness compa-
red to d- and f-block metal nitrate species. Similar
trends are shown in other systems. When PEG is added
to the reaction system Metal nitrate is capable to form
PEG bound Metal nitrates due to complexation accor-
ding to the following reaction. The species thus formed
could act as an effecttive catalyst to accelerate the re-
action by generating nitronium ion. Nitronium thus fo-
rmed converts Cinnamic acid into beta nitro styrene as
shown in the following sequence of steps shown in
Scheme 3.

K. C. RAJANNA ET AL.
146
R-CH=CH-COOH R C H = C HCO
O
[H-(OCH2-CH2)n -O - M( NO3)x-1] +
M(NO3)x-1
H-(OCH2-CH2)n -O
+ NO2+
NO2+
C O 2
R C H= C H N O2
+ N O3fast
W here R = Alky l (or ) Aryl group ; MNO3 = Metal
fast
+
NO3 [H-(OCH2-CH2)n -O - M( NO3)x-1] +
+ NO2+
[H-(OCH2-CH2)n -O - M( NO3)x-1]
H+
H+MNO3
[H-(OCH2-CH2)n -O - M(NO3)x-1] ++ PEG
H2O
2HNO3
H-(OCH2-CH2)n -OH+ [M(NO3)x] K
(PEG) (Metal Nitrate)
[H-(OCH2-CH2)n -O - M( NO3)x-1] +HNO3
[PEG-Metal Nitrate}
Scheme 3. The formation of Nitronium converts Cinnamic acid into beta nitro styrene.
4. Conclusions
Poly ethylene glycols (PEG-200, 300, 400, 600, 4000
and 6000) supported reactions were conducted with cer-
tain α, β-unsaturated acids in presence of metal nitrates
under mineral acid free and solvent free microwave irra-
diated (MWI) and grinding (mortar –pestle) conditions.
The aromatic acids underwent nitro decarboxylation and
afforded β-nitro styrene derivatives in very good yield
while α, β-unsaturated aliphatic carboxylic acids gave
corresponding nitro derivatives. Addition of PEG accele-
rated the rate of the reaction enormously. Reaction times
substantially decreased from several hours to few minu-
tes followed by highly significant increase in the produ-
ct yield. Among the several PEGs, PEG-300 has been
found to be much more effective than other PEGs.
5. Electronic Supplementary Material
Elaborated data pertains to nitro decarboxylation of cer-
tain α, β-unsaturated acids in presence of metal nitrates
under mineral acid free and solvent free MWI and
grinding (mortar-pestle) conditions are presented sepa-
rately in Tables 5-22, which is furnished as supplemen-
tary data.
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