Comprehensive experimental work has made it possible for us to introduce a selective,
efficient and solvent-free oxidation of geraniol and cinnamyl alcohol into valuable saturated
aldehydes by PP/4CSP. Furthermore, solid potassium permanganate used is less skin irritant
than its solution (safe for use), easy to operate the procedure, and specially generates desired
products with good yields in short time under the assistance of microwave irradiation at 94 oC,
e.g. max. 67 % of geranial and max. 61 % of cinnamaldehyde. In order to increase oxidative
ability of solid potassium permanganate, the amount of KMnO4 was used much more than
equivalent molar amount of alcohols, moreover copper(II) sulfate pentahydrate was necessary to
promote the oxidative ability of solid potassium permanganate
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Journal of Science and Technology 54 (2C) (2016) 320-327
SELECTIVE AND EFFICIENT OXIDATION OF UNSATURATED
ALCOHOLS AS CONSTITUENTS IN ESSENTIAL OILS
Luu Thi Xuan Thi
Department of Organic Chemistry, Faculty of Chemistry, University of Science - VNUHCM,
227 Nguyen Van Cu St., Dist. 5, Ho Chi Minh City, Vietnam
Email: ltxthi@hcmus.edu.vn
Received: 31 May 2016; Accepted for publication: 23 October 2016
ABSTRACT
Essential oil unsaturated alcohols have been oxidized efficiently into the corresponding
unsaturated aldehydes by potassium permanganate supported copper(II) sulfate pentahydrate.
Unsaturated aldehydes such as geranial and cinnamaldehyde being valuable components in food,
cosmetic, perfumery and pharmaceutical chemistry, have been obtained in good yields (> 60%)
under two activation methods: microwave irradiation and conventional heating.
Keywords: potassium permanganate, copper(II) sulfate, microwave irradiation, unsaturated
alcohol.
1. INTRODUCTION
The selective oxidation of alcohols into aldehydes or ketones is one of the most important
transformations in organic syntheses [1], especially the oxidation of unsaturated alcohols into the
corresponding unsaturated carbonyl compounds, e.g. the conversion of geraniol or nerol into
geranial or neral, and the conversion of cinnamyl alcohol into cinnamaldehyde. These generated
unsaturated aldehydes are important intermediates for the production of perfumes, fragrances
and pharmaceuticals [2, 3].
Various oxidants have been proposed for the oxidation of unsaturated alcohols, for instance
lead tetraacetate [4], potassium permaganate in alkaline media or supported by
bentonite/CuSO45H2O in the presence of solvent [5, 6], N-methylmorpholine N-oxide catalysed
by RuCl3 in dimethylformamide [7], and tetrapropylammonium perruthenate (TPAP) were
studied [8]. From both economics and environmental viewpoints, green oxidants have been paid
attention and developed by using molecular oxygen catalyzed by sodium nitrite and 2,3-
dichloro-5,6-dicyano-1,4-benzoquinone [9], or in supercritical carbon dioxide [10, 11], using
hydrogen peroxide with solid catalysts and supports, [12-14] and using 4-acetylamino-2,2,6,6-
tetramethylpiperidine-1-oxoammonium tetrafluoroborate with silica gel [15, 16].
In continuation of our works on transformation of natural compounds into valuable
compounds for laboratory as well as industry, we have selected potassium permanganate
absorbed on copper(II) sulfate pentahydrate, called xPP/yCSP (x molar amount of potassium
Selective and efficient oxidation of unsaturated alcohols
321
permanganate adsorbed on y molar amount of copper(II) sulfate pentahydrate) as oxidant for the
solvent-free oxidation of natural unsaturated alcohols, typical geraniol and cinnamyl alcohol into
geranial and cinnamaldehyde under conventional heating or microwave irradiation (Scheme 1).
Potassium permanganate is a powerful, commercially available, in-expensive and green oxidant
[17, 18], however its oxidation ability is prohibited owing to its less solubility in water and in
organic solvent. In order to overcome this problem, copper(II) sulfate pentahydrate was selected
to be solid support, Lewis acid and water resource. Very importantly, KMnO4 absorbed on
copper (II) pentahydrate is very easy to handle and safe for use, moreover removal of manganese
dioxide after reaction accomplishment is carried out more easily [19].
KMnO4/CuSO4.5H2O
MW or Δ
R OH R
CHO
Scheme 1. Solvent-free and selective oxidation of unsaturated alcohols into the corresponding aldehydes
by potassium permanganate adsorbed on copper(II) sulfate pentahydrate.
2. MATERIALS AND METHODS
2.1. Instrumentation and chemicals
2.1.1. Instrumentation
Microwave irradiations were generated by means of a Maxidigest MX-350 microwave
oven. GC/MS analyses were performed on Hewlett Packard 6890N and GC analyses were
performed on Shimadzu GC-17A.
2.1.1. Chemicals
- All chemicals used were from Sigma-Aldrich.
- Typical preparation of KMnO4/CuSO45H2O: Copper(II) sulfate pentahydrate (0.12 mol,
30.0 g) was dissolved completely in de-ionized water. Then, KMnO4 (0.03 mol, 4.74 g) was
added, followed by a sufficient volume of de-ionized water to obtain a homogeneous solution.
The solution was stirred for 10 minutes at 80oC. Subsequently, water was removed from the
solution by rotational evaporation, until the weight of the remaining solid mass was equal to the
sum of the weights of the original ingredients. The obtained solid mass was ground in a mortar
into a fine homogeneous powder of PP/4CSP [19].
2.2. Typical procedures
A test tube (h = 15.0 cm, d = 1.2 cm) containing a suitable quantity of finely ground
PP/4CSP and the unsaturated alcohol (following the molar ratio as in Table 1 and 2) were placed
in Maxidigest microwave oven. For each experiment, the irradiation program was applied to
determine the most efficient reaction conditions, see Table 1 and 2. Subsequently, the reaction
was extracted with diethyl ether (4 x 15 mL) and filtered through celite layer (2 cm). The extract
was removed solvent by rotational evaporation, and then, the remaining crude product was
analyzed by GC-FID and GC-MS.
Luu Thi Xuan Thi
322
The identity and purity of geranial and cinnamaldehyde reported were ensured by GC/MS
and GC-FID. Because their spectroscopy data are well known, a further presentation and
discussion of the spectra is not necessary.
3. RESULTS AND DISCUSSION
3.1. Oxidation of geraniol into geranial
Initially, geraniol was selected as typical unsaturated alcohol for the oxidation by potassium
permanganate adsorbed on copper(II) sulfate pentahydrate under two activation methods:
microwave irradiation and conventional heating. Based on the previous literature, the efficiency
of copper(II) sulfate pentahydrate supported KMnO4 oxidant also depends on the molar ratio
between potassium permanganate and copper(II) sulfate pentahydrate [19]. Further experiments
demonstrated that the molar ratio between KMnO4 and CuSO45H2O in KMnO4/CuSO45H2O-
promoted solvent-free oxidation of geraniol into geranial to take place most efficiently is 1:4
(Figure 1). The appropriate molar ratio of potassium permanganate and copper(II) sulfate
pentahydrate chosen was found compatible with that reported in the literature on the oxidation of
alcohol by PP/4CSP [19].
Figure 1. Influence of the molar ratio between KMnO4 and CuSO45H2O in KMnO4/CuSO45H2O on the
efficiency of the oxidation of geraniol into geranial under solvent-free conditions assisted by microwave
irradiation at 45 W for 10 min (geraniol: 3 mmol, KMnO4: 3 mmol).
This oxidant, in the following referred to as PP/4CSP was chosen as the standard oxidant in
our subsequent experiments. Initially, based on the reaction equation, the molar ratio of geraniol
and PP/4CSP was selected at 3:2; however, the reaction conversion was converted incompletely.
A series of experiments on the molar ratio between geraniol and PP/4CSP were performed by
varying the molar ratios sequentially at 45 W for 10 minutes under microwave irradiation (Entry
1-6, Table 1). The results displayed that using an appropriate amount of PP/4CSP increased the
reaction conversion and yield, but using excessive amount of PP/4CSP led to over-oxidation to
form geranic acid and 6-methyl-5-hepten-2-one. Finally, the appropriate molar ratio of geraniol
and PP/4CSP selected and used for further experiments is 3:10. In the next series of experiments,
power of microwave irradiation as well as reaction time were investigated to find out the most
efficient reaction conditions (Entry 6-11, Table 1). The results showed that geranial formed from
11
13
16
19
17
0
4
8
12
16
20
1:1 1:2 1:3 1:4 1:5
Yi
el
d
(%
)
KMnO4/CuSO4.5H2O (mol/mol)
Selective and efficient oxidation of unsaturated alcohols
323
the oxidation of geraniol by using PP/4CSP was obtained in good yield (67%) under fourteen-
minute microwave irradiation.
Table 1. The reaction factors influenced on the oxidation of geraniol by PP/4CSP in solvent-free media.a
OH
CHO
(1a)
(2)
(3a)
KMnO4/CuSO4.5H2O
MW or Δ
Entry Geraniol
(mmol)
KMnO4
(mmol)
CuSO45H2O
(mmol)
Power (Temp)b
W (oC)
Time
(min)
Yieldc (3a)
(%)
1 3 2 8 45 (84) 10 15
2 3 4 16 45 (84) 10 21
3 3 6 24 45 (88) 10 31
4 3 8 32 45 (90) 10 44
5 3 10 40 45 (90) 10 51
6 3 12 48 45 (94) 10 46
7 3 10 40 30 (78) 10 33
8 3 10 40 60 (110) 10 38
9 3 10 40 45 (90) 12 53
10 3 10 40 45 (94) 14 67
11 3 10 40 45 (100) 16 64
12d 3 10 40 94 10 42
13d 3 10 40 94 20 60
14d 3 10 40 94 30 51
a The reactions were performed under microwave irradiation.
b Temp. = the temperature of the reaction mixture was measured by thermometer immediately after the
stop of the reaction.
c Yields were calculated based on GC-FID analyses.
d The reactions were performed under conventional heating.
3.2. Oxidation of cinnamyl alcohol into cinnamaldehyde.
Based on the achievement of the oxidation of geraniol, we continued to select cinnamyl
alcohol, a natural unsaturated alcohol as model substrate. Similarly, the molar ratio of cinnamyl
alcohol and PP/4CSP were investigated at 60 W for 10 minutes under microwave irradiation
(Entry 1-5, Table 2) in detail in order to find out the good molar ratios. The results showed that
using excessive amount of PP/4CSP led to reducing yield of cinnamaldehyde. The main reasons
are explained that excessive amount of PP/4CSP oxidized directly a new-born cinnamaldehyde
into cinnamic acid under microwave irradiation. Further experiments on power of microwave
oven and reaction time as in Entry 7-11, Table 2 showed that cinnamaldehyde formed from the
Luu Thi Xuan Thi
324
oxidation of cinnamyl alcohol by using PP/4CSP was obtained in good yield (61%) under
twelve-minute microwave irradiation.
Table 2. The reaction factors influenced on the oxidation of cinnamyl alcohol by PP/4CSP in solvent-free
media.a
OH
CHO(2)KMnO4/CuSO4.5H2O
MW or Δ
(1b) (3b)
Entry Cinnamyl
alcohol
(mmol)
KMnO4
(mmol)
CuSO45H2O
(mmol)
Power (Temp)b
W (oC)
Time
(min)
Yieldc (3b)
(%)
1 3 2 8 60 (86) 10 40
2 3 4 14 60 (90) 10 45
3 3 6 24 60 (90) 10 49
4 3 8 32 60 (92) 10 41
5 3 10 40 60 (96) 10 21
6 3 6 24 45 (84) 10 29
7 3 6 24 75 (92) 10 59
8 3 6 24 90 (98) 10 54
9 3 6 24 75 (90) 8 41
10 3 6 24 75 (94) 12 61
11 3 6 24 75 (96) 14 51
12d 3 6 24 94 10 60
13d 3 6 24 94 12 62
14d 3 6 24 94 20 59
a The reactions were performed under microwave irradiation.
b Temp. = the temperature of the reaction mixture was measured by thermometer immediately after the
stop of the reaction.
c Yields were calculated based on GC-FID analyses.
d The reactions were performed under conventional heating.
Microwave irradiation inevitably affects a rise of the reaction temperature of the reaction
mixture, and it would therefore be of interest to check whether the drastically shortened reaction
times could be affected simply by the higher reaction temperatures. Thus a series of experiments
were performed under conventional heating at the same reaction temperature, same reaction time
with those under microwave irradiation or at various reaction time to get higher yield for both
oxidation of geraniol (Entry 12-14, Table 1) and cinnamyl alcohol (Entry 12-14, Table 2). The
summary results of two activation methods represented in Table 3 showed that these conversions
were easily occurred at high temperature, but with internal heating, microwave irradiation
Selective and efficient oxidation of unsaturated alcohols
325
influenced efficiently on reaching high temperature in shorter time than conventional heating
did.
Table 3. Summary results of the oxidation of geraniol and cinnamyl alcohols by PP/4CSP under
solvent-free condition.
Alcohols Molar ratio of
alcohol : PP/4CSP
Yield % (Time, Temperature)
Microwave Conventional heating
Geraniol 3:10:40 67 (14 min, 94oC) 60 (20 min, 94oC)
Cinnamyl alcohol 3:6:24 61 (12 min, 94oC) 62 (12 min, 94oC)
In the next step, a comparison table of our work with the previous literature on the
oxidation of geraniol illustrated that besides the yield of geranial obtained in our work was
slightly higher than those in the previous literature, PP/4CSP is also regarded as a green and
inexpensive oxidant, and used for solvent-free oxidation reactions, especially assisted by
microwave irradiation in order to reduce the cost of operation and get better yields in short time
(Table 4). While tetrapropylammonium perruthenate (TPAP) as oxidant combined with N-
methylmorpholine N-oxide (NMO) used for oxidation of geraniol were not stable, e.g. NMO is
hygroscopic, and TPAP can explode when heated; besides dichloromethane and acetonitrile as
reaction solvents are toxic and hazardous in case of eye contact, inhalation or ingestion [8]. In
addition, using oxygen molecule or hydrogen peroxide are usually appreciated highly based on
the principles of green chemistry, however these oxidation reactions must be performed in the
special instrument being able to resist high pressure [10, 11], or promoted by expensive and non-
commercially available catalysts [11,13].
Table 4. Comparison table of previous literatures on the oxidation of geraniol and cinnamyl alcohol.
Oxidant Geraniol Cinnamyl alcohol
PP/4CSP, solvent-free, MW 67 % (14 min, 94 oC) 61 (12 min, 94 oC)
TPAP, NMO, CH2Cl2, CH3CN 65 % (20 - 45 min., r.t.) [8] -
O2/scCO2, 5 wt% Pd/Silica mixed
with 0.2 g silica
59 % (3 - 4 hrs, 80 oC) [10] -
O2/scCO2 with CrMCM-41 52 % (6 hrs, 80 oC) [11] -
H2O2 with WO3-SiO2-700 63 % (2 hrs, 70 oC) [13] -
4. CONCLUSIONS
Comprehensive experimental work has made it possible for us to introduce a selective,
efficient and solvent-free oxidation of geraniol and cinnamyl alcohol into valuable saturated
aldehydes by PP/4CSP. Furthermore, solid potassium permanganate used is less skin irritant
than its solution (safe for use), easy to operate the procedure, and specially generates desired
products with good yields in short time under the assistance of microwave irradiation at 94 oC,
e.g. max. 67 % of geranial and max. 61 % of cinnamaldehyde. In order to increase oxidative
ability of solid potassium permanganate, the amount of KMnO4 was used much more than
Luu Thi Xuan Thi
326
equivalent molar amount of alcohols, moreover copper(II) sulfate pentahydrate was necessary to
promote the oxidative ability of solid potassium permanganate.
Acknowledgements. The authors are grateful to Prof. Fritz Duus, Roskilde University, Denmark for
chemicals support.
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TÓM TẮT
SỰ OXID HÓA CHỌN LỌC VÀ HIỆU QUẢ TRÊN CÁC ALCOL BẤT BÃO HÒA LÀ CÁC
CẤU TỬ CHÍNH TRONG TINH DẦU
Lưu Thị Xuân Thi
Bộ môn Hóa Hữu cơ, Khoa Hóa học, Trường Đại học Khoa học Tự nhiên Tp. HCM,
227 Nguyễn Văn Cừ, Quận 5, Tp.HCM, Việt Nam
Email: ltxthi@hcmus.edu.vn
Alcol bất bão hòa có trong tinh dầu được oxid hóa rất hiệu quả thành các aldehyd bất bão
hòa tương ứng bằng permanganat kali tẩm trên sulfat đồng (II) ngậm năm phân tử nước. Các
aldehyde bất bão hòa như geranial và cinnamaldehyd là các hợp chất có giá trị trong thực phẩm,
mỹ phẩm, hương liệu và hóa dược được tạo thành với hiệu suất khá cao (> 60 %) dưới hai
phương pháp kích hoạt: chiếu xạ vi sóng và đun nóng cổ điển.
Từ khóa: potassium permanganate, copper (II) sulfate, microwave irradiation, unsaturated
alcohol.
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