32
Chapter 1 Introduction and Review of Literature Section 1.1: Introduction Section 1.2: Synthesis and Characterization of β-Amino Alcohols.
Chapter 1
Introduction and Review of Literature
Section 1.1: Introduction
Section 1.2: Synthesis and Characterization of β-Amino Alcohols.
Chapter 1
1
Section 1.1: Introduction
The ever rising prices of petrochemical feed stock and green house effect has turned out to be
the driving force for exploration of new alternative methodologies for getting important
industrial chemicals. Oleochemistry is a well-founded and well-developed branch of
chemistry and has been well exploited for industrial utilization. During the past decade,
production and utilization of oleochemicals have grown in size and diversity.1 Fat-derived
chemicals are essential to a variety of industrial areas such as protective coatings, surfactants,
plasticizers, lubricant additives, cosmetics, pharmaceuticals, soaps, detergents, textiles,
plastics, organic pesticides, urethane derivatives and a variety of synthetic intermediates.2 In
the industrial field, there has been competition between oleochemicals and petrochemicals.
The ever-increasing cost of petrochemicals has diverted the attention of chemists to the
synthesis of new oleochemicals derived from natural fats and oils.3
Fatty acids, fatty acid methyl esters, amines and alcohol as well as glycerol as a by-product
are the basic oleochemicals.4 The sources of oils and fats are various vegetable and animal
raw materials with the vegetable raw materials being the most important ones with respect to
the amounts involved. The annual global production of the major vegetable oils (from palm,
soy, rapeseed, cotton, peanut, sunflower, palm kernel, olive, and coconut) amounted to 84.6
million tons (Mt) in 1999/2000 and increased to 153.17 Mt in 2011/12.5 In addition, about 3.8
Mt of minor plant oils (from sesame, linseed, castor, corn) and about 22.1 Mt of animal fats
(tallow, lard, butter, fish) were produced and consumed in 1999, growing moderately to 4.4
Mt and 24.5 Mt, respectively, in 2008.6 These vegetable oils and most animal fats are mainly
produced in these large amounts for food purposes. Only castor and linseed oil are almost
exclusively used for industrial applications.7
As the triglycerides are the major constituent of oils, they provide major chunk of
commercial oleochemicals. Oleochemical transformations occur preferentially at the ester
1 Biermann, U.; Bornscheuer, U.; Meier, M. A. R.; Metzger, J. O.; Schafer, H. J.; Angew. Chem. Int. Ed. 2011,
50, 3854-3871. 2 Hosamani, K. M.; Hosamani, S. K. Ind. Eng. Chem. Res. 1994, 33, 1062-1066.
3 Gunstone, F. D.; Fatty Acid and Lipid Chemistry, 1
st ed.; Blackie Academic & Professional: London, 1996, pp.
1-243. 4 Gunstone, F. D. Oleochemical Manufacture and Applications, Academic Press, Sheffield, 2001, pp. 1-22.
5 United States Department of Agriculture, Oilseeds: World Markets and Trade Monthly Circular
http://www.fas.usda.gov/ oilseeds/circular/Current.asp. 6 Oil World Annual, WORLD OILS & FATS, 2009:http://econ.mpob.gov.my/economy/annual/stat2009/ei/
_world09.htm. 7 Gunstone, F. D. Lipid Technol. 2008, 20, 264.
Introduction and Review of Literature
2
functionality of triglycerides,8 hydrolysis yield fatty acids and glycerol and transesterification
to fatty acid methyl esters.9 Fatty acids are transformed to soaps, esters, amides and amines
by reacting at carboxy group. Hydrogenation of fatty acids and their methyl esters gives fatty
alcohols, which are used for the production of surfactants.10
These primary oleochemicals serve as the basic raw material for the formation of secondary
oleochemicals. The double bonds in triacylglycerols are other potential sites for chemical
modification. The major modification carried out to the double bond is hydrogenation and
epoxidation reaction. Hydrogination is the main source of the reaction for the production of
vegetable ghee and margarine. The plant oils, containing epoxy groups, formed from the
epoxidation of the double bonds in vegetable oils, are other important oleochemicals.11
Epoxidized vegetable oils have received growing interest in recent years. At the moment, one
of the most important epoxidized vegetable oil is soybean oil; its production in 1999 was
nearly 200,000 t which has now increased by about 56% in the year 2010.12
The epoxidized
soybean oil is a promising intermediate for chemical modification, because the epoxy groups
are susceptible to ring opening reactions.13
Epoxides have a wide range of industrial applications and are used as renewable feedstock for
the manufacture of intermediate products such as alcohols, glycols, alcoxyalcohols,
hydroxyesters, N-hydroxyalkylamides, mercaptoalcohols, hydroxynitriles, alkanolamines,
and carbonyl compounds.14
Epoxides can also be used as high-temperature lubricants, and the
products obtained from ring opening can be employed as low-temperature lubricants.15
8 Baumann, H.; Buhler, M.; Fochem, H.; Hirsinger, F.; Zoebelein, H.; Falbe, J. Angew. Chem. Int. Ed. 1988, 27,
41-62. 9 Anneken, D. J.; Both, S.; Christoph, R.; Fieg, G.; Steinberner, U.; Westfechtel, A. Ullmann’s Encyclopedia of
Industrial Chemistry, Online Ed. Wiley-VCH, Weinheim (Germany), 2006. 10
Noweck, K.; Grafahrend, W. Ullmann’s Encyclopedia of Industrial Chemistry, Online Ed. Wiley-VCH,
Weinheim (Germany), 2006. 11
Mungroo, R.; Pradhan, C. N.; Goud, V. V.; Dalai, K. A. J. Am Oil Chem Soc. 2008, 85, 887-896. 12
Goud, V. V.; Patwardhan, A. V.; Pradhan, N. C. J. Am Oil Chem Soc. 2006, 83, 635-640. 13
(a) Biswas, A.; Adhvaryu, A.; Gorden, S. H.; Erhan, S. Z.; Willett, J. L. J. Agric. Food Chem. 2005, 53, 9485-
9490. (b) Sharma, B. K.; Adhvaryu, A.; Erhan, S. Z. J. Agric. Food Chem. 2006, 54, 9866-9872. (c) Hwang, H.
S.; Erhan, S. Z. Ind. Crops Prod. 2006, 23, 311–317. (d) Wu, X.; Zhang, X.; Yang, S.; Chen, H.; Wang, D. J.
Am Oil Chem Soc. 2000, 77, 561-563. (e) Sharma, B. K.; Adhvarya, A.; Erhan, S. Z. J. Agric. Food Chem.
2006, 83, 129-136. (f) Doll, K. M.; Sharma, B. K.; Erhan, S. Z. Ind. Eng. Chem. Res. 2007, 46, 3513-3519. (g)
Biswas, A.; Sharma, B. K.; Willet, J. L.; Erhan, S. Z.; Cheng, H. N. Green Chem. 2008, 10, 298-303. (h)
Biswas, A.; Sharma, B. K.; Willet, J. L.; Vermillion, K.; Erhan, S. Z.; Cheng, H. N. Green Chem. 2007, 9, 85-
89. 14
Piazza, G. T. Recent Developments in the Synthesis of fatty acids derivatives. ed. By Knothe, G & Derksen. J.
T. P. AOCS Press, Champaign 1999, pp. 182-185. 15
(a) Sharma, B. K.; Liu, Z.; Adhvarya, A.; Erhan, S. Z. J. Agric. Food Chem. 2008, 56, 3049-3056. (b) Hwang,
H. S.; Erhan, S. Z. Ind. Crops Prod. 2006, 23, 311–317. (c) Hwang, H. S.; Erhan, S. Z. J. Am. Oil Chem. Soc.
2001, 78, 1179–1184. (d) Hwang, H. S.; Adhvaryu, A.; Erhan, S. Z. J. Am. Oil Chem. Soc. 2003, 80, 811–815.
Chapter 1
3
Epoxidized vegetable oil has also been used to synthesize polymer composites,16
hydrogels,17
and oleochemical carbonates18
. Epoxidized oils and their ester derivatives are used as
plasticizers and stabilizers of plastics19
and so they are used in the production of packing
materials such as wrapping foils.20
A simple perusal of the literature revealed that although
epoxy ring opening reaction of fatty acids/fatty acid methyl ester has been extensively used
for the preparation of a variety of oleochemicals21
yet, there was only a single report for the
synthesis of 1,2-amino alcohols.22
Further, Yoshimura et al23
has reported the preparation of
cationic surfactant using long chain epoxides.
Keeping these facts in view, we planned the present work with the following objectives.
1. To synthesize new long chain amino alcohols and cationic Surfactants from renewable as
well as petrochemical raw materials using epoxides as intermediates by cost effective and
energy saving methodology.
2. To characterize the structure of these new molecules by several available spectroscopic
techniques.
3. To evaluate surface properties of cationic amphiphiles by using techniques like surface
tension, conductivity and fluorescence method.
4. To study interaction of cationic gemini surfactants with DNA and evaluate their
cytotoxicity.
5. To measure thermal stabilities of cationic surfactants as synthesized above.
The work done to achieve the above objectives has been organized in two parts in the thesis.
Part I of the work deals with the synthesis and characterisation of long chain β-amino
alcohols by epoxy ring-opening reactions of epoxy fatty acid methyl ester.
16
(a) Liu, Z. S.; Erhan, S. Z.; Xu, J.; Calvert, P. D. J. Appl. Polym. Sci. 2002, 85, 2100-2107. (b) Liu, Z.; Erhan,
S. Z.; Xu, J. Polymer 2005, 46, 10119-10127. (c) Liu, Z.; Erhan, S. Z.; Akin, D. E.; Barton, F. E. J. Agric. Food
Chem. 2006, 54, 2134-2137. (d) Khot, S. N.; Lascala, J. J.; Can, E.; Morye, S. S.; Williams, G. I.; Palmese, G.
R. J. Appl. Polym. Sci. 2001, 82, 703-723. (e) Bunker, S. P.; Wool, R. P. J. Polym. Sci. 2002, 40, 451-458. 17
Liu, Z. S.; Erhan, S. Z. U. S. Patent Application 20070077298, 2007. 18
Dierker, M. Lipid Technol. 2004, 16, 130-134. 19
Piazzo, G. J.; Nunez, A.; Foglia, T. A. J. Am. Oil Chem. Soc.1999, 76, 551-555. 20
Piazzo, G. J.; Foglia, T. A.; Nunez, A. Biotechnol. Lett. 2000, 22, 217-221. 21
(a) Earle, F.R. J. Am. Oil. Chem. Soc. 1970, 47, 510–513. (b) Ayorinde, F. O.; Nana,V. E.; Nicely, D. P.;
Woods, S. A.; Nawaonicha, O. E. J. Am. Oil. Chem. Soc. 1997, 74, 531–538. (c) Singh, S.; Mahajan, S.; Kaur,
H. J. Am. Oil. Chem. Soc. 1999, 76, 103-107. (d) Guidotti, M.; Psaro, R.; Ravasio, N.; Sgobbo, M.; Carniato, F.;
Bisio, C.; Gatti, G.; Marchese, L. Green Chem. 2009, 11, 1173-1178. 22
Biswas, A.; Sharma, K. B.; Doll, M. K.; Erhan, Z. S.; Willett, L. J.; Cheng, N. H. J. Agric. Food Chem. 2009,
57, 8136–8141. 23
Yoshimura, T.; Ohno, A.; Esumi, K. Langmuir 2006, 22, 4643-4648.
Introduction and Review of Literature
4
While, in part II of the thesis we have discussed the synthesis and evaluation of new cationic
surfactants using the epoxy ring opening reactions.
Chapter 1
5
Part I
Review of Literature
Section 1.2: Synthesis and Characterization of β-Amino Alcohols.
β-Amino alcohols are an important class of organic compounds,24
the moiety is found in a
wide variety of biologically active alkaloids and peptides.25
They find applications, as a
building block in the organic synthesis26
of various natural products and pharmaceuticals.27
They are also useful as chiral auxiliaries and as ligands for transition metals for asymmetric
synthesis and catalysis.28
They are easily converted to many other molecules, including
amino acids and amino sugars.29
β-Amino alcohols also find applications as β-adrenergic
blockers, and they are widely used in the management of cardiovascular disorders,30
hypertention,31
angina pectoris, and cardiac arrhythmias.32
The transformation of an epoxy
ring to the respective β-amino alcohols is also a crucial step in the synthesis of anti-HIV
agents,33
protein kinase C inhibitor balanol,34
antimalarial agents,35
glycosidase inhibitor,36
liposidomycin B class of antibiotics,37
naturally occurring brassinosteroids,38
taxoid side
chain,39
diverse heterocycles40
and indoles.41
β-Amino alcohols are also useful as
intermediates in the synthesis of perfumes,42
dyes,43
photo developers,43
and oxazolidones.
24
(a) Azizi, N.; Saidi, M. R. Org. Lett. 2005, 7(17), 3649-3651. (b) Sekar, G.; Singh, V. K. J. Org. Chem. 1999,
64, 287-289 25
Olofsson, B.; Somfai, P. J. Org. Chem. 2002, 67, 8574-8583. 26
Reddy, L. R.; Reddy, M. A.; Bhanumathi, N.; Rao, K. R. New J. Chem. 2001, 25, 221-222. 27
Rodrı´guez, J. R.; Navarro, A. Tetrahedron Lett. 2004, 45, 7495–7498. 28
(a) Sundararajan, G.; Vijayakrishn, K.; Vargheseb, B. Tetrahedron Lett. 2004, 45, 8253–8256. (b) Ager, D. J.;
Prakash, I.; Schaad, D. R. Chem. Rev. 1996, 96, 835. (c) Chakraborti, A. K.; Kondaskar, A. Tetrahedron Lett.
2003, 44, 8315. 29
(a) Golebiowski, A.; Jurczak, J. Synlett 1992, 241. (b) Casiraghi, G.; Zanardi, F.; Rassu, G.; Spanu, P Chem.
Rev. 1995, 95, 1677. 30
Connolly, M. E.; Kersting, F.; Bollery, C. T. Prog. Cardiovasc. Dis. 1976, 19, 203. 31
De Cree, J.; Geukens, H.; Leempoels, J.; Verhaegen, H. Drug DeV. Res. 1986, 8, 109-117. 32
Owen, D. A. L.; Marsden, C. D. Lancet 1965, 1259. 33
Ruediger, E.; Martel, A.; Meanwell, N.; Solomon, C.; Turmel, B. Tetrahedron Lett. 2004, 45, 739. 34
Wu, M. H.; Jacobsen, E. N. Tetrahedron Lett. 1997, 38, 1693. 35
Lindsay, K. B.; Pyne, S. G. Tetrahedron 2004, 60, 4173. 36
Zhu, S.; Meng, L.; Zhang, Q.; Wei, L. Med. Chem. Lett. 2006, 16, 1854. 37
Moore, W. J.; Luzzio, F. A. Tetrahedron Lett. 1995, 36, 6599. 38
Mori, K.; Sakakibara, M.; Okada, K. Brassinolide and its analogs. V. Tetrahedron. 1984, 40, 1767. 39
Yamaguchi, T.; Harada, N.; Ozaki, K.; Hashiyama, T. Tetrahedron Lett. 1998, 39, 5575. 40
Lieoscher, J.; Jin, S.; Otto, A. J. Heterocycl. Chem. 2000, 37, 509. 41
Schirok, H. J. Org. Chem. 2006, 71, 5538. 42
Yang, Y.; Wahler, D.; Reymond, J. L. Helv. Chim. Acta. 2003, 86, 2928. 43
Ibaya, T.; Mizutani, T.; Inagi, T. Assignee, Yokkaichi Chemical Co., Ltd., Japan. JP Patent 02288850, 1990.
Introduction and Review of Literature
6
The long chain 2-amino alcohols possess a wide range of bioactivities i.e immunosuppresive,
anti-inflammatory, cytotoxities and induction of apoptosis.44
β-Amino alcohols have been synthesized via using different compounds i.e amino acids,45
α-
amino carbonyl,46
alkoxy carbonyl,47
epoxides48
and cyclic sulphates49
. Ring opening of
epoxides serve as a convenient method for the synthesis of 2-amino alcohols. The mechanism
for the aminolysis of epoxides involves the activation of epoxide ring with the help of acid
catalyst, which facilitate the nucleophile attack of amine to α or β carbon of the epoxide ring
depending upon the electronic and steric factor.50
Mechanism
Owing to the wide range of applications of amino alcohols, significant developments for their
synthesis by aminolysis of epoxide have been reviewed by several research groups.51
Bonollo et al reported a green route for the synthesis of long chain amino alcohols52
[4a, 5a
(major) & 4a*, 5a
* (minor); Scheme 1.2a] by reacting the terminal epoxy alkane (1a&2a)
with aniline (3a) under neat conditions at 60 °C for 40-170 hour.
44 Constantinou, K. V. Lett. Peptide Sci. 2003, 9, 143. 45
(a) Abiko, A.; Masamune, S. Tetrahedron Lett. 1992, 33, 5517. (b) McKennon, M. J.; Meyers, A. I. J. Org.
Chem. 1993, 58, 3568. (c) Seki, H.; Koga, K.; Matsuo, H.; Yamada, S. Chem. Pharm. Bull. 1965, 13, 995. (d)
Delair, P.; Einhorn, C.; Einhorn, J.; Luche, J. L. J. Org. Chem. 1994, 59, 4680. 46
Reetz, M. T.; Drewes, M. W.; Lennick, K.; Schmitz, A.; Holdgru¨n, X. Tetrahedron: Asymmetry 1990, 1, 375. 47
(a) Davis, F. A.; Haque, M. S.; Przelawski, R. M. J. Org. Chem. 1989, 54, 2021.(b) Jackson, W. R.; Jacobs,
H. A.; Matthews, B. R.; Jayatilake, G.S. Tetrahedron Lett. 1990, 31, 1447. 48
(a) Harris, C. E.; Fisher, G. B.; Beardsley, D.; Lee, L.; Goralski, C. T.; Nicholson, L. W.; Singaram, B. J. Org.
Chem. 1994, 59, 7746. (b) Coote, S. J.; Davies, S. G.; Middlemus, D.; Naylor, A. J. Chem. Soc., Perkin Trans. 1
1989, 2223. 49
(a) Gao, Y.; Sharpless, K. B. J. Am. Chem. Soc. 1988, 110, 7538. (b) Denmark, S. E. J. Org. Chem. 1981, 46,
3144. (c) Lowe, G.; Salamone, S. J. J. Chem. Soc., Chem. Commun. 1983, 1392. (d) Kim, B. M.; Sharpless, K.
B. Tetrahedron Lett. 1989, 30, 655. 50
Katritzky, A. R.; Rees, C. W. Comprehensive Heterocyclic Chemistry Ed. By Lwowski, W. Pergamon Press,
Ltd., Headington Hill Hall, Oxford Volume 7, 1984, pp 867. 51
(a) Agar, D. J.; Prakash, I.; Schaad, D. R. Chem. Rev. 1996, 96, 835-875 (b) Bergmeier, S. C. Tetrahedron
2000, 56, 2561-2576 (c) Pastor, I. M.; Yus, M. Current Organic Chemistry, 2005, 9, 1-29 52
Bonollo, S.; Fringuelli, F.; Pizzo, F.; Vaccaro, L. Green Chem. 2006, 8, 960-964.
Chapter 1
7
Regioselective synthesis of several long chain β-amino alcohols (7b-11b; Scheme 1.2b) was
reported by Rodriguez et al27
by reacting decenyl oxide (1b) with substituted aniline (2b-6b)
using indium tribromide as catalyst and dichloromethane as a solvent at room temperature.
Conte et al53
regioselectively synthesized several fluorinated long chain amino alcohols (8c-
13c; Scheme 1.2c), by ring opening of long chain [(perfluoroalkyl)methyl] oxirane (1c) with
some primary and secondary aliphatic amines (2c-7c) at 85-100 °C.
53
Conte, L.; Maniero, F.; Zaggia, A.; Bertani, R.; Gambaretto, G.; Berton, A.; Seraglia, R. J. Fluorine Chem.
2005, 126, 1274-1280.
Introduction and Review of Literature
8
Table 1.2(i): Ring opening of [(perfluoroalkyl)methyl] oxiranes with some primary and
secondary aliphatic amines. R1 R2 Time (hr) Product, Yield (%)
C2H5 C2H5 12 (8c), 79%
But C2H4O(CO)C(CH3)=CH2 17 (9c), 84%
H CH2CH=CH2 5 (10c), 67%
C2H5 C2H4OH 2 (11c), 92%
C2H4OH C2H4OH 6 (12c), 98%
Azizi & Saidi24a
regiolectively synthesized several short chain aliphatic derivatives (8d-16d)
by reacting aliphatic amines (3d-7d) with aliphatic epoxides (1d&2d) in water (Scheme
1.2d).
Table 1.2(ii): Reactions of Aliphatic Epoxides with Aliphatic amines in water. Epoxide Amine Product Yield %
(3d)
(8d)
96
(4d)
(9d)
93
(5d)
(10d)
94
(6d) (11d)
89
(2d)
(3d)
(12d)
97
(4d)
(13d)
90
Chapter 1
9
(5d)
(14d)
88
(6d) (15d)
90
(7d)
(16d)
92
The preparation of β-amino alcohols (8d-16d) in water is desirable, since using H2O instead
of an organic solvent has become more important due to environmental considerations in
recent years.
Reddy et al reported regiolective synthesis of several β-amino alcohols26
(13e-28e, Scheme
1.2e), by the cleavage of epoxides with aromatic amines using indium trichloride as a catalyst
in dichloromethane at room temperature.
Table 1.2(iii): Indium trichloride catalysed epoxide opening with aromatic amines. R1 R2 Product Yield %
For n = 1 H Ph 13e 78
H C6H4-o-CH3 14e 81
H C6H4-o-OCH3 15e 80
H α-naphthyl 16e 76
H C6H4-p-NO2 17e 75
For n = 2 H Ph 18e 90
H C6H4-o-CH3 19e 88
H C6H4-p-CH3 20e 94
H C6H4-o-OCH3 21e 90
H C6H4-p-OCH3 22e 96
H C6H4-m-Br 23e 92
H C6H4-p-Br 24e 94
H C6H4-p-F 25e 95
H C6H4-p-NO2 26e 80
H α-naphthyl 27e 84
H β-naphthyl 28e 92
The unusual feature of this reaction as reported by them is that only aromatic amines opened
the epoxide ring, whereas aliphatic amines such as diethyl amine, benzyl amine, and
Introduction and Review of Literature
10
pyrrolidine failed to react with the epoxides at room temperature. The lack of reactivity of
aliphatic amines may be due to stronger complexation with the catalyst as a consequence of
their higher basicity.
Sekar & Singh24b
reported regiolective synthesis of β-amino alcohols (4f&5f, Scheme 1.2f),
by reacting cyclic epoxides (1f&2f) with aniline (3f) using Cu(OTf)2 or Sn(OTf)2 as a
catalyst.
Solvent-free direct regioselective ring opening of various epoxides (1g-4g) with
benzimidazole (5g) to prepare 1-(β-hydroxyalkyl) benzimidazoles (6g-9g) was reported by
Torregrosa et al54
(Scheme 1.2g).
Table 1.2(iv): Ring opening of various epoxides with benzimidazole under solvent-free
conditions. Epoxide Product Yield %
O
Ph
(1g)
N
NOH
Ph
(6g)
62
OPhO
(2g) N
NOH
OPh
(7g)
71
54
Torregrosa, R.; Pastor, I. M.; Yus, M. Tetrahedron 2007, 63, 469-473.
Chapter 1
11
O
(3g)
N
NOH
(8g)
74
(4g)
N
N
OH
(9g)
86
Sreedhar et al55
reported ring opening of styrene oxide (1h) with various amines (2h-5h)
using monodispersed silica nanoparticles in water (Scheme 1.2h). In this work,
monodispersed silica nanoparticles were synthesised and used as catalyst for the synthesis of
β-amino alcohols under ambient conditions in shorter reaction times. The use of water as
‘green’ solvent allows easy recycling of the catalyst. Aryl amines reacted with styrene oxide
in a regioselective manner to give the corresponding β-amino alcohols (6h-9h) with
preferential nucleophilic attack at benzylic position (entry 1) whereas, the aliphatic amines on
reaction with styrene oxide gave the product in good yields with preferential attack at the
non-benzylic terminal carbon (entries 2-3, Table 1.2 (v)).
Table 1.2(v): Ring opening of styrene oxide with various amines at room temperature
using silica particles in water.
Entry Amine Product Time (min) Yield (%) Ratio
h:h*
1
(2h)
(6h)
50 75 100:0
2
n-BuNH
n-Bu (3h)
n-BuN
n-BuOH
(7h)
25 80 10:90
55
Sreedhar, B.; Radhika, P.; Neelima, B.; Hebalkar, N. J. Mol. Catal. A: Chem. 2007, 272, 159-163.
Introduction and Review of Literature
12
3 NH2( )3
(4h)
HN
( )3
OH
(8h)
30 75 35:65
4 ( )5
NH2
(5h)
( )5NH
OH
(9h)
25 77 30:70
Chakraborti et al56
reported 2-phenyloxirane based β-amino alcohols (6i-9i; Scheme 1.2i),
using silica gel as catalyst. The catalyst was separated at the end of the reaction, reactivated
by heating at 100 °C under vacuum for 10 hour and reused for the fresh batch.
Catalytic asymmetric ring opening of meso-epoxides (1j-3j) with aromatic amines (4j-8j) in
the presence of 1 mol% of Sc(OSO3C12H25)3 and 1.2 mol% of a chiral bipyridine ligand in
water gave the corresponding β-amino alcohols (9j-15j; Scheme 1.2j) in high yields with
excellent enantioselectivities.57
Table 1.2(vi): Asymmetric ring opening of meso-Epoxides with aromatic amines.
Entry Epoxide Amine Product Yield % ee %
1
(1j) (4j)
(9j)
89 91
56
Chakraborti, A. K.; Rudrawar, S.; Kondaskar, A. Org. Biomol. Chem. 2004, 2, 1277-1280. 57
Azoulay, S.; Manabe, K.; Kobayashi, S. Org. Lett. 2005, 7(21), 4593-4595.
Chapter 1
13
2
(5j)
(10j)
88 96
3
(6j)
(11j)
81 93
4
(7j)
(12j)
83 91
5
(8j)
(13j)
85 86
6
(2j)
(4j)
(14j)
75 91
7
(3j)
(4j)
(15j)
61 60
Ring opening of 5,6-dihydro-5,6-epoxy-1,10-phenanthroline (1k) with 4-methylaniline (2k)
and 4-methoxyaniline (3k; Scheme 1.2k) in water at room temperature without any Lewis
acid catalyst gave only one diastereomer of amino alcohols [monohydrate of 6-(methyl-
phenylamino)-5,6-dihydro-1,10-phenanthrolin-5-ol (4k) and 6-(4-methoxyphenyl-amino)-
5,6-dihydro-1,10-phenanthrolin-5-ol (5k)].58
58
Shee, N. K.; OluwafunmilayoAdekunle, F. A.; Das, D.; Drew, M. G. B.; Datta, D. Inorg. Chim. Acta 2011,
375, 101-105.
Introduction and Review of Literature
14
Robinson et al59
reported synthesis of β-amino alcohol (3l) by reacting aniline (2l) with
1a,2,3,7b-tetrahydronaphtho[1,2-b]oxirene (1l) in the presence of mesoporous aluminosilicate
as catalyst at room temperature.
Bedore et al60
reported microreactor-assisted ring opening of 1,4-dihydronaphthalene (1m)
with indoline (2m) to synthesize β-amino alcohol (3m; Scheme 1.2m). Furthermore, 1-2% of
regioisomer of (3m) was also isolated but not quantified. Comparison of microwave batch
reaction reveals that conditions obtainable in the microreactor can match or improve yield in
many cases.
Table 1.2(vii): Reaction conditions for ring opening of 1,4-dihydronaphthalene (1m)
with indoline (2m) in both microwave and microreactor system.
Entry Conditionsa
(psi) Amine equiv Temp (°C) Flow rateb (mL/min)
Time
(min) Product 3m (%) Conversion (%)
1 Batch (mw) 1.2 150 - 30 54 58
2 mreactor (250) 1.2 150 4 30 39 40
3 mreactor (250) 1.2 195 4 30 66 72
4 mreactor (500) 1.2 245 4 30 71 93 a All reactions were run in ethanol at 1M concentration in epoxide,
b combined flow rate of both reagents.
59
Robinson, M. W. C.; Timms, A. D.; Williams, M. S.; Graham, A. E.; Tetrahedron Letters 2007, 48, 6249-
6251. 60 Bedore, M. W.; Zaborenko, N.; Jensen, K. F.; Jamison, T. F. Org. Process Res. Dev. 2010, 14, 432-440.
Chapter 1
15
Regioselective glycidic ether based amino alcohols (6n-9n) were prepared by reacting
glycidic derivatives (1n-4n) with aniline (5n) in the presence of Zn(BF4)2.xH2O as catalyst at
room temperature under solvent-free conditions (Scheme 1.2n).61
The attack by the
nucleophile at the less substituted carbon atom of the epoxide ring resulted in the formation
of only single product.
Table 1.2(viii): Zn(BF4)2.xH2O Catalysed ring opening of various epoxides with aniline.
Epoxide Time
(min) Product Yield (%)
(1n)
45
(6n)
83
(2n)
60
(7n)
89
(3n)
30
(8n)
87
(4n)
30
(9n)
92
Regioselective synthesis of glycidyl aryl ethers based amino alcohols (8o-12o), by reacting
several glycidyl aryl derivatives (1o-4o) with various amines (5o-7o) in the presence of
samarium triflate as catalyst at 0 °C under solvent-free conditions was reported by Yadav et
al (Scheme 1.2o).62
This protocol has also been applied for the synthesis of various β-
blockers.63
61
Pujala, B.; Rana, S.; Chakraborti, A. K. J. Org. Chem. 2011, 76, 8768-8780. 62 Yadav, J. S.; Reddy, A. R.; Narsaiah, A. V.; Reddy, B. V. S. J. Mol. Catal. A: Chem. 2007, 261, 207-212. 63
Corey, E. J.; Zhang, F. Angew. Chem. Int. Ed. 1999, 38, 1931.
Introduction and Review of Literature
16
Table 1.2(ix): Samarium triflate catalysed regioselective ring opening of epoxides.
Epoxide Amine Product Time
(h)
Yield
(%)
(1o)
(5o)
O
OH
NH
(8o)
2.0 89
(2o)
(6o)
NO2
O
HO
NH
(9o)
2.5 90
O
O
BnO
BnO (3o)
(6o)
OBnO
BnO
HO
NH
(10o)
2.0 90
O
O
MeO
O
(4o)
(6o)
O
MeO
HO
NH
(11o)
2.0 92
(4o)
(7o)
O
MeO
O
HO
N
N
(12o)
2.5 89
Regioselective microwave-assisted ring opening of benzyl glycidyl ether (1p) with various
amines (2p-9p) without catalyst to synthesize a series of 1-aminopropan-2-ols (10p-17p;
Scheme 1.2p) was reported by Robin et al64
.
64
Robin A.; Brown, F.; Bahamontes-Rosa, N.; Wu, B.; Beitz, E.; Kun, J. F. J.; Filtsch, S. L. J. Med. Chem.
2007, 50, 4243-4249.
Chapter 1
17
Table 1.2(x): Synthesis of β-amino alcohols 10p-17p.
Pachon et al65
reported ring opening of ethyl 3-phenylglycidate (1q) with aromatic and
aliphatic amines (2q-4q) in the presence of zinc(II) chloride as catalyst, to form the
corresponding isomeric mixture of β-amino alcohols (5q-7q and 5q*-7q
*; Scheme 1.2q).
Low reactivities were observed during this reaction. The low reactivities has been attributed
65 Pachon, L. D.; Gamez, P.; van Brussel, J. J. M.; Reedijk, J. Tetrahedron Lett. 2003, 44, 6025-6027.
Amine Product Yield
(%)
NH2 (2p)
OBn
OHHN
(10p)
89
NH2
(3p)
OBn
OHHN
(11p)
59
O
NH2
(4p)
OBn
OH
O
HN
(12p)
79
NHHN
(5p) OBn
OH
N
HN
(13p)
85
ONH2
(6p)
OBn
OH
O
HN
(14p)
58
S
NH2
(7p)
OBn
OHS
HN
(15p)
73
NNH2
(8p)
OBn
OHNNH
(16p)
47
NH2
(9p)
OBn
OHHN
(17p)
95
Introduction and Review of Literature
18
to chelating properties of ethyl 3-phenylglycidate which reduce the activation of the oxirane
ring by the zinc catalyst.
Table 1.2(xi): Zinc-catalysed ring opening of epoxide 1q.
Amine Product Ratio q:q*
Yield %
NH2
(2q)
Ph
OH
COOEt
HN
(5q)
91:9 40
HN
(3q) Ph
OH
COOEtN
(6q)
89:11 44
NH2
(4q) Ph
OH
COOEt
HN
(7q)
90:10 26
Ring opening of unsymmetrical 2-(but-3-en-1-yl)oxirane (1r) with aniline (2r) using two
different catalysts DABCO (1,4-diazabicyclic[2,2,2]octane) or tertiary amine (1 mol%) in
water gave the corresponding product (3r) in good yield under mild reaction conditions
(Scheme 1.2r).66
In this process regioselective formation of single isomer was observed due
to the attack of the nucleophile on the less substituted epoxide carbon.
66
Wu, J.; Xia, H. G. Green Chem. 2005, 7, 708-710.
Chapter 1
19
Ring opening of 2-((allyloxy)methyl)oxirane (1s) with various aromatic amines (2s-5s) in
water using heteropoly acids as catalyst was reported by Saidi & Azizi,67
leading to the
formation of the corresponding positional isomers of β-amino alcohols (6s-9s; Scheme 1.2s)
with moderate to excellent yields (76-93)%.
Fagnou & Lautens reported68
that [Rh(CO)2Cl]2 is an effective catalyst for the ring opening
of vinyl epoxides (1t-5t) with aromatic amines (6t-8t) under neutral conditions at room
temperature (Scheme 1.2t). The reaction occurs with excellent diastereo- and regioselectivity
(>20:1) gave the trans-1,2-amino alcohols for a wide range of substrates. However, aliphatic
amines failed to react under these conditions. This was due to the strong binding of aliphatic
amines to rhodium metal, causing the catalyst poisoning. Since aromatic amines are less basic
than aliphatic amines, this mode of binding would be significantly reduced.
Table 1.2(xii): Reactions of Vinyl Epoxides with Aromatic Amines.
S.No Epoxide Product Yield %
1 O
(1t)
(9t)
91
2 PhO
(2t)
Ph
NMePh
OH (10t)
93
67
Azizi, N.; Saidi, M. R. Tetrahedron 2007, 63, 888-891. 68 Fagnou, K.; Lautens, M. Org. Lett. 2000, 2, 2319-2321.
Introduction and Review of Literature
20
3 EtO
O
O (3t)
(11t)
91
4 O
O
O
(4t) (12t)
89
5
O( )2
(5t)
NMePh
OH( )2
(13t)
92
Enantioselective copper-catalysed ring opening of racemic ethynyl epoxides (1u) with amines
(2u-12u) using (R)-DTBM-MeO-BIPHEP (BIPHEP = 2,2’-Bis(diphenylphosphino)-1,1’-
diphenyl) as a chiral ligand gave the corresponding chiral β-ethynyl-β-amino alcohols (13u-
23u; Scheme 1.2u) in high yields with up to 94% ee.69
Table 1.2(xiii): Enantioselective Copper-Catalysed ring opening reactions of 1u with
amines. S.no R1 R2 Time (h) Yield (%) ee (%)
1 Ph H 1 95 (13u) 79
2 4-MeC6H4 H 3 96 (14u) 75
3 4-MeOC6H4 H 2 85 (15u) 57
4 4-ClC6H4 H 3 94 (16u) 87
5 4-BrC6H4 H 2 95 (17u) 89
6 4-CF3C6H4 H 3 93 (18u) 94
7 3-CF3C6H4 H 2 94 (19u) 86
8 4-MeOC(O)C6H4 H 2 95 (20u) 93
9 2-MeOC(O)C6H4 H 2 97 (21u) 79
10 4-CNC6H4 H 46 96 (22u) 88
11 4-NO2C6H4 H 18 94 (23u) 85
69
Hattori, G.; Yoshida, A.; Miyake, Y.; Nishibayashi, Y. J. Org. Chem. 2009, 74, 7603-7607.
Chapter 1
21
March-Cortijos & Snape70
synthesized asymmetric β-amino tertiaray alcohols via ring-
opening of an unsymmetrical epoxide with primary and secondary amines (Scheme 1.2v).
The result revealed that primary amines gave symmetrical triol products following an
undesired acyl migration reaction, whereas secondary amines gave the desired chiral
(racemic) products.
Table 1.2(xiv): Results of amine addition to epoxide 1v.
Entry Amine Product Yield (%)
1 NH2
(2v)
HO OHOHHN
(6v
*)
93
2 NH2
(3v)
HO OHOHHN
(7v
*)
96
3 NH
(4v)
HO OAcOHN
(8v)
80
4 NH
(5v)
HO OAcOHN
(9v)
55
Dialkylated amine precursors (7w-11w) were synthesized by Koning et al71
(Scheme 1.2w)
by reacting two equivalents of epoxide (1w) with the polyamines (2w-6w) in ethanol. All
these reactions with epoxide were carried out exclusively at the primary amine sites. Trans
opening of epoxide was assumed to occur, and each product was formed as a mixture of
diastereoisomers.
70
March-Cortijos, A.; Snape, T. J. Org. Biomol. Chem. 2009, 7, 5163-5165. 71 De Koning, C. B.; Hancock, R. D.; van Otterlo, W. A. L. Tetrahedron Lett. 1997, 38, 1261-1264.
Introduction and Review of Literature
22
Table 1.2(xv): Dialkylation of Polyamines with epoxide 1w.
Polyamine Product, (Yield)
NH
NH2H2N
(2w)
(7w) 58%
NHNH2 NH2
(3w)
(8w) 51%
NH2H2N (4w)
(9w) 56%
NH2NH2 (5w)
(10w) 100%
NH
NH
H2N NH2
(6w)
(11w) 58%
Ring opening reactions of various epoxides (1x-4x) with amino acids (5x-14x) in the
presence of Ca(OTf)2 as catalyst to synthesize corresponding amino alcohols (15x-29x,
Scheme 1.2x) were reported by Babic et al.72
Furthermore, in reactions where racemic
epoxides (1x-4x) and enantiometrically pure amino acid esters were used as starting
compounds, the products were equimolar mixture of two diasteroisomers. In cases where
racemic amino acid esters were used, the products were equimolar mixtures of four
diasteroisomers (products 23x, 24x and 27x). In future, this method can be used in a straight
forward way for the preparation of hydroxyethylamine dipeptide isosteres.
72
Babic, A.; Sova, M.; Gobec, S.; Pecar, S. Tetrahedron Lett. 2006, 47, 1733-1735.
Chapter 1
23
Table 1.2(xvi): Hydroxyethylamine dipeptide isosteres obtained via Scheme 1.2x.
Entry Epoxide (R1) Protected amino acid (R2, R3) Product Yield (%)
1 PhOCH2 (1x) CH3, Bn (L-Ala) (5x) 15x 61
2 CH3, Et (L-Ala) (6x) 16x 68
3 CH3, t-Bu (L-Ala) (7x) 17x 54
4 CH2Ph, Me (L-Phe) (8x) 18x 65
5 CH(CH3)2, Bn (L-Val) (9x) 19x 76
6 PhtCH2 (2x)a H, Bn (Gly) (10x) 20x 52
7 CH3, Bn (L-Ala) (5x) 21x 74
8 CH(CH3)2, Bn (L-Val) (9x) 22x 63
9 (CH2)2SCH3, Et (D, L-Met) (11x) 23x 72
10 (CH2)2SCH3, Bn (D, L-Met) (12x) 24x 67
11 CH2Ph, Et (L-Phe) (13x) 25x 62
12 CH3, t-Bu (L-Ala) (7x) 26x 61
13 PhtCH2CH2O (3x)b,c
(CH2)2SCH3, Et (D, L-Met) (11x) 27x 71
14 CH3, Bn (D-Ala) (14x) 28x 53
15 Bn2NCH(CH3) (4x)d CH3, Bn (L-Ala) (5x) 29x 77
a Refers to yields of isolated diastereoisomeric mixtures after circular chromatography.
b Pht = Phthalimido group.
c 1c was synthesised according to reported procedures.
d 1d was synthesised according to reported procedures.
Enantioselective ring-opening reactions of 1-aryloxy-2,3-epoxypropanes (1y-7y) with
arylamines (8y&9y) in presence of rat liver microsomes to synthesize 2-(S)-propanol amines
(10y-20y; Scheme 1.2y) was reported by Kamal et al.73
Table 1.2(xvii): Liver microsomes mediated ring opening of racemic epoxides with
arylamines. Entry Ar Product, Yield % ee
1 For R = H 4-AcNHC6H4 (10y), 43% 77
2 4-ClC6H4 (11y), 42% 57
3 2-MeCOC6H4 (12y), 46% 52
4 2-PhCOC6H4 (13y), 27% 65
5 α-naphthyl (14y), 46% 75
6 For R = Cl Ph (15y), 40% 86
7 4-AcNHC6H4 (16y), 37% 51
8 4-MeOC7H4 (17y), 38% 61
73
Kamal, A.; Rao, A. B.; Rao, M. V. Tetrahedron Lett. 1992, 33, 4077-4080.
Introduction and Review of Literature
24
9 2-MeCOC6H4 (18y), 48% 88
10 2-PhCOC6H4 (19y), 33% 68
11 α-naphthyl (20y), 41% 85
Kas’yan et al74
reported ring opening reactions of p-nitrophenyloxirane with amines
containing fragments with bicyclic skeleton (Scheme 1.2z). Regioselective aminolysis of
epoxide (1z) with amines (2z-7z) to synthesize amino alcohols (8z-13z) containing skeleton
fragments of norbornene, norbornane, and epoxynorbornane was carried out in 2-propanol
solution at room temperature.
Table 1.2(xviii): Reactions of p-nitrophenyloxirane with amines. Amines Product Yield %
79.4
84.2
82.4
67.4
79.6
88.6
74
Kas’yan A. O.; Golodaeva, E. A.; Tsygankov, A. V.; Kas’yan L. I. Russian J. Org. Chem. 2002, 38, 1606-
1614.
Chapter 1
25
90.9
74.8
Martina et al75
reported the synthesis of highly water-soluble multidentate amino alcohol β-
cyclodextrin (β-CD) derivatives (Scheme 1.2a’) via nucleophilic epoxide ring opening
reactions with mono-6-amino mono-6-deoxy-permethyl-β-CD (2a’) and mono-6-amino
mono-6-deoxy-β-CD (3a’) under microwave (MW) irradiation. A regioselective epoxide
opening reaction was observed in the reaction with styrene oxide while the stereoselectivity
was strictly dependent on substrate structure.
75
Martina, K.; Caporaso, M.; Tagliapietra, S.; Heropoulos, G.; Rosati, O.; Cravotto, G. Carbohydr. Res. 2011,
346, 2677-2682.
Introduction and Review of Literature
26
The binding properties of the β-CD were enhanced by linking amino alcohol subunits which
markedly improved its solubility.
Table 1.2(xix): Results of alkylation of mono-6-amino mono-6-deoxy-permethyl-β-CD
(2a’) and mono-6-amino mono-6-deoxy-β-CD (3a’) with styrene (1a’) and cyclohexene
oxide (6a’). Entry Reagent Eq. Epoxide Reaction condition, time Product, Yield
1 2a’ 1 DMF, 85 °C, 4 h, MW (4a’), 52%
2 3a’ 5 DMF, 85 °C, 4 h, MW (5a’), 32%
3 2a’ 4 DMF, 85 °C, 4 h, MW (7a’), 27%
4 3a’ 10 DMF, 85 °C, 4 h, MW (8a’), 30%
A survey of the literature revealed that although several epoxy ring containing fatty acid
methyl esters have been used for the synthesis of a variety of oleochemicals21
, yet, except for
the most recent report by Biswas et al22
there is no report on the epoxy ring opening reaction
in fatty acid methyl esters with amines. Unusual fatty acids like epoxy fatty acids are valuable
to chemical industry. The epoxidised oils/fatty acids are obtained either from natural
sources76
or by the epoxidation of unsaturated natural oils like soybean and linseed oil.77
Among the naturally occurring epoxy vegetable oils the most important are vernomia species,
which are rich source of vernolic acid (cis-12,13-epoxyoctadeca-cis-9-enoic).78
The seeds of
Vernonia galamensis79
contain substantially higher amounts of vernolic acid (74%) than
compared to Vernonia anthelmintica80
(67%) and Euphorbia lagascae81
(60%). The seed oil
of Bernordia pulchella (Euphorbiaceae) contains about 91% of vernolic acid82
, the largest
percentage of epoxy fatty acid content, reported in seed oils till date. The coronaric (cis-9,10-
epoxyoctadeca-cis-12-enoic) acid, the isomer of vernolic acid, has been reported in Turnera
ulmifolia (22.3%) seed oils.83
The vernolic acid in its varying amount has also been reported
from the seed oils of Geranium sanguineum84
(7%), Kigelia pinnata85
(22.3%), Malva
sylvestris86
(1.6%), Hibiscus canabinus87
(4.16%), and Hibiscus sabdariffa80
(3.52%). The
76
Biermann, U.; Friedt, W.; Lang, S.; Luhs, W.; Machmuller, G.;Metzger, J. O.; Ruschgen, K. M.; Schafer, H.
J.; Schneider, M. P. Angew Chem Int Ed. 2000, 39, 2206-2224. 77
Perdue, R. E.; Carlson, K. D.; Gilbert, M. G. Ec Bot 1986, 40, 54-68. 78
Badami, R. C.; Patil, K. B. Prog Lipid Res. 1981, 19, 119-153. 79
Thompson, A. E.; Dierig, D. A.; Johnson, E. R.; Dahlquist, G. H.; Kleiman, R. Ind. Crops Prod. 1994, 3, 185-
200. 80
Higgins, J. J. Agronomy J. 1968, 60, 55-58. 81
Pascual-Villalobos, M. J.; Ortiz, J. M.; Correal, E. Seed Sci. Technol. 1993, 21, 53-60. 82
Spitzer, V.; Aitzetmiiller, K.; Vosmann, K. J. Am. Oil Chem. Soc. 1996, 73, 1733. 83
Hosamani, K. M. Phytochemistry 1993, 34, 1363-1365. 84
Tsevegsuren, N.; Aitzetmuller, K. Lipids 2004, 39, 571 85
Afaque, S.; Siddiqui, M. M.; Ahmad, I.; Siddiqui, M. S.; Osman, S. M. Eur. J. Lipid Sci. Technol. 1987, 89,
433-435. 86
Mukarran, M.; Ahmad, M. J. Am. Oil Chem. Soc. 1984, 61, 1060. 87
Wang, M. L.; Morries, B.; Tonnis, B.; Davis, J.; Pederson, G. A. J. Agri. Food Chem. 2012, 60, 6620-6626.
Chapter 1
27
co-occurrence of coronaric and vernolic acid (about 2.5%) have been found in peanut
(Arachis hypogaea) germplasm seed oil.88
Seed oils of Lactuca scariola, L. Sativa and
Siegesbeckia orientalis were found to contain epoxy acids in 10.0% (6.0% coronaric + 4.0%
vernolic), 27.4% (16.9% coronaric + 10.5% vernolic) and 20.0% (16% coronaric + 4.0%
vernolic) amount, respectively, alongwith normal fatty acids.89
Seed oil rich in epoxy fatty acids have raised interest among the oil chemists being important
for the industrial utilization. Long chain epoxy fatty acids can be transformed into a number
of chemical derivatives such as epoxy resins, lubricant, lubricant additives, insecticides,
insect repellents, crop oil concentrates, adhesives, coatings, slow release of pesticides and
herbicides, metal coatings and plasticized phenolic resins.90
The derivatives formed during
ring opening of epoxides can also be used to construct some non-shrinking dental composite
materials91
and biobased industrial materials.92
Swern et al93
have evaluated the carcinogenic
activity of epoxy compounds.
Earlier, some work has been carried out in our laboratory to synthesise oligoethylene glycols
(5b’-7b’) from the seed oil of vernonia anthelmintica (Scheme 1.2b’).94
88 Hammond, E. G.; Duvick, D.; Wang, T.; Dodo, H.; Pittman, R. N. J. Am. Oil Chem. Soc, 1997, 74, 1235-
1239. 89
Ansari, M. S.; Ahmad, S.; Ahmad, F.; Ahmad, F.; Ahmad, M.; Osman, S. M. Fat Sci. Technol. 1987, 89, 116-
118. 90
Carlson, K. D.; Chang, S. P. J. Am. Oil Chem. Soc. 1985, 62, 934-939. 91
Schweikl, H.; Schmalz, G. Mutation Research 2002, 521, 19-27. 92
Piazza, J. G.; Foglia, A. T. J. Am. Oil Chem. Soc. 2006, 83, 1021-1025 93
Swern, D. Weider, R.; Donough, M. M.; Meranze, D. R.; Shimkin, M. B. Cancer Res. 1970, 30, 1037. 94
Singh, S. J. Am. Oil Chem. Soc. 1997, 74, 609-611.
Introduction and Review of Literature
28
The oligoethylene glycols (5b’-7b’) were further utilised to synthesize tetrahydrofuran ring
containing oligoethylene glycol ethers (17b’-19b’).21c
Erhan et al95
reported the reaction of epoxidised soybean oil (ESBO, 1c’) with acid
anhydrides (2c’-8c’) in the presence of catalytic amount of boron trifluoride diethyl etherate
to get the diester derivatives (9c’-15c’).
95
Erhan, S. Z.; Sharma, B. K.; Liu, Z.; Adhvarya, A. J. Agric. Food Chem. 2008, 56, 8919-8925.
Chapter 1
29
These diester derivatives were studied for their low-temperature properties, oxidation
stability, and friction-wear properties. The chemically modified soybean oil derivatives
having diester substitution at the sites of unsaturation have potential in the formulation of
industrial lubricants.
Biswas et al13a
reported synthesis of diethylamine-Functionalized soybean oil from
epoxidized soybean oil (Scheme 1.2d’). Epoxidized soybean oil (ESBO) was reacted with
diethyl amine (1d’) in the presence of catalytic amount of ZnCl2 at 80 °C to give the
corresponding diethyl amine derivative (2d’) of epoxidised soybean oil. The functionalised
soybean oil exhibit excellent antioxidant and lubricant properties. It has also been found to be
effective antifriction agent.
Synthesis of hydroxy thio-ether derivatives of vegetable oil was reported by Erhan et al.13b
In
this process common organic thiols [1-butanethiol (1e’), 1-decanethiol (2e’), 1-
octadecanethiol (1e’)] were reacted with epoxidised soybean oil (ESBO) in the presence of
perchloric acid as catalyst at 45 °C to get the hydroxy thio-ether derivatives (4e’-6e’; Scheme
1.2e’).
Introduction and Review of Literature
30
Doll et al13f
reported several branched methyl α-hydroxy stearate esters (6f’-9f’; Scheme
1.2f’). These α-hydroxy stearates were directly synthesised by reacting methyl epoxy stearate
(1f’) with several organic acids i.e levulinic acid (2f’), propionic acid (3f’), hexanoic acid
(4f’) and octanoic acid (5f’).
Biswas et al96
reported an environmentally friendly pathway for the preparation of azide
derivatives of fatty esters (3g’) by reacting epoxidised methyl oleate (1g’) and sodium azide
(2g’) in the presence of water by using ionic liquid as catalyst (Scheme 1.2g’).
96
Biswas, A.; Sharma, B. K.; Willett, J. L.; Advaryu, A.; Erhan, S. Z.; Cheng, H. N. J. Agric. Food Chem. 2008,
56, 5611-5616.
Chapter 1
31
We in our present study has reacted the methyl 9, 10-epoxyoctadecanoate and methyl 10, 11-
epoxyundecanoate with a variety of aliphatic (butyl, octyl), cyclic (pyrrolidine, piperidine,
morpholine) and aromatic (p-chloro aniline, p-anisidine, benzyl amine and aniline) amines to
get the respective β-amino alcohols (described in the next chapter).
