Literature review

As growing demand for fuels and chemicals with limited natural sources we need to find out
the alternative source to fulfil requirement of growing population as well as reduce the
society dependence on oil [1]. Many researchers were reported that the main raw material for
the production of crude oil is fatty alcohol [1] [2][3]. Fatty alcohols (long chain alcohols) or
n-alkanols are usually high molecular weight, straight chain primary alcohols which are
mainly derived from fats and oils used in pharmaceutical, plastic or detergent industries.
Most fatty alcohols are saturated in that they have no double bonds present in their structure
[4]. Selective oxidation is one of the alternative ways to find out the valuable intermediates
(aldehydes, Ketone, esters and fatty acids) for fine chemicals, pharmaceutical and
agrochemical sectors. Oxidation of alcohols into corresponding aldehydes is one of the
alternatives important for group transformation in organic synthesis [5]. There are several
kind of catalyst mainly used for oxidation of fatty alcohols such as enzymatic, homogeneous
and combine catalytic systems, heterogeneous catalysts. The oxidation mainly carried out
first alkans get converted into alcohols and alcohols get converted into aldehydes and then
acids and esters [1-5].
Vicente Corts Corberen et al. [5] report on heterogeneous selective oxidation of fatty
alcohols with liquid phase oxidation of 1- tetradecanol. They show that 1 tetradecanol use as
model molecule for fatty alcohol to reduce the scarcity of the available fossil resources and
the environmental impact of their use. Gold deposited CeO2- Al2O3 as a support catalyst use
for the conversion of fatty alcohol was synthesized by using anion exchange method. The
catalytic oxidation test was conducted under atmospheric pressure at 80-120C with four
neck round bottom flask equip with reflux condenser, oxygen feed, thermometer and septum
cap. They work on several parameters such as effect of alcohol carbon chain length, effect of
alcohol/metal (A/M) ratio, effect of solvent and effect of reaction temperature with selectivity
(80%) and conversion (38%) depending on reaction conditions. Also mention that the alcohol
reactivity relatively decreases with increase of carbon atom probably due to static effect. J.
M. Pena et al. [6] work on the different factors affecting on the adsorption of fatty alcohols.
They also studied several parameters as mention above but the catalyst use for oxidation was
carbon black pigments. In order to obtain a crystallisation of the alkyl group, the linear
structure and length of the aliphatic chain of the fatty acid molecule length (equal or superior
to C17) are required, resulting in a higher energy of adsorption. They were also shown that
the dispersive interaction between the aliphatic chain and surface basal grapheme layers of
carbon black has also shown to occurred.
Wang et al. [7] work on the gold nanoparticles deposited on MnO2 nanorod materials with
different loading of gold particles by hydrothermal process. Liquid phase aerobic oxidation of
different alcohols was tested under solvent free conditions using autoclave assisted system.
Au/MnO2-R catalyst shows higher reactivity for benzylic and allylic alcohols than for
aliphatic alcohols. Cyclohexanol and 1-octanol appeared to be poor substrates, yielding the
corresponding carbonyl compounds in only 10.7% and 2.4% yields for 8 h, respectively. In
addition, the primary linear aliphatic alcohol 1-octanol showed a lower activity compared
with the secondary aliphatic alcohol 2-octanol (yield 55.7 %).1-octanol shows the lower

activity as compare to 2- octanol with lesser amount of aldehyde. Yang et al. [8] also work on
aerobic oxidation of 2-octanol over carbon nanotubes supported Ru (ruthenium) catalyst.
Parmiggiani et al. [9] transition metal based catalyst was showing good results for aerobic
oxidation of alcohols (CH3(CH2)8CH2OH). In which they report that the Ru is less expensive
than Au, Pd or Pt; however, one of the few reports of Ru/C-catalyzed procedures was
presented by Sajiki and co-workers [10], they showed that 10% Ru/C as a catalyst in toluene
(at 50 C) 59% of yield was occurred under an oxygen atmosphere was able to convert
various secondary and primary aliphatic alcohols by oxidation.
Jenzer and co-workers [11] work on palladium catalyzed oxidation of octyl alcohols in
supercritical carbon dioxide in which catalytic test was carried out isothermally in tubular
flow reactor. Oxidation of octyl alcohols to carbonyl compounds (1-octanal, 2- and 3octanone) at atmospheric pressure was done by using platinum, ruthenium, palladium as
dopant with alumina as support. In this paper they report that the Pd-catalyzed aerobic
oxidation in scCO2 (sc-supercritical) is limited to the transformation of secondary alcohols to
ketones. Dimitratose and co-workers [12] was reported that the selective liquid phase
oxidation of supported nanoparticles. The oxidation of 1-octanol using Pd/NiZn catalyst at
80C with almost 99% conversion and oxidation of 3-octanol with Au/CeO2 catalyst shows
97% conversion. The selectivity to aldehydes/keton was almost 98-99%. Yamaguchi and coworkers [13] also reports the same results with the oxidation of 1-octanol the selectivity and
yield was almost 98-99%.
In green sustainable processes for oxidation reactions has increase research rapidly with an
almost 10-fold increase of papers on the conventional oxidation of alcohols subject from
1998 to 2012, but reports on selective oxidation of fatty alcohols with more than eight carbon
atoms (C8+) are really scarce: only 15 references since 1990 and no any single paper on
tetradecanol oxidation [1, 5 and 14].
Villa and co-workers [15] reports on fragrances by selective oxidation of long chain alcohols.
In this study they were investigate the activity and selectivity Ru and Pt based carbon catalyst
in the selective oxidation of long chain alcohols (C8, C10, C12). To improve the durability of
catalyst the modification of Pt/Ac (Ac-Activated carbon) and Ru/Ac with gold nanoparticles
was carried during synthesis of catalyst. Ru/AC and AuRu/AC showed good selectivity to
corresponding aldehydes (>95%) as shown in table 1 and because of that these catalysts are
promising for manufacturing of fragrances. The activity of the catalysts seems to be
influenced by the length of the aliphatic chain being C8>C10>C12.They were also carried
some experiments with the effect of different solvents on 1-octanol i. e. toluene and dioxane
/water. The recyclability of catalyst was possible by complete toluene washing at 100C, that
showing almost >99% selectivity towards aldehyde as shown in table 2.
Table.1
Catalyst

Substrate

Au/Ac
Ru/Ac
AuRu/Ac
Pt/Ac

1-octanol
1-octanol
1-octanol
1-octanol

Activity (mol
mol-1 h-1)
3
114
63
141

Conversion
5
55
66
75

Selectivity %
(Aldehyde)
>99
>99
47

AuPt/Ac
Au/Ac
Ru/Ac
AuRu/Ac
Pt/Ac
AuPt/Ac
Au/Ac
Ru/Ac
AuRu/Ac
Pt/Ac
AuPt/Ac

1-octanol
1-decanol
1-decanol
1-decanol
1-decanol
1-decanol
1-dodecanol
1-dodecanol
1-dodecanol
1-dodecanol
1-dodecanol

127
1
84
59
68
28
2
65
61
46
25

85
3
46
68
70
81
4
33
49
56
62

50
94
98
40
52
96
98
36
45

*Reaction conditions: 0.6 mol/L, metal/alcohol ratio 1/100 (mol/mol), T =100C, p(O2)=200 kPa.

Table 2
Catalyst

Treatment

Ru/Ac

Fresh catalyst
none
Washing
Reduced by H2 at 300C
Fresh catalyst
none
Washing
Reduced by H2 at 300C

AuRu/Ac

Conversion
(%) after 12h
55
10
15
51
66
25
58
62

Selectivity
(%) Aldehyde
>99
>99
>99
>99
>99
>99
>99
>99

*Reaction conditions: 0.6 mol/L in toluene, metal/alcohol ratio 1/100 (mol/mol), T = 100 C, p(O2) = 200 kPa

Croma and co-workers [16] shows that the organic reactions are also possible with the
supported gold nanoparticles. These supported nanoparticles have a green and sustainable
chemistry on catalytic activity of supported gold nanoparticles. These nanoparticles have a
unique ability to promote addition to multiple C-C bonds for oxidation of alcohols. Kan and
co-workers [17] work on the catalytic oxidation of -eicosanol (C20 alcohol) into ecosanic
acid in the presence of Ti-MCM-41 (MCM- mesoporous nanoparticles). Several parameters
were studied such as effect of temperature, effect of reaction time and catalyst amount.
Transition metal loaded Ti-MCM-41 i.e. Cr shows higher activity for the oxidation of eicosanol (C20 alcohol).
Dijksman et al. [18] work on the efficient ruthenium TEMPO ((2, 2, 6, 6Tetramethylpiperidin-1-yl) oxy) catalysed aerobic oxidation of aliphatic alcohols into
aldehydes and ketone. TEMPO shows almost 100 percent conversions of aliphatic alcohols to
aldehydes as shown in table 3.
Table 3
Entry
1
2
3

Substrate
Octan-1-ol
Me2C=CHCH2OH
3-MeOC6H4CH2OH

Product

Time/h

Octanal
Me2C=CHCHO
3-MeOC6H4CHO

7
7
4

Conversion %
(Aldehyde)
95
96
100

4
5
6

4-MeOC6H4CH2OH
4-MeC6H4CH2OH
4-O2NC6H4CH2OH

4-MeOC6H4CHO
4-MeC6H4CHO
4-O2NC6H4CHO

3
4
7

100
100
68

*Reaction conditions: 15 mmol substrate, 1.5 mol% RuCl2 (PPh3)3, 4.5 mol% TEMPO, 30 ml PhCl, 10 ml min-1 O2N2
(8:92; v/v), P = 10 bar, T = 100 C

Dimitratos and co-workers [19] shows that the Pd and Pt catalyst modified by alloying with
Au in selective oxidation of 1-octanol to octanal. With the varying amount of Au-Pd and AuPt loading 1-octanol gets converted into octanal and the solvent use for this particular
reaction is toluene or water. Degussa 5% Pt with solvent toluene shows almost 100%
selectivity and 8% conversion. Villa and co-workers [20] work on the effect of reaction
parameters on catalytic activity and selectivity on Au-Pd/Ac for alcohol oxidation. This work
was quite similar to Dimitratos et.al [19] as oxidation of 1-octanol to octanal using bimetallic
catalyst. One point they was discuss in this article, with the addition of NaOH as solvent
more amount of acid formation was take place and without addition of solvent aldehyde was
formed.
Mallat and Baiker [21] work on oxidation of alcohols with molecular oxygen on solid
catalysts. They are report that bimetallic catalyst with good support shows 100% selectivity
for oxidation of aliphatic alcohols to aldehyde. Little catalyst with appropriate yield and
selectivity was shown in table 4. 1-octanol and 1-dodecanol oxidation was carried by using
PhCH3 (phenyl methane) as solvent but only in case of Pt the C7H16 solvent was used. Yangli and co-workers [22] work on the oxidation of long chain primary alcohols to acid over the
quaternary peroxotungstophosphate catalyst system. In which they were work on C6 to C20
alcohols.
Table 4
Catalyst

Substrate

T (K)

5% Pt-1% Bi/Al2O3
Ru0.35MnFe1.5Cu0.15Ox
Ru3+-hydroxyapatite
Pr4N+RuO4-/or mosil(SiO2)
RuO4/polymer
Pt
RuCo1.5Ox

1-octanol
1-octanol
1-octanol
1-octanol
1-octanol
1-dodecanol
1-dodecanol

333
295
333
348
358
333
383

Yield
(%)
76
51
94
70
91
77
50

Selectivity
(%)
85
100
99
100
100
93

Hara and co-workers [23] work on the creation of highly stable monomeric Pd(II) species in
an anion exchangeable hydroxy double salt interlayer: application to aerobic oxidation under
an air atmosphere. Oxidation of alcohol to aldehyde was done by using active Pd(II)
supported on mixed basic salt NiZn, which is classified by anion exchangeable layer hydroxy
double salt, was synthesized by simple interaction of anionic hydroxyl complex. The aerobic
alcohol oxidation was possible due to strong electrostatic interaction between NiZn host and
anionic Pd(II) species. Nishimura et al. [24] also work on Pd(II) catalysed oxidation of
alcohols under an oxygen atmosphere in a fluorous biphase system (FBS). In transition metal-

catalysed reactions in a fluorous biphase systems (FBS) have become one of the most
important methods for facile catalyst separation from the reaction mixture and recycling of
the catalyst. FBS is a two-phase system; the metal catalyst coordinated by perfluoroalkylated
ligands can dissolve into the fluorous phase and be easily recovered by the separation of the
organic phase containing the product after the reaction. They were reported, the aerobic
oxidation of alcohols in toluene to give the corresponding aldehydes and ketones using a
catalytic amount of Pd(OAc)2 or (Palladium acetate), pyridine and 3 A molecular sieves
under an oxygen atmosphere. Oxidation of octadecan-1-ol and dodecan-2-one was done and
corresponding aldehyde formation was carried out with isolated yield of 70 and 55%.
Kang and co-workers [25] work on catalytic oxidation of alcohols with polymer supported
Ru complex under mild conditions. In which polymer supported ruthenium containing
complex PSPhenRu was synthesized (where PS = chloromethyl polystyrene resin, Phen =
1, 10-phenanthroline) and was characterized by FT-IR, ICP, and XPS. This supported
complex used for oxidation of dodecanol to dodecanal and other long chain aliphatic and
aromatic alcohols to corresponding aldehydes. Oxidation using such complex these reaction
gives 100% conversion and selectivity. They also report that the supported ruthenium
complex can also be recycled in this oxidation system.
Reference
[1] V. C. Corbern, M. E. Gonzlez-Prez, S. Martnez-Gonzlez, and A. Gmez-Avils,
Green oxidation of fatty alcohols: Challenges and opportunities, Appl. Catal. Gen.,
vol. 474, pp. 211223, Mar. 2014.
[2] A. Behr, A. Westfechtel, and J. Prez Gomes, Catalytic Processes for the Technical
Use of Natural Fats and Oils, Chem. Eng. Technol., vol. 31, no. 5, pp. 700714, May
2008.
[3] A. Corma, S. Iborra, and A. Velty, Chemical Routes for the Transformation of
Biomass into Chemicals, Chem. Rev., vol. 107, no. 6, pp. 24112488, May 2007.
[4] S. M. Mudge, Fatty Alcohols a review of their natural synthesis and environmental
distribution.
[5] V. C. Corbern, A. Gmez-Avils, S. Martnez-Gonzlez, S. Ivanova, M. I. Domnguez,
and M. E. Gonzlez-Prez, Heterogeneous selective oxidation of fatty alcohols:
Oxidation of 1-tetradecanol as a model substrate, Catal. Today.
[6] J. M. Pea, N. S. Allen, M. Edge, C. M. Liauw, and B. Valange, Factors affecting the
adsorption of fatty acids, alcohols and aromatic compounds on to carbon black pigments
(flow micro-calorimetry studies), Dyes Pigments, vol. 49, no. 1, pp. 2949, Apr. 2001.
[7] L.-C. Wang, L. He, Q. Liu, Y.-M. Liu, M. Chen, Y. Cao, H.-Y. He, and K.-N. Fan,
Solvent-free selective oxidation of alcohols by molecular oxygen over gold
nanoparticles supported on -MnO2 nanorods, Appl. Catal. Gen., vol. 344, no. 12, pp.
150157, Jul. 2008.
[8] X. Yang, X. Wang, and J. Qiu, Aerobic oxidation of alcohols over carbon nanotubesupported Ru catalysts assembled at the interfaces of emulsion droplets, Appl. Catal.
Gen., vol. 382, no. 1, pp. 131137, Jun. 2010.
[9] C. Parmeggiani and F. Cardona, Transition metal based catalysts in the aerobic
oxidation of alcohols, Green Chem., vol. 14, no. 3, pp. 547564, Jan. 2012.
[10] S. Mori, M. Takubo, K. Makida, T. Yanase, S. Aoyagi, T. Maegawa, Y. Monguchi, and
H. Sajiki, A simple and efficient oxidation of alcohols with ruthenium on carbon,
Chem. Commun., no. 34, pp. 51595161, Sep. 2009.

[11] G. Jenzer, M. S. Schneider, R. Wandeler, T. Mallat, and A. Baiker, PalladiumCatalyzed Oxidation of Octyl Alcohols in Supercritical Carbon Dioxide, J. Catal.,
vol. 199, no. 1, pp. 141148, Apr. 2001.
[12] N. Dimitratos, J. A. Lopez-Sanchez, and G. J. Hutchings, Selective liquid phase
oxidation with supported metal nanoparticles, Chem. Sci., vol. 3, no. 1, pp. 2044,
Nov. 2011.
[13] K. Yamaguchi and N. Mizuno, Supported Ruthenium Catalyst for the Heterogeneous
Oxidation of Alcohols with Molecular Oxygen, Angew. Chem., vol. 114, no. 23, pp.
47204724, Dec. 2002.
[14] Fatty alcohols oxidation, Mar-2013. .
[15] A. Villa, C. E-Chan-Thaw, M. Schiavoni, S. Campisi, D. Wang, and L. Prati,
Fragrances by selective oxidation of long-chain alcohols, Chin. J. Catal., vol. 35, no.
6, pp. 945951, Jun. 2014.
[16] A. Corma and H. Garcia, Supported gold nanoparticles as catalysts for organic
reactions, Chem. Soc. Rev., vol. 37, no. 9, pp. 20962126, Aug. 2008.
[17] Q. Kan, Y. Bi, Z. Ying, T. Wu, and K. Zhen, Catalytic oxidation of -eicosanol into
eicosanic acid in the presence of Ti-MCM-41 or active component supported Ti-MCM41 catalysts, Microporous Mesoporous Mater., vol. 4445, pp. 609617, Apr. 2001.
[18] A. Dijksman, I. W. C. E. Arends, and R. A. Sheldon, Efficient rutheniumTEMPOcatalysed aerobic oxidation of aliphatic alcohols into aldehydes and ketones, Chem.
Commun., no. 16, pp. 15911592, Jan. 1999.
[19] N. Dimitratos, A. Villa, D. Wang, F. Porta, D. Su, and L. Prati, Pd and Pt catalysts
modified by alloying with Au in the selective oxidation of alcohols, J. Catal., vol. 244,
no. 1, pp. 113121, Nov. 2006.
[20] A. Villa, N. Janjic, P. Spontoni, D. Wang, D. S. Su, and L. Prati, AuPd/AC as
catalysts for alcohol oxidation: Effect of reaction parameters on catalytic activity and
selectivity, Appl. Catal. Gen., vol. 364, no. 12, pp. 221228, Jul. 2009.
[21] T. Mallat and A. Baiker, Oxidation of alcohols with molecular oxygen on solid
catalysts, Chem. Rev., vol. 104, no. 2004, pp. 30373058.
[22] Y. Bi, M. Zhou, H. Hu, C. Wei, W. Li, and K. Zhen, Oxidation of Long Chain Primary
Alcohols to Acids over the Quaternary Ammonium Peroxotungstophosphate Catalyst
System, React. Kinet. Catal. Lett., vol. 72, no. 1, pp. 7382, Jan. 2001.
[23] T. Hara, M. Ishikawa, J. Sawada, N. Ichikuni, and S. Shimazu, Creation of highly
stable monomeric Pd(II) species in an anion-exchangeable hydroxy double salt
interlayer: Application to aerobic alcohol oxidation under an air atmosphere, Green
Chem., vol. 11, no. 12, pp. 20342040, Dec. 2009.
[24] T. Nishimura, Y. Maeda, N. Kakiuchi, and S. Uemura, Palladium(II)-catalysed
oxidation of alcohols under an oxygen atmosphere in a fluorous biphase system (FBS),
J. Chem. Soc. [Perkin 1], no. 24, pp. 43014305, Jan. 2000.
[25] Q. Kang, J. Luo, Y. Bai, Z. Yang, and Z. Lei, Catalytic oxidation of alcohols with
polymer-supported ruthenium complex under mild conditions, J. Organomet. Chem.,
vol. 690, no. 26, pp. 63096313, Dec. 2005.