Methoxymethylation of substituted alcohols using dimethoxymethane over Mo(VI)/ZrO2

Article abstract of DOI:10.14233/ajchem.2018.21091

The methoxymethylation reaction of alcohols was studied on Mo/ZrO2 (MZ) catalysts. The catalyst containing 5, 10 and 15 % Mo(VI) ions was prepared by solution combustion method. These solid acid catalytic materials were characterized by NH3- TPD, powder XRD, BET, FTIR spectroscopy, scanning electron microscopy, transmission electron spectroscopy and ICP- OES techniques. These catalysts were evaluated for their catalytic activity in the synthesis of methoxymethylation reactions of various substituted alcohols with dimethoxymethane in shorter reaction times (20 min) at moderate temperature (40 °C) with excellent yields (around 99 %). The main features of the Mo/ZrO2 catalyzed reaction are high yields, ease of scale up to gram scale, recyclable catalysts, inexpensive reagents, ecofriendly catalysts and a solvent free approach for the synthesis of methoxymethylated products.

Full text of DOI:10.14233/ajchem.2018.21091

Asian Journal of Chemistry; Vol. 30, No. 3 (2018), 655-660
A
SIAN
J
OURNAL OF HEMISTRY
C
https://doi.org/10.14233/ajchem.2018.21091
Methoxymethylation of Substituted Alcohols using Dimethoxymethane over Mo(VI)/ZrO2
4
1,3
M. SHYAMSUNDAR1,2,3, S.Z. MOHAMED SHAMSHUDDIN1,3*, A. ANANDA and S.R. PRATAP
1Chemistry Research Laboratory, HMS Institute of Technology, NH-4, Kyathsandra, Tumakuru-572 104, India
2The Oxford College of Engineering, Bommanahalli, Hosur Road, Bangalore-560 068, India
3Research and Development Centre, Bharathiar University, Coimbatore-641 046, India
4Dayananda Sagar Academy of Technology and Management, Kanakapura Main Road, Bangalore-560 082, India
*Corresponding author: E-mail: mohamed.shamshuddin@gmail.com
Received: 12 October 2017;
Accepted: 6 January 2018;
Published online: 31 January 2018;
AJC-18761
The methoxymethylation reaction of alcohols was studied on Mo/ZrO2 (MZ) catalysts. The catalyst containing 5, 10 and 15 % Mo(VI)
ions was prepared by solution combustion method. These solid acid catalytic materials were characterized by NH3-TPD, powder XRD,
BET, FTIR spectroscopy, scanning electron microscopy, transmission electron spectroscopy and ICP-OES techniques. These catalysts
were evaluated for their catalytic activity in the synthesis of methoxymethylation reactions of various substituted alcohols with
dimethoxymethane in shorter reaction times (20 min) at moderate temperature (40 °C) with excellent yields (around 99 %). The main
features of the Mo/ZrO2 catalyzed reaction are high yields, ease of scale up to gram scale, recyclable catalysts, inexpensive reagents, eco-
friendly catalysts and a solvent free approach for the synthesis of methoxymethylated products.
Keywords: Solution combustion method, Methoxymethylation, Dimethoxymethane, Mo(VI)/ZrO2, Solid acid catalysts.
promoted catalysts which are considered to be green catalysts
[12-16]. Molybdenum and tungstate based zirconia catalysts
are used for several organic reactions such as acetylation,
alkylation, esterification, transesterification, 1,3-dioxalanes,
biphenyl urea, etc. It is suitable for both liquid as well as vapour
phase reactions. Nevertheless, the use of modified zirconia
catalysts for fine chemical synthesis has not been studied
extensively so far there have been only a few research results
on the application of modified zirconia as catalysts in acid
catalyzed o-methoxymethylation reactions. Finally, zirconia
and its modified forms exploit green solid acid catalysts for
organic synthesis and transformation reactions in the liquid
phase under solvent-free or with environmentally benign solvents
represent an ultimate green chemical technology procedure
from both environmental as well as economical point of view.
In recent studies the protection of alcohols and phenols
is one of the most frequently employed reactions in organic
synthesis and is normally achieved by protecting groups.
Especially, methoxymethyl (MOM) ethers are commonly used
in protecting alcohols in the synthesis of natural products. The
methoxymethyl moiety is a commonly used protecting group
for alcoholic hydroxyl groups in the organic synthesis [17].
There are several methods to synthesize methoxymethyl ether
with various substituted alcohols in the presence of a variety
of catalysts [18,19]. A number of catalytic methods have been
INTRODUCTION
Solid acids as heterogeneous catalysts are extremely useful
in large quantity of applications, especially in the production
of fine and specialty chemicals [1,2]. Among various solid
acid catalysts metal oxides exhibit exceptional acidic properties
are more interesting with a variety of applications as catalysts
as well as a catalyst supports [3,4]. One class of solid acid
catalysts that have received lots of interest in metal oxides i.e.
zirconia and their modified forms. Zirconia is the only metal
oxide that possesses all four chemical properties specifically
acidic, basic, reducing and oxidizing ability [5-9]. Zirconia
and its modified form catalysts have received more interest in
which exhibit exceptional acidic properties. These catalysts
are finding frequent applications in many catalytic processes
involving liquid vapour and gas phase reactions [10,11].
A promoted zirconia solid acid in particular has been the
target catalysts among various solid acids described in earlier
reports due to their established advantages. Sulphate free-
zirconia based solid acids such as MoOx/ZrO2, VOx/ZrO2 and
WOx/ZrO2 have been synthesized and used as solid acid
catalysts in a little liquid and vapour phase reactions.Although
this sulphate free-zirconia is superior solid acid catalysts and
free form de-activation, unlike sulphated zirconia. The best
alternative catalyst for sulfated zirconia might be molybdate

656 Shyamsundar et al.
Asian J. Chem.
developed for the synthesis of methoxymethyl ethers are Na-Y
zeolite [20], molybdenyl(VI) acetylacetone [21], anhydrous
FeCl3 [22], envirocat EPZGR [23], sulfated metal oxides [24],
Bi(OTf)3] [25], Sc(OTf)3 [26], melamine trisulfonic acid [27],
TiO2/SO42- [28], etc.
meter (Philips X’pert) using CuKα radiation (λ = 1.5418 Å)
using graphite crystal monochromator with a scanning range
of 20-70°. The TSA of the catalytic materials were obtained
from NH3-TPD method using Mayura analytical temperature
program desorption unit. NOVA 1000 Quanta chrome high-
speed gas sorption analyzer instrument was used to measure
the specific surface area of all the prepared catalytic materials.
The FT-IR spectrums were recorded over a range of 4000-400
cm-1 using a Nicolet IR200 instrument by the KBr pellet tech-
nique. The amount of zirconia present in all the solid acid
catalysts was estimated by Inductively Coupled Plasma-Optical
Emission Spectrometer (ICP-OES) analysis techniques using
Thermo-iCAP 6000 Series instrument. SEM images and EDAX
of all the prepared catalytic materials were obtained using a
JEOL JXA-8530 microscope. TEM images of all prepared
catalytic materials were performed on PHILIPS CM200 electron
microscope at an acceleration voltage of 20-200 kV.
For this reason, the attention of the researchers is directed
towards the development of green as well as cleaner catalytic
technologies for the synthesis of methoxymethyl ethers. In
view of these impacts, alumina zirconia has been selected as an
inexpensive, green, eco-friendly, efficient and reusable catalytic
system for the present study. Conversely, only a few literatures
have scrutinized simple preparation of methoxy-methylation
reactions.Although various reagents have been used to synthesize
methoxymethyl ethers, they suffer from one or more disadvan-
tages such as stringent reaction conditions, moisture sensitive
metallic reagents, tedious work up procedures, long reaction times,
use of expensive reagents, poor yields, high reaction temperature,
etc. Consequently, the research for new catalysts and preparation
methods that develop eco-friendly protocol is still in demand.
The main goal of the current study has been made to prepare
Mo/ZrO2 (MZ) by solution combustion method [29]. All the
catalytic materials were characterized by their own physico-
chemical techniques such as crystallinity, surface acidity, funct-
ionality, percentage of metal ions and morphology. This catalytic
material has been used in methoxymethylation reactions of
various substituted alcohols by using dimethoxymethane at
moderate temperature (40 ºC) within a shorter reaction time (20
min). Mo/ZrO2 is simple versatile low cost, ecofriendly and
reusable catalysts. The reactivation and reusability of Mo/ZrO2
solid acids were also taken up.
Catalytic activity studies of ZrO2 and 5, 10 and 15 %
Mo(VI)/ZrO2: A calculated amount of alcoholic compounds
(1 mmol), dimethoxymethane (10 mmol) and solid acid catalysts
(ZrO2, 5, 10 and 15 % Mo(VI)/ZrO2) were transferred to a dried
round bottom flask fitted with a water cooled condenser and
the reaction mixture stirred at moderate temperature of 40 °C
with nitrogen (Scheme-I). The progress of the reaction was
monitored by thin layer chromatography. Once completion of
the reaction the catalysts were recovered from the reaction
mass by adding acetone solvent. The crude product was purified
by column chromatography by using suitable mobile phase
pet ether: ethyl acetate (80:20). Hence obtained products were
1
characterized by H, 13C NMR and GC-MS for the selected
compounds.
EXPERIMENTAL
OCH3
O
OCH3
All the chemicals used were L.R. grade as well as analytical
grade zirconyl nitrate, ammonium molybdate, dimethoxy
methane and various substituted alcohols were supplied by
LOBA chemie India Pvt. Ltd.
Mo(VI)/ZrO2
40 °C
CH3OH
R-OH
R
Methanol
Methoxymethyl ether
OCH3
Alcohol
Dimethoxymethane
Preparation of catalyst: Typically, 10 % of Mo/ZrO2 was
prepared with specified amount of zirconyl nitrate (9.0 g),
ammonium molybdate (0.45 g) with required amount of a urea
(7.5 g as a fuel) taken in a Pyrex glass container as reported
by Patil et al. [30]. Combustion was carried out in a preheated
muffle furnace (400 °C). Where in foamy solid was formed.
Thus obtained foamy solid was powdered and calcined in a
muffle furnace at 873 K for 5 h. Similarly, 5 and 15 % Mo/
ZrO2 were prepared by the above method. The catalytic material
such as ZrO2, Mo(VI)/ZrO2 prepared by solution combustion
method and it is abbreviated as Z and 5 Mo/ZrO2, 10 Mo/ZrO2
and 15 Mo/ZrO2.
Scheme-I
RESULTS AND DISCUSSION
Total surface acidity studies and ICP-OES studies: The
total surface acidity (TSA) values of solid acid catalytic materials
used in the present study are given in the Table-1.
The acidity values increase by incorporation of Mo ions
to zirconia catalysts shows a strong impact on acidic properties.
Acid sites compared with the zirconia and different % of Mo
incorporation to zirconia. On the other hand, it was observed
that zirconia consists of weak and medium acid sites. Whereas,
5 and 10 % Mo/ZrO2 consists of ‘moderate’ to ‘strong’ acid sites
the value has been increased drastically up to 10 %. Thereafter,
The crystallinity was analyzed by obtaining powder X-ray
diffraction (PXRD) patterns recorded by X-ray powder diffract
TABLE-1
CHARACTERIZATION OF SOLID ACIDS USED FOR THE PRESENT STUDY
Acid site distribution
Solid acid
BET surface area
Mo(VI) (%)
Weak
0.02
–
–
–
Medium
0.41
0.05
0.25
0.28
Strong
–
0.69
0.75
0.82
Total surface acidity (mmol/g)
ZrO2
0.45
0.97
1.26
1.15
42
78
105
89
–
4.6
9.56
14.65
5 % Mo/ZrO2
10 % Mo/ZrO2
15 % Mo/ZrO2

Vol. 30, No. 3 (2018)
Methoxymethylation of Substituted Alcohols using Dimethoxymethane over Mo(VI)/ZrO2 657
in case of 15 % Mo/ZrO2 acidity value was found to be slightly
decreased due to presence of excess molybdenum oxide
[29,31]. The total surface acidity values were shown in the
order of
1638
O-H
824
3421
15 % MZ
10 % MZ
1373
O-H
ZrO2 < 5 % Mo/ZrO2 < 15 % Mo/ZrO2 < 10 % Mo/ZrO2
O-H
Percentage of Mo present in the catalyst samples is also
given in Table-1. There is no significant loss during calcination
of the Mo/ZrO2 catalysts at 873 K. It is to be noted that the
definite amount of metal ions such as 4.6, 9.65 and 14.65 %
Mo ions is less than the amount expected from the amount to be
used.
BET surface area: The surface area of the catalytic
materials used for the present study is given in the Table-1.
The results attributed that zirconia shows the least surface area
among the catalytic materials which was used for the present
work. The catalytic materials were used 10 Mo/ZrO2 shows a
highest surface area than 5-15 Mo/ZrO2. It is also observed
that when the percentage of Mo(VI) is increased above 10 %
Mo/ZrO2, it is found that surface area to be decreased, which
is due to excess of molybdenum content on zirconia. The decrease
in the surface area with an increase in the concentration of
molybdenum cation beyond 10 % is due to blockage of pore
structures as reported by Zapien et al. [32].
O-H
O-H
O-H
5 % MZ
ZrO2
1270
O-H
O-H
739
500
0
1000 1500 2000 2500 3000 3500 4000
Wavenumber (cm–1)
Fig. 2. FTIR spectra of ZrO2, 5, 10 and 15 % Mo(VI)/ZrO2
The bands at about 739 and 1373 cm-1 are due to stretching
mode of Zr-O-Zr zirconium oxide confirmed the structure of
zirconia phases respectively. The broad band at 824 cm-1 were
shown that the Mo-O-MO stretching mode of vibration for
MoO3. The band at about 1638 cm-1 attributed acidic hydroxyl
proton and about 3421 cm-1 stretching mode of hydrogen
bonding exists in all the catalysts [33,34].
Powder XRD studies: Powder XRD patterns of the solid
acid catalysts are shown in Fig. 1. ZrO2 consisted of both mono-
clinic (M) and tetragonal (T) phases. Sharp diffraction lines at
2θ = 28.3, 24.46 and 31.58° correspond to the monoclinic phase
and the lines at 2θ = 30.27 and 49.21º are because of tetragonal
phase of ZrO2. As the findings in the earlier literature [32],
incorporation of Mo(VI) ions into ZrO2 results in transition of
monoclinic phase of ZrO2 to tetragonal phase of ZrO2. It is
interesting to note that when an increase in the percentage of
Mo(VI) cation promotes a stronger influence on the tetragonal
phase. In case of 10 % and 15 % Mo/ZrO2 peaks corresponding
to monoclinic phase have been totally eliminated and only meta-
stable tetragonal phase could be seen.
SEM/TEM studies: SEM images of zirconia and its
modified forms such as 10 Mo/ZrO2 are shown in Fig. 3.
Zirconia and its modified form Mo/ZrO2 shows the presence
of irregular shaped coarse grains with inter-granular porosity.
Mo/ZrO2 catalysts non-uniform particles are micrometer in
size and show porous in nature. TEM analysis clearly shows
big crystalline particles of zirconia and molybdenum ions are
dispersed with negligible agglomeration on the surface of the
zirconia with the particle size 45-58 nm (Fig. 4). The change
in morphology shows higher surface area of Mo/ZrO2 when
compared to ZrO2 [35,36].
FT-IR studies: The Fourier Transform Infrared spectra
of ZrO2 and 5, 10, 15 % of Mo(VI)/ZrO2 are shown in Fig. 2.
15 % MZ
10 % MZ
5 % MZ
Fig. 3. SEM images of ZrO2 and 10 % Mo/ZrO2
ZrO2
0
20
40
(°)
60
80
2
θ
Fig. 1. Powder-XRD patterns of solid acid catalysts [Z, 5 % Mo/ZrO2, 10
% Mo/ZrO2, 15 % Mo/ZrO2 calcined at 550 °C for 4 h. * tetragonal,
# monoclinic phase of zirconia]
Fig. 4. TEM images (a) ZrO2 (b) 10 % Mo(VI)/ZrO2

658 Shyamsundar et al.
Asian J. Chem.
Effect of nature of catalysts (ZrO2, 5, 10 and 15 %
Mo/ZrO2): In order to investigate, the catalytic activity of all
the materials such as ZrO2, 5 Mo/ZrO2, 10 Mo/ZrO2 and 15
Mo/ZrO2 were compared in O-methoxymethylation reaction
of substituted alcohols with dimethoxymethane. Dimethoxy-
methane serves both as a solvent as well as methoxymethyla-
ting reagent (Scheme-I). To optimize the reaction conditions
for the improved yield of O-methoxymethyl ether derivatives,
2-[(methoxymethoxy)methyl]furan and dimethoxymethane
used as model substrates in presence of 0.05 g of catalysts.
The mixture was refluxed under nitrogen at moderate tempe-
rature 40 °C for 20 min.
It was interesting to note that the highest yield 99.2 % of
2-[(methoxymethoxy) methyl] furan was observed with 10 %
Mo/ZrO2 by solution combustion method (Table-2). However,
when O-methoxymethylation reaction were carried out without
any catalysts, it shows very less yield of 2-[(methoxymethoxy)-
methyl]furan (19 %). This indicates O-methoxymethylation
is a catalyzed reaction. It is worth to mention that Mo/ZrO2
catalysts allylic and tertiary alcohols also smoothly converted
to O-methoxymethyl ethers without any trace amount of elimi-
nation products.
1-(4-Chloro-2-(methoxymethoxy)phenyl)ethanone:
Physical state: liquid; yield (%): 89; time (min): 20; 1H NMR
(CDCl3, 300 MHz): δ (ppm) 3.41 (s, 3H), 6.02 (s, 2H), 2.538
(s, 3H), 6.94 (d, 1H, 1.6 Hz), 6.89 (dd, 1H, J1 = 8.8 Hz, J2 =
1.6 Hz), 7.69 (d, 1H, 8.4 Hz). 13C NMR (CDCl3, 400 MHz): δ
(ppm) 55.6, 95.00, 161.56, 115.4, 139.7, 121.2, 131.25, 118.8,
29.06, 199.274. GC-MS (m/z) Calculated for C10H9O3Cl
[M+H-+]: 213.02, found 214.0.
2-Bromo-4-(methoxymethoxy)-1-methylbenzene:
Physical state: liquid; yield (%): 90; time (min): 20; 1H NMR
(CDCl3, 300 MHz): δ (ppm) 2.35 (s, 3H), 3.42 (s, 3H), 6.02
(s, 2H), 6.59 (dd, 1H, J1 = 8.4 Hz, J2 = 2.4 Hz), 6.84 (d, 1H, 8
Hz), 6.82 (d, 1H, 1.6Hz). 13C NMR (CDCl3, 400 MHz): δ (ppm)
55.65, 22.248, 95.06, 159.9, 117.5, 125.0, 16.52, 130.4, 132.3
and 113.2. GC-MS (m/z) Calculated for C9H9O2Br [M+H-+]:
231.98, found 229.9.
1-Cyclopropyl-2-(methoxymethoxy)benzene: Physical
1
state: liquid; yield (%): 89; H NMR (CDCl3, 300 MHz): δ
(ppm) 0.63 (m, 2H), 0.63 (m, 2H), 1.50 (m, 1H), 3.3 (s, 3H),
6.02 (s, 2H, 7.6 Hz), 7.02 (m, 2H).6.74 (d, 2H), 6.69 (d, 2H),
6.97 (d, 2H) 13C NMR (CDCl3, 400 MHz): δ (ppm) 5.7, 8.8,
8.8, 55.6, 95.3, 154.7, 113.7, 126.2, 120.5, 126.1 and 131.3.
GC-MS (m/z) Calculated for C11H12O2 [M+H-+]:178.1, found
178.9.
TABLE-2
O-METHOXYMETHYLATION OF 2-(METHOXYMETHOXY)
METHYL) FURAN OVER 10 % Mo/ZrO2 CATALYSTS
2-(Methoxymethoxy)-1,2-diphenylethanone: Physical
state: liquid; yield (%): 99.1; time (min): 20; 1H NMR (CDCl3,
300 MHz): δ (ppm) 3.45 (s, 3H), 5.45 (s, 2H), 5.63 (s, 1H),
7.19 (m, 3H), 7.39-7.48 (d, 2H, 6 Hz). 7.86 (m, 2H) 13C NMR
(CDCl3, 400 MHz): δ (ppm) 55.6, 94.6, 87.4, 194.3, 136.6,
129.7, 129.4, 127.7, 129.3, 127.7, 136.8, 128.8, 128.7, 128.8,
133.3 and 128.7. GC-MS (m/z) Calculated for C16H16O3 [M+H+]:
256.07, found 257.1.
Solid acid
catalysts
Total surface
acidity (mmol/g)
% Yield of 2-(methoxy-
methoxy)methyl)furan (%)
ZrO2
0.45
0.97
1.26
1.19
58.5
75.6
99.2
91.3
5 % Mo/ZrO2
10 % Mo/ZrO2
15 % Mo/ZrO2
Reaction conditions: Reaction temperature = 40 °C, reaction time = 20
min, molar ratio of alcohols and dimethoxy methane (1:10 mmol)
2-Fluoro-6-(methoxymethoxy)benzonitrile: Physical
1
state: liquid; yield (%): 88; H NMR (CDCl3, 300 MHz): δ
(ppm) 3.41 (s, 3H), 6.02 (s, 2H), 6.71-6.72 (m, 2H, 8 Hz),
7.41 (dd, 1H, J1 = 14.4 Hz, J2 = 6 Hz). 13C NMR (CDCl3, 400
MHz): δ (ppm) 55.6, 94.5, 164.9, 110.6, 135.7, 108.5, 161.5,
81.5, 115.8. GC-MS (m/z) Calculated for C9H8NO2F [M+H-
+]: 181.04, found 181.16
2-Chloro-3-(methoxymethoxy)methyl pyridine:
Physical state: liquid; yield (%): 99.2; time (min): 20; 1H NMR
(CDCl3, 300 MHz): δ (ppm) 3.41 (s, 3H), 5.45 (s, 2H), 4.63
(d, 2H), 8.19 (dd, 1H, J1 = 8 Hz, J2 = 4.8 Hz), 7.71 (d, 1H, 7.6
Hz), 8.75 (d, 1H, 5.2 Hz). 13C NMR (CDCl3, 400 MHz): δ
(ppm) 55.6, 97.3, 62.2, 133.38, 138.014, 138.05, 121.9, 150.05,
148.34. GC-MS (m/z) Calculated for C8H10NO2Cl [M+H-+]:
187.02, found 188.04
1,3-Di-tert-butyl-2-(methoxymethoxy)-5-methyl-
benzene: Physical state: liquid; yield (%): 89; 1H NMR (CDCl3,
300 MHz): δ (ppm) 1.34 (s, 18H), 3.48 (s, 3H), 6.02 (s, 2H),
2.33 (s, 3H), 13C (CDCl3, 400 MHz): δ (ppm) 55.6, 95.6, 24.9,
31.4, 31.74, 35.25, 135.91, 124.80, 129.0, 146.8. GC-MS (m/
z) Calculated for C17H28O2 [M+H-+]: 264.14, found 265.21.
1-(4-(2-(Methoxymethoxy)ethyl)benzyloxy)benzene:
Physical states: liquid; yield (%): 98; time (min): 20; 1H NMR
(CDCl3, 300 MHz): δ (ppm) 3.42 (s, 3H), 5.45 (s, 2H), 3.70
(d, 2H), 2.72 (d, 2H), 7.05 (d, 1H), 7.14 (d, 1H), 7.05 (d, 1H),
7.14 (d, 1H), 5.20 (s, 2H), 6.77 (d, 1H), 6.77 (d, 1H), 7.15 (d,
Synthesis of O-methoxymethylated compounds over
10 % Mo/ZrO2: In general a mixture of various alcohols,
dimethoxymethane (1:10 mole ratio) and 0.05 g of 10 Mo/
ZrO2 was added and the mixture was refluxed at 40 °C for an
appropriate time under nitrogen. The progress of the reaction
was monitored by TLC. After completion of the reaction the
mixture was cooled to room temperature filtered and the solid
catalyst was washed with diethyl ether (5 mL). The filtrate
was washed with brine solution and dried over anhydrous
sodium sulphate. The solvent was evaporated in rota-vapour
to get the residue. Thus obtained crude product was purified
in silica gel (60-120) column chromatography by using suitable
mobile phase pet ether-ethyl acetate (80:20) mixture. The
isolated products are characterized by 1H and 13CNMR, GC-
MS spectroscopic.
Spectral data
2-Iodo-3-(methoxymethoxy)pyridine: Physical state:
1
liquid; yield (%): 90; time (min): 20; H NMR (CDCl3, 300
MHz): δ (ppm) 3.42 (s, 3H), 6.02 (s, 2H), 7.289 (t, 1H, 4.4
Hz), 7.372 (d, 1H, 8 Hz), 8.271 (d, 1H, 3.6 Hz). 13C NMR
(CDCl3, 400 MHz): δ (ppm) 55.6, 94.1, 164.1, 121.6, 123.0,
142.3, 108.7, GC-MS (m/z) Calculated for C7H7NO2I [M+H-+]:
264.94, found 265.

Vol. 30, No. 3 (2018)
Methoxymethylation of Substituted Alcohols using Dimethoxymethane over Mo(VI)/ZrO2 659
1H), 7.15 (d, 1H), 6.82 (m, 1H); 13C (CDCl3, 400 MHz): δ
(ppm) 55.6, 97.6,72.2, 36.1, 138.4, 128.0, 127.1, 70.9, 160.7,
114.3, 129.8, 121.2. GC-MS (m/z) Calculated for C7H20O3
[M+H-+] 272.14, found 273.21.
1-((E)-3-(Methoxymethoxy)prop-1-enyl)benzene:
Physical states: liquid; yield (%): 97.8; 1H NMR (CDCl3, 300
MHz): δ (ppm) 3.42 (s, 3H), 5.45 (s, 2H), 4.04 (d, 2H), 6.25
(d, 1H), 6.62 (d, 1H), 7.30 (d, 1H), 7.21 (d, 1H), 7.14 (m, 1H).
13C (CDCl3, 400 MHz): δ (ppm) 55.6, 97.8, 70.2, 123.9, 129.7,
135.2, 126.1, 128.0, 128.9, 128.7, 126.3. GC-MS (m/z) Calcu-
lated for C11H14O2 [M+H-+] 178.14, found 178.10.
1-Bromo-4-[(methoxymethoxy)methyl]benzene:
Physical states: liquid; yield (%): 98.6; time (min): 20; 1H NMR
(CDCl3, 300 MHz): δ (ppm) 3.43 (s, 3H), 5.45 (s, 2H), 4.63
(d, 1H), 7.08 (d, 1H), 7.36 (d, 1H, J = 7.2 Hz), 7.08 (d, 1H),
7.36 (d, 1H). 13C (CDCl3, 400 MHz): δ (ppm) 55.6, 97.3, 71.3,
129.7, 131.6, 122.2, 131.6, 129.7, 136.5. GC-MS (m/z)
Calculated for C9H11BrO2 [M+H-+]: 229.99, found 229.10.
2-[(Methoxymethoxy)methyl]furan: Physical states:
liquid; yield (%): 99.2; 1H NMR (CDCl3, 300 MHz): δ (ppm)
3.3 (s, 3H), 4.48 (s, 2H), 6.19 (d, 1H), 6.25 (d, 1H), 7.30 (d,
1H, J = 8.8 Hz), 13C (CDCl3, 300 MHz): δ (ppm) 55.6, 94.8,
67.2, 152.8, 109.2, 108.2, 110.7, 144.1. GC-MS (m/z)
Calculated for C7H10O3 [M+H-+]:142.14, found 142.04.
4-Bromo-2-methoxy-1-[(methoxymethoxy)methyl]-
benzene; Physical state: liquid; yield (%): 97.8; time (min):
20; 1H NMR (CDCl3, 400 MHz): δ(ppm) 3.38 (s, 3H), 5.45 (s,
2H), 3.73 (s, 3H), 6.97 (dd, 1H, J1 = 8 Hz, J2 = 1.2 Hz), 6.87
(d, 1H, J = 8Hz).4.63 (d, 2H) 13C NMR (CDCl3, 400 MHz):
δ(ppm) 55.6, 97.3, 61.061, 56.2, 122.7, 123.9, 130.71, 123.22,
117.51, 159.93. GC-MS (m/z) Calculated for C10H13BrO3
[M+H-+]: 261.1, found 262.0.
Methoxymethoxy(methyl)cyclobutane: Physical state:
liquid; yield (%): 98.2; 1H NMR (CDCl3, 400 MHz): δ(ppm)
3.32 (s, 3H), 5.45 (s, 2H), 3.33 (d, 2H), 2.28 (m, 1H), 1.79-
2.04 (m, 2H), 1.91-2.01 (m, 2H), 1.79-2.04 (m, 2H), 13C NMR
(CDCl3, 400 MHz): δ(ppm) 55.6, 98.0, 76.7, 33.0, 24.7, 19.4,
24.7. GC-MS (m/z) Calculated for C7H14O2 [M+H-+]: 131.1,
found 130.0.
Comparison of 10 Mo/ZrO2 catalysts with reported
catalysts: In order to obtained the good yield with the advan-
tages of 10 Mo/ZrO2 catalysts compare with theearlier protocols
(Table-3). Interestingly, good yields obtained from the 10 Mo/
ZrO2 catalysts with some of the sterically hindered alcohols such
as tertiary and allylic alcohols.
at reactivated catalysts.After reactivations of used catalyst were
compared with weight of the catalysts there is no change
in weight after 6 reaction cycles. The reused catalysts were
100 % selective towards the product formation. The yield of
2-[(methoxymethoxy)methyl] furan over 10 % Mo/ZrO2 was
found to minimal extent shows a stable and suitable for reuse
after 6 reaction cycles of PXRD pattern shows intense peak of
tetragonal phase has shown after 6th reaction cycle are shown
in Fig. 5.
200
150
100
50
0
0
10
20
30
40
(°)
Fig. 5. 10 % Mo/ZrO2 used after 6 reactions cycles
50
60
70
2θ
Conclusion
In summary, Mo/ZrO2 is a simple ecofriendly and green
catalyst was prepared by the solution combustion method. 10 %
Mo/ZrO2 shows a high surface acidity than 5 % and 15 % Mo/
ZrO2. Hence these catalytic materials have been used for the
methoxymethylation reaction between the various substituted
alcohols and dimethoxymethane were methoxymethylated
with excellent yields of desired products. A good correlation
between the surface acidity, surface area and tetragonal phase
of the PXRD. These catalytic materials was recovered and
reused up to six reaction cycles without loss of its catalytic
activity. Mo/ZrO2 is an environment benign catalyst, because
of their mild reaction conditions, experimentally simple
procedure and high yield of products with shorter reaction
times.
ACKNOWLEDGEMENTS
Reusability and Reactivation of 10 Mo/ZrO2 solid acid
catalysts: The solid acid catalysts recovered from the liquid
reaction mass washed with acetone, dried at 120 °C for 2 h
calcined at 550 °C for 1 h and used in methoxymethylation
reaction with fresh reaction mixture to study the performance
The authors are grateful to Department of Chemistry HMS
Institute of Technology and VGST Project, Government of
Karnataka, Poornaprajna Institute of Analytical Research
Bangalore, India for PXRD analysis, BIT College for BET &
TABLE-3
COMPARISON OF 10 Mo/ZrO2 CATALYSTS WITH REPORTED CATALYSTS
S. No.
Catalyst used
10 % Mo(VI)/ZrO2
Sulphonic acid sodium montmorinillonite
Molybdenyl acetylacetonate
Sulphated Titania
Reaction condition
Solvent free, 40 °C
Chloroform
Chloroform
Solvent free, 40 °C
Solvent free, 40 °C
Yield (%)
99.2
92.0
85.0
90.0
Time (h)
0.20
2.00
4.00
3.00
Ref.
Present work
[[2277]]
1
2
3
4
5
[[2211]]
[27]
[27]
[20]
[20]
Na-Y zeolite
80.0
8.00

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