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Henry Reaction between Benzaldehyde and Nitromethane over Solid Base

Catalysts: A Green Protocol

Article in Green and Sustainable Chemistry · January 2018

DOI: 10.4236/gsc.2018.82010

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 Green and Sustainable Chemistry, 2018, 8, 139-155
http://www.scirp.org/journal/gsc
ISSN Online: 2160-696X
ISSN Print: 2160-6951

Henry Reaction between Benzaldehyde and

Nitromethane over Solid Base Catalysts: A
Green Protocol

Magda H. Abdellattif1*, Hany Mahmoud Mohamed2

Pharmaceutical chemistry department, Deanship of Scientific research Taif University, Taif, KSA
1

Chemistry Department, Faculty of Science, Taif University, Taif, KSA

2

How to cite this paper: Abdellattif, M.H. Abstract

and Mohamed, H.M. (2018) Henry Reac-
tion between Benzaldehyde and Nitrome- The development of environmentally benign solid base catalysts instead of the
thane over Solid Base Catalysts: A Green soluble bases for C-C bond formation in organic reactions especially Henry
Protocol. Green and Sustainable Chemistry,
reactions with nitroalkanes compounds is of intense research activity in the
8, 139-155.
https://doi.org/10.4236/gsc.2018.82010 bulk and fine chemical chemistry in order to achieve the selectivity of the de-
sired product and the reduction of the salts formed due to soluble bases neu-
Received: February 18, 2018 tralization. While using of LDHs catalysts in the synthesis of nitro alcohols is
Accepted: April 27, 2018
Published: April 30, 2018
of great interest because LDHs (double layered hydroxides) is of unique
properties and an excellent catalytic property. The nitroalcohols are obtained
Copyright © 2018 by authors and in a very good yield while using catalyst either by conventional at 90˚C in liq-
Scientific Research Publishing Inc.
uid phase, microwave or sonoenergy without solvent methods, and the results
This work is licensed under the Creative
Commons Attribution International yields are compared. A series of different nitro alcohols from (a - o) were
License (CC BY 4.0). prepared, the catalytic test reaction were carried out using benzaldehyde and
http://creativecommons.org/licenses/by/4.0/ their derivatives with nitromethane and their derivatives. A series of LDHs
Open Access
catalysts were prepared also and studying of the catalytic effect on the reac-
tions was carried out. Properties of the compounds prepared were characte-
rized by IR, MNR, and GC-MS.

Keywords
C-C Bond Formation, Henry Reaction, Base Catalyst

1. Introduction
The fine chemical industry has experienced remarkable interest over the past few
years due to the high requirements for products like pharmaceuticals, pesticides,
fragrances, flavorings and food additives [1].

DOI: 10.4236/gsc.2018.82010 Apr. 30, 2018 139 Green and Sustainable Chemistry
M. H. Abdellattif, H. M. Mohamed

The classical methods for the C-C coupling in Henry reaction using soluble
bases such as alkali metal hydroxides, carbonates, bicarbonates, alkoxides, alka-
line earth metal hydroxide, and aluminium ethoxides, complexes, and also or-
ganic bases such as primary, secondary and tertiary amines usually resulted in
dehydrated products [2]. Therefore, careful control of the basic properties of the
reaction medium is vital to obtain better yields of β-nitroalcohols. However, the
efforts done by the researchers in the literature required longer reaction times
and produced moderate yields [3] [4]. The stoichiometric organic synthesis
largely applied so far resulted in large quantities of inorganic salts as byproducts;
the disposal of such material causes a serious problem due to the important en-
vironmental issues [5].
The remarkable progress in the competition in the industry has pushed the
researchers to develop more effective catalytic processes in the synthesis of fine
chemicals.
The products of the Henry reaction, representing C-C bond formation, are
important materials extensively used in many organic syntheses [6]. The greatest
challenge in the selective synthesis of 2-nitroalkanols in the multiple product op-
tions such as aldol olefin and its polymer and Cannizaro products is the selec-
tion of the right type of base [7].
Significant improvements to the Henry reaction have been achieved by using
silyl nitronates in the presence of fluoride ion or altematively α-α doubly depro-
tonated primary nitroalkanes [8].
Both of these procedures have proved to be useful for the stereo selective
preparation of vicinal amino alcohols under drastic conditions, which reduced
diastereoselectivity with aromatic aldehydes. In order to obtain better yields and
diastereoselectivity of 2-nitroalcohols, it is necessary to develop new procedures
employing heterogeneous catalysts with basic character [9].
The homogenous catalytic methodologies reported in the literature have many
disadvantages, such as disposal of waste and difficulty to recover the catalyst
from the products. In the last decade, there were notable improvements in the
development of heterogeneous catalyst for Henry reaction [10].
Heterogeneous catalysis induced by solid catalysts such as basic alumina [11],
alumina-KF [12] and homogeneous phase transfer catalysis with surfactants [13]
in bi-phase system, the two divergent approaches being explored are aimed at
achieving higher atom selectivity. The solid base catalysts provide an alternative
to the classical soluble bases with emphasize to avoid the environmental prob-
lems caused by salt formation and hazardous conditions [14]. Previous wok in
the synthesis of fine chemicals using layered double hydroxides revealed the
importance of such materials and discovered its environmentally favorable
routes in comparison to the other catalysts [15]-[20].

2. Results and Discussion

Henry reaction is a base-catalyzed C-C bond-forming reaction between nitroal-

DOI: 10.4236/gsc.2018.82010 140 Green and Sustainable Chemistry

 M. H. Abdellattif, H. M. Mohamed

kanes and aldehydes or ketones. It is similar to the Aldol Addition, and also re-
ferred to as the Nitro Aldol Reaction.
If acidic protons are available (H), the products tend to eliminate water to give
nitroalkenes. Therefore, only small amounts of base should be used if the isola-
tion of the β-hydroxy nitro-compounds is desired, Scheme 1.
To generalize this reaction methodology three experiments were carried out
using different LDHs catalysts which may also be called hydrotalcite, and their
thermally activated form (calcined) were very active and very useful in many
different organic synthesis reactions. Henry reaction was carried out under three
conditions by these catalysts, by conventional method, and microwave method
[21].
Cu LDHs series was used in this research which were: uncalcined HT-Solgel
Cu:Mg:Al (1:2:1), calcined Cu:Mg:Al (1:2:1), clacined Cu:Mg:Al (2:1:1) and fi-
nally calcines Cu:Al (3:1). Table 1 represents the nitroalkanes and the aldehydes
used.
To compare the three types of this condensation reaction yield, it should be
taken in consideration from literature the most optimum temperature for this
reaction by conventional method was 90˚C. While in this research temperature
in conventional method decreased by using catalysts, Table 1 represented the
yield of this nitro aldol condensation reaction using three methods.
The use of uncalcined HT was not efficient enough like the other catalyst used
and the reaction yields and time were near to the reaction yield and time in the
absence of any catalyst and solvents in spite of temperature change and de-
creased to 60˚C, as shown in Table 4. Using of different calcined catalysts at
fixed weight 0.5 g, temperature 50˚C for conventional method, fixed microwave
temperature many different results but in a good and acceptable yield % for all
of the catalysts used as illustrated in Tables 5-7. These good results directed us
to make a comparison between the catalysts themselves and their activities to-
ward the nitroaldol reaction.
The higher activity of LDHs catalysts were observed because of their structure
flexibility as a host compound during the formation of final nirtoalcohol. It was
observed also at fixed amount of catalyst used, fixed temperature, and fixed
M.W conditions, changing of the catalyst type led to decrease in time of the
reaction required to be finished and increase of the reaction yield.

O2N H
H O Base, catlayst C Ar
C + R C
R NO2 o
R1
HC Ar Convn. 90 C or M.W. OH
R1

If R=H
M.W
O2N C CH Ar -H2O

R1

Scheme 1. Henry reaction and its mechanism.

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M. H. Abdellattif, H. M. Mohamed

Table 1. Compounds Structures.

Compound R R1 Ar

A H H 4-cholorobenzaldehyde

B CH3 H 4-cholorobenzaldehyde

c CH3 CH3 4-cholorobenzaldehyde

D H H 3, 5 Dibromo benzaldehyde

E CH3 H 3, 5 Dibromo benzaldehyde

F CH3 CH3 3, 5 Dibromo benzaldehyde

G H H 5-Bromo-3-nitro, Salicylaldehyde

H CH3 H 5-Bromo-3-nitro, Salicylaldehyde

I CH3 CH3 5-Bromo-3-nitro, Salicylaldehyde

J H H 2-Nitro-benzaldehyde

K CH3 H 2-Nitro-benzaldehyde

L CH3 CH3 2-Nitro-benzaldehyde

M H H 4-methoxy benzaldehyde

N CH3 H 4-methoxy benzaldehyde

O CH3 CH3 4-methoxy benzaldehyde

Table 2. Comparison between different methods time and yield without any catalysts.

Conventional at 90˚C Microwave

Compound Time Time
Yield % Yield %
Min. Min.

a 480 62 6.5 80

b 360 66 6.5 82

c 480 65 5.5 86

d 420 61 6 80

e 360 59 4.5 84

f 360 67 4.5 83

g 360 66 5.5 83

h 300 58 5.5 87

i 420 63 5 87

j 360 70 4.5 81

k 420 64 5 81

l 360 61 4.5 82

m 360 66 4 84

n 360 66 6 82

o 480 66 4.5 83

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 M. H. Abdellattif, H. M. Mohamed

Table 3. Comparison between different methods time and yield using uncalcined
HT-Solgel (0.5 g).

Conventional 60˚C Microwave

Compound
Time min. Yield % Time Min. Yield %

a 300 61 4.5 90

b 360 64 4.5 88

c 360 48 3.5 88

d 270 60 4 92

e 300 58 4.5 90

f 360 56 3.5 88

g 360 63 3.5 84

h 300 59 3.5 90

i 240 65 3.5 90

j 270 70 3.3 80

k 300 64 3 83

l 300 69 4 93

m 300 71 3 94

n 300 68 4 90

o 300 72 3 92

Table 4. Comparison between different methods time and yield using Cu:Mg:Al (1:2:1)
(0.5 g).

Conventional 60˚C Microwave

Compound
Time min. Yield % Time min. Yield %

a 270 70 3.5 95

b 270 73 3.5 94

c 240 72 3.5 92

d 240 75 3 94

e 240 79 3.5 93

f 180 77 2.5 93

g 210 76 2.8 94

h 210 68 3.5 93

i 210 69 3 92

j 240 76 2.6 91

k 270 75 3 91

l 240 78 3 89

m 240 76 2.4 94

n 210 78 3 93

o 210 76 2.6 94

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M. H. Abdellattif, H. M. Mohamed

Table 5. Comparison between different methods time and yield using calcined Cu:Mg:Al
(1:2:1) (0.5 g).

Conventional 60˚C Microwave

Compound
Time min. Yield % Time min. Yield %

a 180 70 3 95

b 180 73 3.5 95

c 210 72 3.5 96

d 210 75 2.6 94

e 210 79 2.5 93

f 210 77 2.5 96

g 180 76 2.5 96

h 220 68 2.5 95

i 230 69 2.5 94

j 230 76 2.3 95

k 280 75 3 94

l 180 78 2.5 95

m 250 76 2 94

n 200 78 2.5 96

o 200 76 2.5 94

Table 6. Comparison between different methods time and yield using clacined Cu:Mg:Al
(2:1:1) (0.5 g).

Conventional 60˚C Microwave

Compound
Time min. Yield % Time min. Yield %

a 65 82 2.8 95

b 60 83 2 95

c 60 84 2.5 96.5

d 55 83 2.5 95

e 55 83 2 94.5

f 55 85 2 96

g 58 86 2.2 98

h 60 85 2 97.5

i 60 85 2.5 97

j 62 88 2 96

k 66 84 2 95

l 65 86 2 96

m 65 85 2 96

n 63 90 2 94.5

o 63 92 2 96.5

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 M. H. Abdellattif, H. M. Mohamed

Table 7. Comparison between different methods time and yield using clacined Cu:Al
(3:1) (0.5 g).

Conventional 60˚C Microwave

Compound
Time min. Yield % Time min. Yield %

a 55 92 2.2 98.9

b 55 91 2 99

c 58 92 2.2 98.5

d 50 93.5 1.8 99

e 48 92.6 1.5 98.5

f 48 94.8 1.5 98.3

g 46 92 1.5 97.8

h 46 91 1.5 97.5

i 50 88 1.5 98

j 54 89 1.3 99

k 45 91 1.5 99

l 50 89 1.3 99

m 45 88.8 1.1 99

n 40 93 1 98.6

o 40 94 1 98.8

For Cu:Al 3:1 and Cu:Mg:Al 2:1:1 the reaction tended to be completed in a
short time. This can be explained by the catalyst which has higher copper con-
tent was more active in this serious. One also could observe that aldehyde which
has little electron withdrawing group influence and enhance the reaction activi-
ty. By the way microwave yields are the highest every time.
By the way from Table 3 the reaction tented to be finished between 4 - 6.5
min using M.W and 300 - 480 min using conventional method by maximum
yield 87% and 63% respectively. While using solvated catalyst reaction Table 2
completed at 3 - 4 min M.W and 300 min. by using conventional method in a
max. Yield % 94% and 71% respectively. The 99% yield percentage obtained by
using clacined Cu:Al 3:1, using M.W at 1.5 - 2 min. But using of calcined
Cu:Mg:Al (2:1:1) gave 98% yield as a highest yield percentage this may attributed
to the crystalline structure of Cu:Al 3:1 [22]. The difference in reaction catalysts,
yield and time was illustrated in Figures 1-5.
Where:
Figure 1: Compare between different methods time and yield without any
catalysts.
Figure 2: Compare the yield % change during use of different catalysts, by
MW irradiation method.
Figure 3: Compare the time change during use of different catalysts, MW ir-
radiation method.

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M. H. Abdellattif, H. M. Mohamed

Figure 4: Compare time change during use of different catalysts, by conven-

tional method.
Figure 5: Compare the yield % change during use of different catalysts, con-
ventional method.

600

500

TIME/YIELD%
400

300

200

100

0
a b c d e f g h i j k l m n o
COMPOUNDS A - O

time coventionnal yield convenntinal time M.W yield M.W

Figure 1. Comparison between different methods time and yield without any catalysts.

120

100

80
YIELD %,

60

40

20

0
a b c d e f g h i k l m n o
COMPOUNDS A - O
blank HT-1 HT-2 HT-3 HT-4 HT-5

Figure 2. % Yield change during use of different catalysts, MW.

7
TIME/MIN./CATALYST 0-5

0
a b c d e f g h i j k l m n o

COMPOUNDS A-O

Figure 3. Time change during use of different catalysts, MW.

DOI: 10.4236/gsc.2018.82010 146 Green and Sustainable Chemistry

 M. H. Abdellattif, H. M. Mohamed

600

500

TIME/CATALYST 1-5
400

300

200

100

0
a b c d e f g h i j k l m n o
COMPOUNDS A - O
blank HT-1 HT-2 HT-3 HT-4 HT-5

Figure 4. Time change during use of different catalysts, conventional.

100
90
80
70
YIELD%/CAT 1-5

60
50
40
30
20
10
0
a b c d e f g h i k l m n o
COMPOUNDS A - O

blank HT-1 HT-2 HT-3 HT-4 HT-5

Figure 5. % Yield change during use of different catalysts, conventional.

XRD of the catalysts were represented in Figure 6, indicating the diffraction

patterns of HT-1, HT-2, HT3, HT-4 and HT-5, which gave information about the
crystalline nature of these five catalysts. Catalyst showed diffraction pattern at 2θ
35.6˚, 38.8˚, 48.8˚, 53.6˚, 58.5˚, 61.5˚, 66.3˚, 68.1˚ and 75.4˚. The catalyst was also
analyzed after reuse by XRD and it showed no significant change. XRD patterns
catalysts layered structure was obtained (Ref. Pattern 22-0700, JCPDS) [23].
FTIR (Fourier transform infrared spectroscopy) of HT catalyst series sample
(Figure 7) showed a broad band at nearly 3500 cm−1 belonged to stretching vi-
bration OH. This might be because of the water interlayer and hydroxyl groups
in HT series [24]. Small weak band appeared at 1650-1700. This might be related
to the bridging mode H 2 O-CO32 − . Because of the vibrational mode of water a
weak peak at 1590 cm−1 appeared in the infrared spectrum which might be re-
lated to interlayer of water [25]. The peak around 1340 cm−1 belonged to carbo-
nate. All of carbonate bands of HT catalysts were removed completely during
calcinations at 450˚C [26]. This was as a result of complete thermal decomposi-
tion of hydrated catalysts phase into mixed metal oxides, which gave a good in-
dication of the XRD data [27] [28].

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M. H. Abdellattif, H. M. Mohamed

Figure 6. XRD for HT catalysts series.

Figure 7. FTIR of HT-catalyst series.

3. Methodology
All chemicals used were purchased from Sigma Alderich, analytical trade.
1
H-NMR spectra, 13C-NMR spectra were recorded on Bruker AM250 NMR
spectrometer using CDCl3 as solvent for the samples. Mass spectra were re-
corded on Shimadzu LCMS-QP 800 LC-MS, IR for the synthesised compounds

DOI: 10.4236/gsc.2018.82010 148 Green and Sustainable Chemistry

 M. H. Abdellattif, H. M. Mohamed

were recorded in potassium bromide discs on Shimadzu FT IR 8101 PC infrared

spectrophotometer. Elemental analysis was obtained using PerkinElmer 2400 II
series CHN Analyser. Thin-layer chromatography (TLC) was carried out on
pre-coated Merck silica gel F254 plates to 80˚. Melting points of the prepared
compounds were measured on a Gallenkamp melting point apparatus.
1) Catalysts
a) Synthesis
Catalysts were prepared by co-precipitation methods as literature [29] [30],
LDHs have the structures [ M12−+x , M 3x+ (OH)2]x+ [Ax/y]y−. mH2O, where the diva-
lent may be (Mg2+, Cu2+, Fe2+, Co2+, Ni2+, or Zn2+), and the trivalent are metal
cation (e.g., Al3+, Cr3+, Ga3+, Ln3+, Mn3+ or Fe3+) which forms the positively
charged layers, where Ay− are called inorganic or organic anions (e.g., CO32 − ,
Cl−, SO 24 − , RCO −2 ).
i- HT-1 (LDH-As)
Mixing of magnesium nitrate Mg (NO3)2·6H2O 0.2213 mol, and aluminium
nitrate Al (NO3)3 0.0885 mol, in a 0.2213 L of dist. H2O, mix (A). Mixing of
0.7162 mol of NaOH, and 0.2084 mol of Na2CO3, in a 0.221 L, mix (B). Drop
using a burette drops from Mix (A) and Mix (B) to a Round bottom flask 1 L
containing 0.5 L distilled water under vigorous stirring and heating at 60˚C and
measure pH during precipitation to be 10-11. Keep the temperature at 60˚C
overnight (16 h) in water bath. Filter using (Whatmann 1 filter paper) and
washing the cake by hot distilled water till pH = 7. Dry the filtrate at 80˚C in an
oven for 16 h.
ii- Cu:Mg:Al (1:2:1) HT-2, Clacined Cu:Mg:Al (1:2:1) HT-3, and Clacined
Cu:Mg:Al (2:1:1) HT-4
Cu metal modified HT Mg:Al was prepared by memory effect [30], where
typically, 1.0 g the as-prepared HT-As was treated with an aqueous Cu2+ nitrate
or sulfate solution (0.1 mol/L, 100 mL) with stirring at room temperature for 48
h to reconstruct into the layered hydrotalcite structure. The resulting products
were filtered, washed several times with distilled water and dried at 100˚C for 12
h, while the HT-Cu catalyst was obtained.
Then Cu-modified Mg-Al catalysts were prepared in oven at 500˚C for 7 h
under a flowing stream of pure N2.
iii- Clacined Cu:Al (3:1) HT-5
It was prepared also by coprecipitation methods as mentioned in literature,
where mixing of magnesium nitrate Cu SO4·5H2O 0.028 mol, and aluminium ni-
trate Al (NO3)3 0.01 mol, in a dist. H2O, mix (C), mixing of 0.7162 mol of NaOH,
and 0.2084 mol of Na2CO3, in a dist. H2O, mix (D). Drop using a burette drops
from Mix (C) and Mix (D) to a round bottle flask 1L containing 0.5 L distilled
water under vigorous stirring and heating at 60˚C and measure pH during pre-
cipitation to be 10-11. Keep the temperature at 60˚C overnight (16 h) in water
bath. Filter using (Whatmann 1 filter paper) and washing the cake by hot dis-
tilled water till pH = 7 gives (HT-5). Dry the filtrate at 80˚C in an oven for 16 h.
Heat 2 g of the above paste product in oven at 450˚C for 6 h in N2 atmosphere,

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M. H. Abdellattif, H. M. Mohamed

then dissolve in adequate amount of NaOH (0.1 M) to form a paste. Dry the
Paste at 80˚C in an oven for 16 h gives HT-5.
2) Synthesis of β-Nitroalcohol, via Henry Reaction
a) Microwave Irradiation Method
i- Without Catalyst
A mixture of an aldehyde series (10 mmol) and nitroalkane series (10 mmol)
were added to a vesicle, and the mixture was mixed strongly with a glass-rod at
room temperature. The mixture was added in a Teflon vial and irradiated under
350 W microwave till the reaction temperature raised to 120˚C with fixed mi-
crowave pressure. The vial was exposed to microwaves for a required time to
complete the reaction. Check the reaction and monitor it using TLC using (elu-
ent; Diethyl ether: chloroform) every 1 min. until the reaction reached the end.
Then the product mixture was cooled and extracted using ethanol analytical
grade. The process were repeated using different aldehyde and different to form
compounds from a - o.
The product compounds were purified by crystallization using EtOH/DMF
solvent mixture to afford the pure crude β-nitroalcoohls a - o in an excellent
yield.
ii- Using catalyst
Catalysts 0.5 g from HT-1 up to HT-5 were used and added by repeated ade-
quate sequence to a reaction mixture as mentioned above for the series a - o till
the reaction completed as before.
Each time and each run the catalysts were removed by filtration and washing
by hot ethanol after that the excess solvent was removed by vaporization to get
the final solid product. The product compounds were purified by crystallization
using EtOH/DMF solvent mixture to afford the pure crude β-nitroalcoohls a - o
in an excellent yield.
b) Conventional Method
The reaction were carried on electrical heating hotplate with stirrer and the
methods as mentioned above in microwave irradiated were applied without cat-
alyst at 90˚C and with the catalysts series at 60˚C for the series of catalysts and
series of the aldehydes and nitro alkanes. The reactants aldehydes, nitroalkanes
and catalyst were added together in a round flask bottle, closed with rubber sep-
tum connected to a condenser, after the completion of the reaction, the mixture
cooled room air temperature then separated and purified as above mentioned
and also the catalyst was treated as the above method.
i- p -2-Nitroethenylchlorobenzene (C8H6ClNO2)
mp. 262˚C, IR (KBr) υ max/cm−1: 1515 - 1560 (NO2), 1H NMR (DMSO): δ 5.1
(d, 1H, -C=C), 5.6 (d, 1H, -C=C) δ 7.27 - 7.4 (dd, 4H, Ar), 13C NMR (CDCl3): δ
77.8, 111.22, 127.4, 128.2, 131.8, 134.3, 134.7, MS (m/z): 183.01 (M+), Anal.
Calcd for C8H6ClNO2 (183.6), C-52.61; Cl-19.31; H-3.3; N-7.65% Found:
C-52.66; Cl-19.3; H-3.3; N-7.63; %.
ii- 1-(p -Chlorophenyl)-2-nitro-1-propene (C9H 8ClNO2)

DOI: 10.4236/gsc.2018.82010 150 Green and Sustainable Chemistry

 M. H. Abdellattif, H. M. Mohamed

mp. 386˚C, IR (KBr) υ max/cm−1: 1525 - 1570 (NO2), 1H NMR (DMSO): δ 1.7
(d, 3H, CH3), δ 4.9 (q, 1H, -C=CH), δ 7.2 - 7.45 (dd, 4H, Ar), 13C NMR
(CDCl3): H, CH), δ 7.27 - 7.4 (dd, 4H, ArH’s), 13C NMR (CDCl3): δ 25.5, 39.5,
77.82, 81.1 126.66, 130.8, 134.5, MS (m/z): 230.01 (M+), Anal. Calcd for
C10H12ClNO3 (229), C-52.30; Cl-15.44; H-5.27; N-6.10% Found: C-52.2; Cl-15.44;
H-4.01; N-6.8; %.
iii- 1-(4-chlorophenyl)-2-methyl-2-nitropropan-1-ol (C10H 12ClNO3)
mp. 465˚C, IR (KBr) υ max/cm−1: 1530 (NO2), 1H NMR (DMSO): δ 1.1 (s, 3H,
CH3), δ 5.1 (s, H, CH), δ 7.27 - 7.4 (dd, 4H, ArH’s), 13C NMR (CDCl3): δ 25.5,
39.5, 77.82, 81.1 126.66, 130.8, 134.5, MS (m/z): 230.01 (M+), Anal. Calcd for
C10H12ClNO3 (229), C-52.30; Cl-15.44; H-5.27; N-6.10% Found: C-52.2; Cl-15.44;
H-4.01; N-6.8; %.
iv- 2-Nitroethenyl-3,5-dibromobenzene C8H 5Br2NO2
mp. 491,˚C, IR (KBr) υ max/cm−1: 1480 (NO2), 670 (C-Br), 1H NMR (DMSO):
δ δ 5.2 (d, 1H, -C=CH), 6.2 (d, 1H, -C=CH), 7.7 - 7.9 (m, 3H, ArH’s), 13C NMR
(CDCl3): δ 77.8, 112.33, 123, 128, 131.1, 135.4, 139.5, MS (m/z): 306.5 (M+),
Anal. Calcd for C8H5Br2NO2 (307), Br-52; C-31.5; H-1.7; N-4.58% Found:
Br-51.7; C-30.57; H-1.6; N-4.46%.
v- 1-(3,5-Dibromophenyl)-2-nitro-1-propene (C9H 7Br2NO 2 )
mp. 538˚C, IR (KBr) υ max/cm−1: 1545 (NO2), 672 (C-Br), 1H NMR (DMSO):
δ 1.1 (d, 3H,CH3) δ 3.45 (m, 2H, CH2), δ 5.15 (d, 1H, -CH), δ 7.27 - 7.8 (m, 3H,
ArH’s), 13C NMR (CDCl3): δ 18.9, 44.5, 77.8, 84.75, 126.66, 129.8, 131.77, 134.7,
MS (m/z): 338.9 (M+), Anal. Calcd for C9H9Br2NO3 (339), Br-47.2; C-31.85;
H-2.65; N-6.85% Found: Br-47.14; C-31.89; H-2.68; N-4.13; %.
vi- 1-(3,5-dibromophenyl)-2-methyl-2-nitropropan-1-ol C10H 11Br2NO3
mp. 440.3˚C, IR (KBr) υ max/cm−1: 3550 (OH), 1523-1550 (NO2), 670 (C-Br),
H NMR (DMSO): δ 3.15 (d, 2H, CH2), δ 7.27 - 7.4 (dd, 4H, ArH’s), δ 5.2 (t, 1H,
1

-CH), 13C NMR (CDCl3): δ 25.5, 39.8, 77.8, 88.7, 124.4, 129.8, 131.1, 135.1 , MS
(m/z): 353.3 (M+), Anal. Calcd for C10H11Br2NO3 (353), Br-45.27; C-34.02;
H-3.14; N-3.97% Found: Br-45.3, C-34.01; H-3.15; N-3.95; %.
vii- 1-(3,5-Dibromophenyl)-2-nitro-1-propene (C9H 7Br2NO 2)
mp. 362˚C, IR (KBr) υ max/cm−1: 3600 (OH), 1520 - 1580 (2NO2), 675 (C-Br),
H NMR (DMSO): ): δ 1.75(d, 3H, CH3) , 4.95 (m, H, C=CH), δ 7.7 - 7.9 (m, 3H,
1

ArH’s), 13C NMR (CDCl3): δ 24.9, 77.8, 119.83, 123, 128, 130, 131.5, 139.5, MS
(m/z): 320.91 (M+), Anal. Calcd for C9H7Br2NO2 (321), Br-50; C-33.5; H-2.30;
N-4.4% Found: Br-49.79; C-33.68; H-2.20; N-4.36%.
viii- 4-bromo-2-(1-hydroxy-2-nitropropyl)-6-nitrophenol
mp. 609˚C, IR (KBr) υ max/cm−1: 3650 (OH), 1540 (2NO2), 675 (C-Br), 1H
NMR (DMSO): δ 1.75(d, 3H, CH3) , 4.95 (m, H, C=CH), δ 6.5 - 7.2 (dd, 2H,
ArH’s), 13C NMR (CDCl3): δ 18.5, 44.37, 77.82, 84.1, 110.86, 112.4, 117.4, 118.3,
144.3, 146.27, MS (m/z): 319.5 (M+), Anal. Calcd for C9H9BrN2O6 (321),
Br-24.89; C-33.67; H-2.83; N-8.72 Found: Br-24.89; C-33.8; H-2.87; N-8.6%.
ix- 4-bromo-2-(1-hydroxy-2-methyl-2-nitropropyl)-6-nitrophenol

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M. H. Abdellattif, H. M. Mohamed

mp. 765˚C, IR (KBr) υ max/cm−1: 3500 - 3700 (2OH), 1520 - 1580 (2NO2), 690
(C-Br), 1H NMR (DMSO): δ 1.09, (s, 3H,CH3), δ 5.2 (s, 1H, -CH), δ 6.5 - 7.2 (m,
2H, ArH’s), 13C NMR (CDCl3): δ 25.1, 39.48, 88.7, 110.86, 112.36, 117.5, 118.3,
145.3, 147.9, MS (m/z): 334.9 (M+), Anal. Calcd for C10H11BrN2O6 (335),
Br-23.84; C-35.9; H-3.3; N-8.4% Found: Br-Br-23.84; C-35.75; H-3.35; N-8.36%.
x- 2-nitro-1-(2-nitrophenyl) ethanol
mp. 428.8˚C, IR (KBr) υ max/cm−1: 1510 - 1555 (2NO2), 1H NMR (DMSO): δ
3.15 (d, 2H, CH2), δ 5.15 (t, 1H, -CH), δ 6.66 - 7.3 (m, 4H, ArH’s), 13C NMR
(CDCl3): δ 49.5, 77.8, 81.1, 112.87, 116.8, 126.66, 129.4, 150.97, MS (m/z): 212
(M+), Anal. Calcd for C8H8N2O5 (212), C-45.29; H-3.80; N-13.20% Found:
C-45.29; H-3.80; N-13.20; %.
xi- 2-nitro-1-(2-nitrophenyl) propan-1-ol
mp. 552˚C, IR (KBr) υ max/cm−1: 1515 - 1560 (2NO2), 1H NMR (DMSO): δ
1.04, (d, 3H, CH3), δ 3.45 (m, H, CH), δ 5.15 (d, H, CH), δ 6.7 - 7.3 (m, 4H,
ArH’s), 13C NMR (CDCl3): δ 18.1, 44.73, 77.8, 84.74, 112.87, 116.75, 129.3, 150.9,
MS (m/z): 226 (M+), Anal. Calcd for C9H10N2O5 (226.2), C-47.79; H-4.46;
N-12.39% Found: C-47.79; H-4.46; N-12.39%.
xii- 2-methyl-2-nitro-1-(2-nitrophenyl)propan-1-ol
mp. 453.3˚C, IR (KBr) υ max/cm−1: 3650 (OH), 1520 - 1570 (2NO2), 1H NMR
(DMSO): δ 1.04 (s, 3H, CH3), δ 5.15 (s, H, CH), δ 6.7 - 7.2 (m, 4H, ArH’s), 13C
NMR (CDCl3): δ 25.12, 39.9, 77.82, 88.65, 112.86, 116.75, 129.36, 150.99, MS
(m/z): 240.12 (M+), Anal. Calcd for C10H12N2O5 (240), C-50.00; H-5.04;
N-11.66% Found: C- 49.90; H-5; N-11.66%.
xiii- 1-(4-methoxyphenyl)-2-nitroethanol
mp. 443.87˚C, IR (KBr) υ max/cm−1: 1545 (NO2), 1150 (C-O), 1H NMR
(DMSO): δ 3.15 (s, H, CH3), δ 5.2 (t, 1H, -CH), δ 6.57 - 7.2 (m, 4H, ArH’s), 13C
NMR (CDCl3): δ 49.5, 65.5, 77.8, 114.2, 120.86, 129.56, 159.96, MS (m/z): 197.2
(M+), Anal. Calcd for C9H11NO4 (197), C-54.9; H-5.62; N-7.10% Found: C-54.8;
H-5.66; N-7%.
xiv- 1-(4-methoxyphenyl)-2-nitropropan-1-ol
mp. 440˚C, IR (KBr) υ max/cm−1: 1565 (NO2), 1210 (C-O), 1H NMR (DMSO):
δ 1.04(d, 3H, CH3), δ 3.14 (s, 3H, CH3), δ 3.5(m, 1H, -CH), δ 5.3 (d, H, CH), δ
7.27 - 7.4 (m, 4H, ArH’s), 13C NMR (CDCl3): δ 18.02, 44.95, 65.01, 77.8, 84.7,
114.16, 120.86, 129.6, 159.99, MS (m/z): 211.2 (M+), Anal. Calcd for C10H13NO3
(211), C-56.86; H-6.20; N-6.63% Found: C-56.86; H-6.20; N-6.63%.
xv- 1-(4-methoxyphenyl)-2-methyl-2-nitropropan-1-ol
mp. 468.8˚C, IR (KBr) υ max/cm−1: 3650 (OH), 1535 (NO2), 1050 (C-O), 1H
NMR (DMSO), δ 1.04 (s, 3H, CH3), δ 3.14 (s, 3H, CH3), δ 5.2 (s, H, CH), δ 6.9 -
7.3 (m, 4H, ArH’s), 13C NMR (CDCl3): δ 18.02, 44.95, 65.01, 77.8, 84.7, 114.16,
120.86, 129.6, 159.99, MS (m/z): 225.3 (M+), Anal. Calcd for C11H15NO3 (225),
C-58.66; H-6.71; N-6.22% Found: C-58.66; H-6.71; N-6.22; %.

4. Conclusion
In brief, we reported Henry reaction between benzaldehyde and nitromethane

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 M. H. Abdellattif, H. M. Mohamed

over solid base catalysts. Cu:Mg:Al-HT catalyst gave a precious advantage over
all solid base catalysts under investigation especially calcied Cu:Al 3:1 (HT-5).
Microwave irradiation technique introduced us high yields of β- alcohol deriva-
tives using the prepared series of HT solid catalyst in very short time. Strong Ba-
sic characterization of catalyst was responsible for the power of catalytic activity.
HT series kept their physical properties (texture and structure) even after many
catalytic runs, which facilitated gaining of high yields beta nitro alcohols. These
synthesized derivatives are of great importance in industry and medical uses.

Acknowledgements
The authors are very grateful to Taif University, Taif, KSA, because this work
was financial supported by Taif University, Taif, KSA, under project number
1/437/4938. The authors express their great thanks to Prof. Dr. Mohamed
Mokhtar, Chemistry Department, Faculty of Science, King Abdualziz University,
Jeddah, KSA, for help and advices.
The authors presented the abstract as poster at Green and sustainable chemi-
stry conference 13-15 May 2017, Berlin.

Conflict of Interest
The authors declare that, there is no conflict of interest.

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