Synthesis of β-Amino Alcohols from Methyl Epoxy Stearate - Industrial

Feb 22, 2010 - In continuation of our work, we here wish to report solvent-free methodology for the synthesis of a number of β-amino alcohols from in...
0 downloads 0 Views 261KB Size
Download PDF
3106

Ind. Eng. Chem. Res. 2010, 49, 3106–3111

Synthesis of β-Amino Alcohols from Methyl Epoxy Stearate Sukhprit Singh* and Raman Kamboj Department of Chemistry, Guru Nanak DeV UniVersity, Amritsar, 143 005, India

Oils and fats are an important source of renewable raw materials, and the availability of functionalized fatty acids such as epoxy ring containing fatty acids gives us a convenient source of starting materials for the synthesis of various biodegradable derivatives. Methyl esters of the epoxidized oleic acid [methyl 9,10epoxy octadecanoate (1)] on the catalytic epoxy ring opening reaction with various aliphatic [butyl (2), octyl (3)], cyclic [pyrrolidine (4), piperidine (5), morpholine (6)], and aromatic [p-chloroaniline (7), p-anisidine (8), benzyl amine (9), aniline (10)] amines resulted in the formation of the respective β-amino alcohols [methyl 9-(butylamino)-10-hydroxyoctadecanoate (11a)/methyl 10-(butylamino)-9-hydroxyoctadecanoate (11b), methyl 10-hydroxy-9-(octylamino)octadecanoate (12a)/methyl 9-hydroxy-10-(octylamino)octadecanoate (12b), methyl 10-hydroxy-9-(pyrrolidin-1-yl)octadecanoate (13a)/methyl 9-hydroxy-10-(pyrrolidin-1-yl)octadecanoate (13b), methyl 10-hydroxy-9-(piperidin-1-yl)octadecanoate (14a)/methyl 9-hydroxy-10-(piperidin-1-yl)octadecanoate (14b), methyl 10-hydroxy-9-morpholinooctadecanoate (15a)/methyl 9-hydroxy-10-morpholinooctadecanoate (15b), methyl 9-(4-chlorophenylamino)-10-hydroxyoctadecanoate (16a)/methyl 10-(4-chlorophenylamino)9-hydroxyoctadecanoate (16b), methyl 10-hydroxy-9-(4-methoxyphenylamino)octadecanoate (17a)/methyl 9-hydroxy-10-(4-methoxyphenylamino)octadecanoate (17b), methyl 9-(benzylamino)-10-hydroxyoctadecanoate (18a)/methyl 10-(benzylamino)-9-hydroxyoctadecanoate (18b), methyl 10-hydroxy-9-(phenylamino)octadecanoate (19a)/methyl 9-hydroxy-10-(phenylamino)octadecanoate (19b)] as isomeric mixtures. Zinc(II) perchlorate hexahydrate was used as a Lewis acid catalyst to achieve these transformations under solventfree conditions. Introduction Oleochemistry is a well-founded and well-developed branch of chemistry. During the past decade, production and utilization of oleochemicals have grown in size and diversity. Thus, new and interesting oleochemicals are being exploited for industrial utilization. Oleochemicals are essential to a variety of industrial products such as surfactants, plasticizers, lubricant additives, cosmetics, pharmaceuticals, soaps, detergents, textiles, plastics, protective coatings, dispersants, intermediate chemicals, urethane derivatives, and organic pesticides. The ever-rising cost of petrochemicals and the environmental factors have diverted the attention of chemists to the synthesis of new oleochemicals derived from natural fats and oils.1 Several earlier reports2-6 have been published from our laboratory regarding reactions of fatty methyl esters for the synthesis of a variety of oleochemicals. In continuation of our work, we here wish to report solventfree methodology for the synthesis of a number of β-amino alcohols from internal epoxy fatty acid methyl esters (methyl epoxy stearate). β-Amino alcohols are an important class of organic compounds;7,8 the moiety is found in a wide variety of biologically active alkaloids and peptides.9 They find applications as a building block in the organic synthesis10 of various natural products and pharmaceuticals.11 They are also useful as chiral auxiliaries and as ligands for transition metals for asymmetric synthesis and catalysis.12-14 They are easily converted into many other molecules, including amino acids and amino sugars.15 β-Amino alcohols also find applications as β-adrenergic blockers, and they are widely used in the management of cardiovascular disorders,16 hypertension,17 angina pectoris, and cardiac arrhythmias.18 The transformation of an epoxy ring to the respective β-amino alcohol is also a * To whom correspondence should be addressed. Tel.: +919855557324. Fax: +911832258820. E-mail: [email protected].

crucial step in the synthesis of anti-HIV agents,19 the protein kinase C inhibitor balanol,20 antimalarial agents,21 a glycosidase inhibitor,22 the liposidomycin B class of antibiotics,23 naturally occurring brassinosteroids,24 a taxoid side chain,25 diverse heterocycles,26 and indoles.27 β-Amino alcohols are also useful as intermediates in the synthesis of perfumes,28 dyes,29 photo developers,29 and oxazolidones.30 Chakaraborti and co-workers31 have reported that zinc perchlorate hexahydrate [Zn(ClO4)2 · 6H2O] is a weak but better Lewis acid catalyst for the synthesis of β-amino alcohols by the epoxy ring opening reaction. 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 oleochemicals,32-34 yet, except for the most recent report by Biswas et al.,35 there is no report on the epoxy ring opening reaction in fatty acid methyl esters with amines. This is perhaps due to a common side reaction that leads to the formation of fatty amides.36 In our present study we wish to report the synthesis and characterization of several β-amino alcohols by the epoxy ring opening reactions of methyl epoxy stearate. Experimental Section Octadec-Z-9-enoic acid was purchased from Loba Chemicals, Mumbai, India. All amines were purchased from Central Drug House, New Delhi, India. Zinc(II) perchlorate hexahydrate was purchased from Sigma Aldrich, New Delhi, India. Octadec-Z9-enoic acid was esterified by a reported method.37 Epoxide of methyl octadec-Z-enoate was prepared by a previously reported method38 by using hydrogen peroxide in excess in the presence of a catalytic amount of formic acid. Thin-layer chromatography (TLC) was performed on silica-gel-G-coated (0.25-mm-thick) plates with hexane/ethyl acetate (in a ratio of 90:10 or 85:15) as the mobile phase. Spots were visualized by iodine. Instrumentation. FAB (fast atom bombardment) mass spectra were recorded on a JEOL SX-102/DA-6000 mass

10.1021/ie901969x  2010 American Chemical Society Published on Web 02/22/2010

Ind. Eng. Chem. Res., Vol. 49, No. 7, 2010 Scheme 1

3107

a

a R ) C4H9- (2), C8H17- (3), C4H8- (4), C5H10- (5), C4H8O- (6), C6H4-Cl (7), C6H4-OCH3 (8), C6H5CH2- (9), C6H5- (10). R1 ) CH3-(CH2)7-. R2 ) (CH2)7-CO2CH3.

spectrometer/data system using argon/xenon (6 kV, 10 mA) as the FAB gas at the Central Drug Research Institute (CDRI) in Lukhnow, India. An accelerating voltage of 10 kV was used, and the spectra were recorded at room temperature. mNitrobenzyl alcohol (NBA) was used as the matrix. The matrix peaks were observed at m/z 136, 137,154, 289, and 307 in all cases. The IR spectrum was recorded for a thin neat film on a Shimadzu Model FT-IR 8400s (Kyoto, Japan) instrument. 1H and 13C NMR spectra were recorded on a JEOL AL-300 (Tokyo, Japan) NMR system with a solution in CDCl3, using tetramethylsilane (TMS) as an internal standard. General Procedure. Methyl 9,10-epoxyoctadecanoate (1; 5 mmol), was added to various amines (2-10; 5 mmol) in the presence of catalytic amounts of zinc perchlorate. The reaction mixtures were stirred for 1 h at 80 °C under solvent-free conditions. The progress of a reaction was monitored by thin layer chromatography, and the equilibrium stage was achieved in 1 h in all cases. The crude reaction mixture was cooled to 25 °C. The contents were dissolved in 50 mL of chloroform and filtered to recover the catalyst. The catalyst after washing three times with chloroform (10 mL each) was reactivated in an air oven at 60 °C and reused three to five times without any loss in its activity.39 The chloroform layer was transferred to a separating funnel and washed two times with water followed by a wash with a saturated solution of sodium chloride. The organic layer was then dried with sodium sulfate. The evaporation and subsequent fractionation on silica gel (60-120 mesh) column chromatography using hexane and then a hexane:ethyl acetate mixture (at ratios of 100:00 to 70:30) (the stepwise increasing polarity elution method) yielded, first, unreacted epoxide followed by the respective amino alcohols 11a (11b)-19a (19b) in 65-85% isolated yields as pure fractions. Results and Discussion The internal epoxy fatty acid methyl ester methyl 9,10epoxyoctadecanoate (1) in a solvent-free reaction (Scheme 1) with aliphatic [butyl (2), octyl (3)], cyclic [pyrrolidine (4), piperidine (5), morpholine (6)], and aromatic [p-chloroaniline (7), p-anisidine (8), benzyl amine (9), aniline (10)] amines in the presence of zinc(II) perchlorate hexahydrate resulted in the formation of isomeric mixtures of 1,2-amino alcohols [11a (11b)-19a (19b)] in yields ranging from 65 to 85% (Table 1). Each of the products has been characterized by IR, 1H NMR,13C NMR, and mass spectroscopic analysis. The details of their analyses have been given in the Experimental Section. The OH stretching and NH stretching for all the 1,2-amino alcohols were observed at 3440-3200 cm-1. Each of the products also gave a strong stretching for the ester carbonyl at 1730-1740 cm-1. The peaks for the protons attached to C-9 and C-10 were observed as multiplets at δ 3.37 (-CH-OH) and δ 2.68

(-CH-NH) in case of the 1,2-amino alcohols formed by the reaction of methyl 9,10-epoxyoctadecanoate (1) with butyl amine (2). Similarly, the protons attached to the C-9 and C-10 of other products were observed at δ 3.37 (-CH-OH) and δ 2.68 (-CH-NH) for 12a (12b); δ 3.42 (-CH-OH) and δ 2.89 (-CH-N) for 13a (13b); δ 3.15 (-CH-OH) and δ 2.69 (-CH-N) for 14a (14b); δ 3.21 (-CH-OH) and δ 2.72 (-CH-N) for 15a (15b); δ 3.57 (-CH-OH) and δ 3.17 (-CH-NH) for 16a (16b); δ 3.47 (-CH-OH) and δ 3.06 (-CH-NH) for 17a (17b); δ 3.39 (-CH-OH) and δ 2.26-2.38 (-CH-NH) for 18a (18b); δ 3.47 (-CH-OH) and δ 3.23 (-CH-NH) for 19a (19b). The other protons were observed at their usual positions. The C-9 in the case of product 11a (11b) was observed at δ 62.13 while, C-10 for the same molecule was observed at δ 71.55 ppm. Similarly, the C-9 and C-10 of other products were observed at δ 71.51 and δ 74.42 for 12a (12b); δ 67.72 and δ 70.76, 72.50 for 13a (13b); δ 69.05 and δ 69.78 for 14a (14b); δ 69.27 and δ 69.64 for 15a (15b); δ 58.16, 58.29 and δ 73.26 for 16a (16b); δ 59.98 and δ 73.34 for 17a (17b); δ 62.62, 65.87 and δ 71.70, 73.91 for 18a (18b); δ 58.41 and δ 73.39 for 19a (19b).The other carbons were observed at their usual positions. The formation of these products has been confirmed by the mass spectral analysis of each compound. The M+ + 2 ion for the product 11a (11b) was observed at m/z 387, while the M+ and M+ + 2 ions were observed at m/z 441 and 443 for 12a (12b) and m/z 397 and 399 for 14a (14b). The parent ion observed for the product 13a (13b) was at m/z 382, which has been assigned to (M+ - 1); the same in the case of 15a (15b) was observed at m/z 398 and 400 and assigned to M+ - 1 and M+ + 1. Similarly, the largest ions at m/z 439 and 440 observed in the case of product 16a (16b), and m/z 435 and 436 for product 17a (17b), were assigned to M+ and M+ + 1. The mass ions observed at m/z 420 [18a (18b)] and m/z 406 [19a (19b)] were assigned to M+ + 1. The formation of positional isomers has been confirmed by the observation of high-intensity peaks (Table 2) due to the R-cleavage of the C-C bond between C-9 and C-10. The ion 20 is formed when the nitrogen of the reacting amine attacks the C-9 of the epoxide ring, while the ion 21 is formed by a similar attack on C-10. However, oxygencontaining ions were not observed as high-intensity peaks. This may be attributed to the loss of secondary fragments from the oxygen-containing ions. Spectral Results Methyl 9-(Butylamino)-10-hydroxyoctadecanoate (11a)/ Methyl 10-(Butylamino)-9-hydroxyoctadecanoate (11b). Pale yellow viscous liquid; IR (cm-1) neat: 3388, 3317 (OH and NH, str), 1731 (CdO, ester str), 1026, 1097, 1112, 1174 (C-O, str); NMR (CDCl3): δ (ppm) 0.86-0.94 (m, 12H, 2 × CH3 of

3108

Ind. Eng. Chem. Res., Vol. 49, No. 7, 2010

Table 1. Opening of Epoxide Ring of Methyl 9,10-Epoxy Stearate with Different Types of Amines

alkyl and butyl chains), 1.17-1.31 (br s, 44H, CH2 of alkyl and R to -CH3 of butyl chain), 1.37-1.47 (m, 12H, CH2 R to CH-OH, CH-NH and β to -CH3 of butyl chain), 1.59-1.61 (m, 4H, -CH2 β to -COOCH3), 2.25-2.38 (m, 8H,

-CH2COO- and -CH2NH butyl chain), 2.68 (m, 2H, -CH-NH), 3.20 (br s, 2H, -OH), 3.37 (m, 2H -CH-OH), 3.65 (s, 6H, -COOCH3), 3.71 (s, 2H, -NH); 13C NMR (normal/ DEPT-135) (CDCl3): δ (ppm) 13.96 (+ve, terminal CH3 of butyl

Ind. Eng. Chem. Res., Vol. 49, No. 7, 2010

3109

Table 2. Major r-Cleavage Ions for Compounds 11a (11b)-19a (19b)

chain), 17.57 (+ve, terminal CH3), 20.75-38.94 (-ve, CH2 of alkyl and butyl chains), 47.04 (-ve, -CH2NH butyl chain), 51.06 (+ve -COOCH3), 62.13 (+ve, -CH-NH), 71.55, 74.04 (+ve, -CH-OH), 173.57 (-COOCH3); MS m/z (parent ions): 387 (M+ + 2), 368, 328, 242, 228, 198. Methyl 10-Hydroxy-9-(octylamino)octadecanoate (12a)/ Methyl 9-Hydroxy-10-(octylamino)octadecanoate (12b). Pale yellow viscous liquid; IR (cm-1) neat: 3344, 3317 (OH and NH, str), 1738 (CdO, ester str), 1038, 1078, 1112, 1170 (C-O, str); NMR (CDCl3): δ (ppm) 0.88 (m, 12H, 2 × CH3 of alkyl and octyl chains), 1.27-1.31 (br s, 60H, CH2 of alkyl and octyl chains), 1.40-1.46 (m, 12H, CH2 R to CH-OH, CH-NH and β to -NH of octyl chain), 1.61 (m, 4H, -CH2 β to -COOCH3), 2.28 (m, 4H, -CH2COO-), 2.49 (m, 4H, -CH2NH butyl chain), 2.68 (m, 2H, -CH-NH), 3.18 (br s, 2H, -OH), 3.41 (m, 2H -CH-OH), 3.65 (s, 6H, -COOCH3), 3.71 (s, 2H, -NH); 13C NMR (normal/DEPT-135) (CDCl3): δ (ppm) (14.28 (+ve, terminal CH3 of alkyl and octyl chains), 22.75-34.02 (-ve, CH2 of alkyl and octyl chains), 47.00 (-ve, -CH2NH octyl chain), 51.34 (+ve -COOCH3), 71.51 (+ve, -CH-NH), 74.42 (+ve, -CH-OH), 173.86 (-COOCH3); MS m/z (parent ions): 441 and 443 (M+ and M+ + 2), 296, 254. Methyl 10-Hydroxy-9-(pyrrolidin-1-yl)octadecanoate (13a)/ Methyl 9-Hydroxy-10-(pyrrolidin-1-yl)octadecanoate (13b). Dark brown viscous liquid; IR (cm-1) neat: 3234 (OH, str), 1737 (CdO, ester str), 1028, 1089, 1170, 1187 (C-O, str); NMR (CDCl3): δ (ppm) 0.87 (t, 6H, 2 × CH3), 1.25-1.31 (br s, 40H, chain CH2), 1.48 (br s, 10H, CH2 R to CH-OH, CH-N, and -OH), 1.62 (m, 4H, -CH2 β to -COOCH3), 1.90 (m, 8H, 3, 4 CH2 of ring), 2.27 (m, 12H, -CH2COO- and 2, 5 CH2 of ring), 2.89 (m, 2H, -CH-N), 3.42 (m, 2H, -CH-OH), 3.66 (s, 6H, -COOCH3); 13C NMR (normal/DEPT-135) (CDCl3): δ (ppm) 14.02 (+ve, terminal CH3), 22.57-34.18 (-ve, CH2 chain), 45.45, 46.42 (-ve, 3, 4 C of ring), 51.12 (+ve -COOCH3), 55.99, 56.74 (-ve, 2, 5 C of ring), 67.72 (+ve, -CH-N), 70.76 (+ve, -CH-OH), 173.58 (-COOCH3); MS m/z (parent ions): 382 (M+ - 1), 242, 197. Methyl 10-Hydroxy-9-(piperidin-1-yl)octadecanoate (14a)/ Methyl 9-Hydroxy-10-(piperidin-1-yl)octadecanoate (14b). Dark yellow viscous liquid; IR (cm-1) neat: 3272 (OH, str), 1743 (CdO, ester str), 1033, 1105, 1168, 1197 (C-O, str); NMR (CDCl3): δ (ppm) 0.88 (t, 6H, 2 × CH3), 1.18-1.30 (br s, 40H, chain CH2), 1.45 (br s, 10H, CH2 R to CH-OH, CH-N,

and -OH), 1.61 (m, 12H, -CH2 β to -COOCH3 and 3, 5 CH2 of ring), 2.11 (m, 4H, 4 CH2 of ring), 2.28 (m, 4H, -CH2COO-), 2.31 (m, 8H, 2, 6 CH2 of ring), 2.69 (m, 2H, -CH-N), 3.15 (m, 2H, -CH-OH), 3.65 (s, 6H, -COOCH3); 13 C NMR (normal/DEPT-135) (CDCl3): δ (ppm) 13.77 (+ve, terminal CH3), 22.33-34.16 (-ve, CH2 chain), 48.88, 49.77 (-ve, 3, 4, 5 C of ring), 50.77 (+ve -COOCH3), 56.37 (-ve, 2, 6 C of ring), 69.05 (+ve, -CH-N), 69.78 (+ve, -CH-OH), 173.13 (-COOCH3); MS m/z (parent ions): 397 and 399 (M+ and M+ + 2), 381, 324, 254, 241, 210. Methyl 10-Hydroxy-9-morpholinooctadecanoate (15a)/ Methyl 9-Hydroxy-10-morpholinooctadecanoate (15b). Dark red viscous liquid; IR (cm-1) neat: 3415 (OH, str), 1735 (CdO, ester str), 1027, 1097, 1157 (C-O, str); NMR (CDCl3): δ (ppm) 0.88 (t, 6H, 2 × CH3), 1.18-1.31 (br s, 40H, chain CH2), 1.43-1.49 (br s, 10H, CH2 R to CH-OH, CH-N, and -OH), 1.61 (m, 4H, -CH2 β to -COOCH3), 2.26 (m, 4H, -CH2COO-), 2.52 (m, 8H, 2, 6 CH2 of ring), 2.72 (m, 2H, -CH-N), 3.21 (m, 2H, -CH-OH), 3.65-3.69 (s, 14H, -COOCH3 and 3, 5 CH2 of ring); 13C NMR (normal/DEPT135) (CDCl3): δ (ppm) 14.09 (+ve, terminal CH3), 17.64-34.14 (-ve, CH2 chain), 49.06, 49.19 (-ve, 2, 6 C of ring), 51.15 (+ve -COOCH3), 67.39 (-ve, 3, 5 C of ring), 69.27 (+ve, -CH-N), 69.64 (+ve, -CH-OH), 173.53 (-COOCH3); MS m/z (parent ions): 398 and 400 (M+ - 1 and M+ + 1), 286, 256, 242, 212. Methyl 9-(4-Chlorophenylamino)-10-hydroxyoctadecanoate (16a)/Methyl 10-(4-Chlorophenylamino)-9-hydroxyoctadecanoate (16b). Dark brown viscous liquid; IR (cm-1) neat: 3370 (OH and NH, str), 1731 (CdO, ester str), 1029, 1045, 1091, 1170 (C-O, str); NMR (CDCl3): δ (ppm) 0.87 (t, 6H, 2 × CH3), 1.23-1.29 (br s, 40H, chain CH2), 1.46 (br s, 10H, CH2 R to CH-OH, CH-NH, and -OH), 1.60 (m, 4H, -CH2 β to -COOCH3), 2.27 (m, 4H, -CH2COO-), 3.17 (m, 2H, -CH-NH), 3.57 (m, 2H, -CH-OH), 3.65 (s, 6H, -COOCH3), 3.71 (s, 2H, -NH), 6.49-6.52 (d, 4H, 2, 6 H of aromatic ring), 7.04-7.07 (d, 4H, 3, 5 H of aromatic ring); 13C NMR (normal/ DEPT-135) (CDCl3): δ (ppm) 14.24 (+ve, terminal CH3), 22.75-34.26 (-ve, CH2 chain), 51.38 (+ve -COOCH3), 58.16, 58.29 (+ve, -CH-NH), 73.26 (+ve, -CH-OH), 114.34, 114.37 (+ve, 2, 6 C of aromatic ring), 121.81 (-C-Cl C of aromatic ring), 129.20 (+ve, 3, 5 C of aromatic ring), 147.15

3110

Ind. Eng. Chem. Res., Vol. 49, No. 7, 2010

(-C-NH aromatic ring), 173.88 (-COOCH3); MS m/z (parent ions): 439 and 440 (M+ and M+ + 1), 422, 408, 326, 296, 282, 252. Methyl 10-Hydroxy-9-(4-methoxyphenylamino)octadecanoate (17a)/Methyl 9-Hydroxy-10-(4-methoxyphenylamino)octadecanoate (17b). Dark brown viscous liquid; IR (cm-1) neat: 3356 (OH and NH, str), 1736 (CdO, ester str), 1035, 1078, 1122 (C-O, str); NMR (CDCl3): δ (ppm) 0.86 (t, 6H, 2 × CH3), 1.22-1.31 (br s, 40H, chain CH2), 1.50 (br s, 10H, CH2 R to CH-OH, CH-NH, and -OH), 1.54 (m, 4H, -CH2 β to -COOCH3), 2.28 (m, 4H, -CH2COO-), 3.06 (m, 2H, -CH-NH), 3.47 (m, 2H, -CH-OH), 3.65 (s, 6H, -COOCH3), 3.71 (s, 2H, -NH), 3.72 (s, 6H, -OCH3 of aromatic ring), 6.56-6.58 (d, 4H, 2, 6 H of aromatic ring), 7.04-7.07 (d, 4H, 3, 5 H of aromatic ring);13C NMR (normal/DEPT-135) (CDCl3): δ (ppm) 14.21, 14.24 (+ve, terminal CH3), 22.72-34.14 (-ve, CH2 chain), 51.35 (+ve, -COOCH3), 55.58 (+ve, -OCH3 of aromatic ring), 59.98 (+ve, -CH-NH), 73.34 (+ve, -CH-OH), 114.92-115.24 (+ve, 2, 3, 5, 6 C of aromatic ring), 142.64 (-C-NH of aromatic ring),152.40 (4 C of aromatic ring), 173.86 (-COOCH3); MS m/z (parent ions): 435 and 436 (M+ and M+ + 1), 418, 376, 322, 292, 278, 248. Methyl 9-(Benzylamino)-10-hydroxyoctadecanoate (18a)/ Methyl 10-(Benzylamino)-9-hydroxyoctadecanoate (18b). Light yellow viscous liquid; IR (cm-1) neat: 3440 (OH and NH, str), 1740 (CdO, ester str), 1034, 1107, 1160 (C-O, str); NMR (CDCl3): δ (ppm) 0.88 (t, 6H, 2 × CH3), 1.19-1.30 (br s, 40H, chain CH2), 1.35-1.49 (m, 14H, -CH2 R to CH-OH, CH-NH, -CH2 β to -COOCH3 and -OH), 2.26-2.38 (m, 6H, -CH2COO- and -CH-NH), 3.39 (m, 2H, -CH-OH), 3.65 (s, 6H, -COOCH3), 3.70 (s, 2H, -NH), 3.72 (d, 4H, -CH2 of benzyl ring), 7.17-7.29 (m, 10H, 2, 3, 4, 5, 6 H of aromatic ring); 13C NMR (normal/DEPT-135) (CDCl3): δ (ppm) 13.86 (+ve, terminal CH3), 17.39-34.30 (-ve, CH2 chain), 50.98 (-ve, -CH2 of benzyl ring), 51.54 (+ve, -COOCH3), 62.62, 65.87 (+ve, -CH-NH), 71.70, 73.91 (+ve, -CH-OH), 126.82-128.13 (+ve, 2, 3, 4, 5, 6 C of aromatic ring), 139.86 (+ve, 1 C of aromatic ring), 173.51 (-COOCH3); MS m/z (parent ions): 420 (M+ + 1), 402, 342, 306, 276, 232, 91. Methyl 10-Hydroxy-9-(phenylamino)octadecanoate (19a)/ Methyl 9-Hydroxy-10-(phenylamino)octadecanoate (19b). Dark blue viscous liquid; IR (cm-1) neat: 3404 (OH and NH, str), 1739 (CdO, ester str), 1029, 1088, 1105, 1155 (C-O, str); NMR (CDCl3): δ (ppm) 0.86 (t, 6H, 2 × CH3), 1.17-1.30 (br s, 40H, chain CH2), 1.49 (br s, 10H, CH2 R to CH-OH, CH-NH, and -OH), 1.57 (m, 4H, -CH2 β to -COOCH3), 2.25 (m, 4H, -CH2COO-), 3.23 (m, 2H, -CH-NH), 3.47 (m, 2H, -CH-OH), 3.64 (s, 6H, -COOCH3), 3.71 (s, 2H, -NH), 6.57-6.67 (m, 6H, 2, 4, 6 H of aromatic ring), 7.08-7.17 (dd, 4H, 3, 5 H of aromatic ring); 13C NMR (normal/DEPT-135) (CDCl3): δ (ppm) 14.18 (+ve, terminal CH3), 22.73-34.04 (-ve, CH2 chain), 51.35 (+ve, -COOCH3), 58.41 (+ve, -CH-NH), 73.39 (+ve, -CH-OH), 113.56 (+ve, 2, 6 C of aromatic ring), 117.64 (+ve, 4 C of aromatic ring), 129.36 (+ve, 3, 5 C of aromatic ring), 148.53 (-C-NH of aromatic ring), 173.88 (-COOCH3); MS m/z (parent ions): 406 (M+ + 1), 388, 346, 292, 262, 248, 218, 106. Conclusion In the present study we have synthesized long chain fatty acid methyl ester based β-amino alcohols in yields ranging from 65 to 85%.

Acknowledgment The authors are thankful to the Council of Scientific & Industrial Research (CSIR), New Delhi, India, for providing a research grant [01/2077/06] EMR-II for this work. The authors also thank the Central Drug Research Institute (CDRI), Lucknow, India, for the mass spectra of the compounds. Supporting Information Available: Characterization data; IR, 1H, 13C NMR spectra, 13C DEPT of compounds 16a (16b) and mass spectra of all the β-amino alcohols [11a (11b)-19a (19b)] synthesized in the present study. This material is available free of charge via the Internet at http://pubs.acs.org. Literature Cited (1) Hosamani, M. K.; Sattigeri, M. R. Amido-Imidol Tautomerization by Acid-Catalyzed Addition of Nitriles to 16-Hydroxyhexadec-cis-9-enoic Acid: A Novel Route for 9-[Substituted Amido]-16-ol-hexadecanoic Acids, and Their Biological Importance and Possible Industrial Utilization. Ind. Eng. Chem. Res. 2005, 44, 254–260. (2) Ahmad, I.; Singh, S. Use of N-bromosuccinimide to obtain 1, 2-bromocarboxylates from olefinic fatty methyl esters. J. Oil Technol. Assoc. India 1995, 27 (4), 215–220. (3) Singh, S.; Singh, B. Synthesis of Gemini Surfactants from NHalosuccinimide-Dimercaptoethane Cohalogenation of Olefinic Fatty Methyl Esters. Ind. Eng. Chem. Res. 2007, 46, 983–986. (4) Singh, S.; Bhadani, A.; Kamboj, R. Synthesis of β-Bromoglycerol monoethers from R-olefins. Ind. Eng. Chem. Res. 2008, 47, 8090–8094. (5) Singh, S.; Bhadani, A.; Singh, B. Synthesis of wax esters from R-olefins. Ind. Eng. Chem. Res. 2007, 46, 2672–2676. (6) Singh, S. Synthesis of Oligoethylene Glycol Ethers from the Seed Oil of Vernonia anthelmintica. J. Oil Technol. Assoc. India 1997, 74 (5), 609–611. (7) Azizi, N.; Saidi, M. R. Highly Chemoselective Addition of Amines to Epoxides in Water. Org. Lett. 2005, 7 (17), 3649–3651. (8) Sekar, G.; Singh, V. K. An Efficient Method for Cleavage of Epoxides with Aromatic Amines. J. Org. Chem. 1999, 64, 287–289. (9) Olofsson, B.; Somfai, P. A Regio- and Stereodivergent Route to All Isomers of Vic-Amino Alcohols. J. Org. Chem. 2002, 67, 8574–8583. (10) Reddy, L. R.; Reddy, M. A.; Bhanumathi, N.; Rao, K. R. An efficient method for the ring opening of epoxides with aromatic amines catalysed by indium trichloride. New J. Chem. 2001, 25, 221–222. (11) Rodrig´uez, J. R.; Navarro, A. Opening of epoxides with aromatic amines promoted by indium tribromide: a mild and efficient method for the synthesis of β-amino alcohols. Tetrahedron Lett. 2004, 45, 7495–7498. (12) Sundararajan, G.; Vijayakrishn, K.; Vargheseb, B. Synthesis of β-amino alcohols by regioselective ring opening of arylepoxides with anilines catalyzed by cobaltous chloride. Tetrahedron Lett. 2004, 45, 8253– 8256. (13) Ager, D. J.; Prakash, I.; Schaad, D. R. 1, 2-Amino Alcohols and Their Heterocyclic Derivatives as Chiral Auxiliaries in Asymmetric Synthesis. Chem. ReV. 1996, 96, 835. (14) Chakraborti, A. K.; Kondaskar, A. ZrCl4 as A New and Efficient Catalyst for the Opening of Epoxide Rings by Amines. Tetrahedron Lett. 2003, 44, 8315. (15) (a) Golebiowski, A.; Jurczak, J. R-Amino-β-hydroxy acids in the total synthesis of amino sugars. Synlett 1992, 241. (b) Casiraghi, G.; Zanardi, F.; Rassu, G.; Spanu, P. Stereoselective Approaches to Bioactive Carbohydrates and AlkaloidssWith a Focus on Recent Syntheses Drawing from the Chiral Pool. Chem. ReV. 1995, 95, 1677. (16) Connolly, M. E.; Kersting, F.; Bollery, C. T. Prog. CardioVasc. Dis. 1976, 19, 203. (17) De Cree, J.; Geukens, H.; Leempoels, J.; Verhaegen, H. Haemodynamic effects in man during exercise of a single oral dose of narbivolol (R 67555), a new beta-1-adrenoceptor blocking agent: A comparative study with atenolol, pindolol, and propranolol. Drug DeV. Res. 1986, 8, 109– 117. (18) Owen, D. A. L.; Marsden, C. D. Effect of Adrenergic β-Blockade on Parkinsonion Tremor. Lancet 1965, 1259. (19) Ruediger, E.; Martel, A.; Meanwell, N.; Solomon, C.; Turmel, B. Novel 3′-deoxy analogs of the anti-HBV agent entecavir: synthesis of enantiomers from a single chiral epoxide. Tetrahedron Lett. 2004, 45, 739. (20) Wu, M. H.; Jacobsen, E. N. An efficient formal synthesis of balanol via the asymmetric epoxide ring opening reaction. Tetrahedron Lett. 1997, 38, 1693.

Ind. Eng. Chem. Res., Vol. 49, No. 7, 2010 (21) Lindsay, K. B.; Pyne, S. G. Synthesis of (+)-(1R,2S,9S,9aR)octahydro-1H-pyrrolo[1,2-a]azepine-1,2,9-triol: a potential glycosidase inhibitor. Tetrahedron 2004, 60, 4173. (22) Zhu, S.; Meng, L.; Zhang, Q.; Wei, L. Synthesis and evaluation of febrifugine analogues as potential antimalarial agents. Bioorg. Med. Chem. Lett. 2006, 16, 1854. (23) Moore, W. J.; Luzzio, F. A. Synthetic studies directed toward the liposidomycines: preparation and reactions of serine-derived epoxides. Tetrahedron Lett. 1995, 36, 6599. (24) Mori, K.; Sakakibara, M.; Okada, K. Brassinolide and its analogs. V. Synthesis of naturally occurring brassinosteroids employing cleavage of 23, 34-epoxides as key reactions. Synthesis of brassinolide, castasterone, dolicholide, dolichosterone, homodolicholide, homodolichosterone, 6-deoxocastasterone and 6-deoxodolichosterone. Tetrahedron 1984, 40, 1767. (25) Yamaguchi, T.; Harada, N.; Ozaki, K.; Hashiyama, T. Synthesis of taxoids. 3. A novel and efficient method for preparation of taxoids by employing cis-glycidic acid. Tetrahedron Lett. 1998, 39, 5575. (26) Lieoscher, J.; Jin, S.; Otto, A. Synthetic application of chiral pool derived heterocycles. J. Heterocycl. Chem. 2000, 37, 509. (27) Schirok, H. Microwave-Assisted Flexible Synthesis of 7-Azaindoles. J. Org. Chem. 2006, 71, 5538. (28) Yang, Y.; Wahler, D.; Reymond, J. L. β-Amino Alcohol Properfumes. HelV. Chim. Acta 2003, 86, 2928. (29) Ibaya, T.; Mizutani, T.; Inagi, T. (Yokkaichi Chemical Co., Ltd., Japan). Preparation of N-Alkyl-N-(Hydroxyalkyl) Anilines and Analogs. JP Patent 02288850, 1990. (30) Dyen, M.; Swern, E. D. 2-Oxazolidones. Chem. ReV. 1967, 67, 197. (31) Shivani; Pujala, B.; Chakraborti, A. K. Zinc(II) Perchlorate Hexahydrate Catalyzed Opening of Epoxide Ring by Amines: Applications to Synthesis of (RS)/(R)-Propranolols and (RS)/(R)/(S)-Naftopidils. J. Org. Chem. 2007, 72, 3713–3722.

3111

(32) Earle, F. R. Epoxy Oils from Plant Seeds. J. Am. Oil Chem. Soc. 1970, 47, 510–513. (33) Ayorinde, F. O.; Nana, E. Y.; Nicely, P. D.; Woods, A. S.; Price, E. O.; Nawaonicha, C. P. Syntheses of 12-Aminododecanoic and 11Aminoundecanoic Acids from Vernolic Acid. J. Am. Oil Chem. Soc. 1997, 74, 531–538. (34) Singh, S.; Mahajan, S.; Kaur, H. Synthesis of Tetrahydrofuran Ring Containing Oligoethylene Glycol Ethers from the Seed Oil of Vernonia anthelmintica. J. Am. Oil. Chem. Soc. 1999, 76 (1), 103–107. (35) Biswas, A.; Sharma, K. B.; Doll, M. K.; Erhan, Z. S.; Willett, L. J.; Cheng, N. H. Synthesis of an Amine-Oleate Derivative Using an Ionic Liquid Catalyst. J. Agric. Food Chem. 2009, 57, 8136–8141. (36) Piazza, J. G.; Foglia, A. T. Preparation of Fatty Amide Polyols Via Epoxidation of Vegetable Oil Amides by Oat Seed Peroxygenase. J. Am. Oil. Chem. Soc. 2005, 82, 481–485. (37) Singh, S.; Singh, B. Synthesis of β-Bromoethoxylates and β-Chloroethoxylates from olefinic fatty methyl esters. J. Surfactants Deterg. 2006, 9, 51–56. (38) Findley, T. W.; Swern, D.; Scanlan, J. T. Epoxidation of Unsaturated Fatty Materials with Peracetic Acid in Glacial Acetic Acid Solution. J. Am. Chem. Soc. 1945, 67, 412. (39) Bartoli, G.; Boeglin, J.; Bosco, M.; Locatelli, M.; Massaccesi, M.; Melchiorre, P.; Sambri, L. Highly Efficient Solvent-Free Condensation of Carboxylic Acids with Alcohols Catalysed by Zinc Perchlorate Hexahydrate. AdV. Synth.Catal. 2005, 347, 33–38.

ReceiVed for reView December 11, 2009 ReVised manuscript receiVed February 8, 2010 Accepted February 14, 2010 IE901969X