Synthesis of the racemic analog of a honeybee (Apis mellifera) breeding pheromone component

Article abstract of DOI:10.1007/s10600-005-0045-7

The synthesis of 1-palmitoyl-2,3-dioleoylglycerine, the racemic analog of a honeybee breeding pheromone component, from 1,2-O-isopropylideneglycerine was proposed. 2004 Springer Science + Business Media, Inc.

Full text of DOI:10.1007/s10600-005-0045-7

Chemistry of Natural Compounds, Vol. 40, No. 6, 2004
SYNTHESIS OF THE RACEMIC ANALOG OF A HONEYBEE
( ) BREEDING PHEROMONE COMPONENT
Apis mellifera
M. P. Yakovleva,1 A. Kh. Shayakhmetova,1
I. R. Gumerov,2 and G. Yu. Ishmuratov1
UDC 547.426
The synthesis of 1-palmitoyl-2,3-dioleoylglycerine, the racemic analog of a honeybee breeding pheromone
component, from 1,2-O-isopropylideneglycerine was proposed.
Key words: 1,2-O-isopropylideneglycerine,1,2-O-isopropylidene-3-O-palmitoylglycerine, 1-monopalmitoylglycerine,
1-palmitoyl-2,3-dioleoylglycerine, pheromone, racemic analog.
Phermones that are emitted during breeding and control the activity of bees near the hive play an important role in
chemical communication within the bee colony [1-6].
1,2-Dioleoyl-3-palmitoylglycerine was isolated and identified in 1984 as a component of the honeybee (
Apis mellifera
L.) breeding pheromone that can cause them to mass on artificial maternal cells of honeycombs [7].
Syntheses of this compound that include mutual transesterification of trioleoyl- and tripalmitoylglycerines are known
[8]. We propose a synthesis of the title compound that is based on chemoselective transformations of DL-1,2-
isopropylideneglycerine, which is readily accessible from glycerine [9]. The synthetic scheme consists of transesterification in
the presence of sodium ethoxide of the methyl ester of palmitic acid by diprotected triol 2, acid hydrolysis of intermediate 3 to
α-monoglyceride 4, and exhaustive acylation of it by oleoylchloride. The overall yield of 1 calculated per starting 2 was 20%.
O
O
OH
OH
O
O
AcOH/H O
2
[9]
n-C H COOMe
15 31
EtONa
OCCH (CH ) CH
3
OH
OH
2
2 13
O
2
3
CH (CH ) CH CH
OCCH (CH ) CH
2 5
2
2 5
2
3
2
2
OH
OH
n-CH (CH )
2 7
(CH ) COCl
2 7
3
O
CH (CH ) CH CH
2 5
OCCH (CH ) CH
2 5
2
2
3
2
2
O
OCCH (CH ) CH
2 13
2
3
OCCH (CH ) CH CH
2 12 3
2
2
O
O
1
4
EXPERIMENTAL
IR spectra were recorded on a UR-20 instrument as thin layers. NMR spectra were recorded on a Bruker AM-300
1
13
spectrometer (working frequency 300.13 MHz for H and 75.47 MHz for C) in CDCl using as an internal standard the
3
1)InstituteofOrganicChemistry, UfaScientificCenter, Russian AcademyofSciences, RF, 450054, Ufa, pr. Oktyabrya,
71, fax (3472) 35 60 66, e-mail: kharis@anrb.ru; 2) Birsk State Pedogogic Institute, RF, 452320 Birsk, ul. Internatsional′naya,
10. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 488-489, November-December, 2004. Original article
submitted August 3, 2004.
0009-3130/04/4006-0593 ©2004 Springer Science + Business Media, Inc.
593

13
impurity protons in the deuterated solvent (PMR, δ 7.27 ppm) and the average CDCl signal ( C NMR, δ 77.00 ppm). GC
3
was carried out on Chrom-5 instruments [column length 1.2 m, silicone SE-30 (5%) on Chromaton N-AW-DMCS (0.16-
0.20 mm) stationary phase, working temperature 50-300°C] with He carrier gas. Column chromatography was performed on
silica gel L (Czech Rep.) of particle size 40-100 µm; TLC, on Silufol UV-254 plates (Czech Rep.). Elemental analyses of all
compounds agreed with those calculated. Petroleum ether (40-70°C, PE) was used for the reactions.
1,2-O-Isopropylideneglycerine (2) was prepared from glycerine as before [9]. The IR and PMR spectra were
13
practically identical to those previously described [10]. C NMR spectrum (CDCl ): 25.01 and 26.42 (q, CH -C), 62.73 (t,
3
3
CH OH), 65.66 (t, CH O), 76.03 (d, CHO), 109.16 (s, CH C).
2
2
3
1,2-O-Isopropylidene-3-O-palmitoylglycerine (3). A solution of sodium ethoxide that was prepared from Na
(0.09 g, 3.8 mg-at) in absolute EtOH (10 mL) was treated with protected triol (2, 5.00 g, 37.9 mmol) and methylpalmitate
(10.00 g, 37.9 mmol) and heated to 100°C until the alcohol had distilled. The dry solid was extracted with PE (3 × 50 mL) and
-1
evaporated to afford 3 (8.02 g, 57%), mp 31-32°C. IR spectrum (KBr, ν, cm ): 1735 (C=O), 1050 (C–O).
PMR spectrum (CDCl , δ, ppm, J/Hz): 0.88 (3H, t, J = 3, CH CH ), 1.24 (26H, br.s, CH ), 1.32, 1.40 (6H, both s,
3
3
2
2
13
CH –C), 2.30 (2H, t, J = 7, CH COO), 3.52-3.59 (1H, m, CHO), 3.92-4.32 (4H, m, CH O). C NMR (CDCl ): 14.02 (q,
3
2
2
3
CH CH ), 25.27, 26.59 (both q, CH –C), 22.60, 22.70, 24.80, 25.15, 29.02, 29.17, 29.28, 29.37, 29.59, 31.83, 34.00 (all t,
3
2
3
CH ), 34.57 (t, CH COO), 64.41 (t, CH OOC), 66.23 (t, CH O), 73.56 (d, CHO), 109.71 (s, CH –C), 173.57 (COO).
2
2
2
2
3
1-Monopalmitoylglycerine (4). A solution of 3 (5.00 g, 13.5 mmol) in PE (40 mL) was treated with CH COOH
3
(13 mL, 60%), stirred for 24 h at room temperature, diluted with PE (50 mL), washed successively with saturated NaHCO and
3
NaCl solutions, dried over MgSO , and evaporated to afford 4 (2.64 g, 60%), mp 71-72°C (cf. [10]). IR and PMR spectra were
4
13
identical to those reported previously [11]. C NMR spectrum (CDCl ): 13.97 (q, CH ), 22.49, 24.70, 28.93, 29.08, 29.17,
3
3
29.26, 29.47, 31.74 (all t, CH ), 33.91 (t, CH COO), 66.13 (t, CH OH), 69.96 (d, CHOH), 73.46 (t, CH OOC), 173.96 (s,
2
2
2
2
COO).
1-Palmitoyl-2,3-dioleoylglycerine (1). Oleic acid chloride (5.48 g, 19.2 mmol) was added to 4 (2.00 g, 6.0 mmol)
in dry pyridine (30 mL). The mixture was stirred for 10 h, treated with water (8 mL), extracted with PE (3 × 50 mL), washed
successively with HCl (10%) and saturated NaHCO and NaCl solutions, dried over MgSO , and evaporated. The solid was
3
4
chromatographed over SiO (PE:ethylacetate, 9:1) to afford 1 (2.73 g, 52%). PMR spectrum (CDCl , δ, ppm, J/Hz): 0.88 (9H,
2
3
3
t, J = 6.7, CH CH ), 1.20-1.40 (64H, br.s, CH ), 1.90-2.10 (8H, m, CH C=), 2.30 (6H, t, J = 7.2, CH COO), 4.15 (4H, dd,
J = 8.2, J = 1.7, CH OOC), 4.28 (1H, m, CHOOC), 5.36 (4H, t, CH=). C NMR spectrum (CDCl ): 14.12 (q, CH CH ),
3
2
2
2
2
3
4
13
2
3
3
2
22.67 (t, CH CH ), 24.11-24.68 (t, CH ), 27.20 (t, CH C), 34.05, 34.19 (both t, CH COO), 62.07 (t, CH OOC), 68.83 (d,
3
2
2
2
2
2
CHOOC), 130.01 (d, CH=), 173.58, 175.31 (s, COO).
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4.
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