CN101863750B - Synthesis method of oxygen-containing derivative bark beetle pheromone verbena ketene of alpha-pinene and verbenol - Google Patents
Synthesis method of oxygen-containing derivative bark beetle pheromone verbena ketene of alpha-pinene and verbenol Download PDFInfo
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Abstract
The invention provides a synthesis method of an oxygen-containing derivative bark beetle pheromone verbena ketene of alpha-pinene and verbenol, which is a synthesis method of the verbena ketene and the verbenol with high conversion rate, wherein the conversion rate of the alpha-pinene is nearly 100 percent; the yield of (-) -verbena ketene is 57 percent, the yield of (+)-verbena ketene is 60 percent, the yield of (-)-cis verbenol is 89 percent, the yield of (+)-cis verbenol is 79 percent, the yield of (-) -trans verbenol is 51 percent, and the yield of (+)-trans verbenol is 49 percent. The obtained products oxygen-containing derivative bark beetle pheromone verbena ketene of alpha-pinene and verbenol can be used for preventing pinaceae plant pests.
Description
Technical field
The invention belongs to the synthetic method of the containing oxygen derivative of α-pinene, relate to a kind of containing oxygen derivative bark beetle pheromone verbenone of α-pinene and the synthetic method of verbenol.
Background technology
Vertical pit cutting pin small moth (Tomicus piniperda L) is the primary pest of pinaceae plant, is also one of worldwide common injurious forest-insect.Abroad, the pine trees such as this worm main harm Scots pine Pinus sylverstris, maritime pine P.pinaster, Pinus nigra P.nigra and Japanese red pine P.densiflora.At home, vertical pit cutting pin small moth main harm pinus yunnanensis P.yunnanensis, Pinus massoniana Lamb P.massolangbianensis and high illawarra mountain pine P.densata etc.At the end of the seventies in last century, vertical pit cutting pin small moth occurs on a large scale in Yunnan, causes the large-area death of pinus yunnanensis.In recent years, this worm is serious in the harm of China the Northeast, brings about great losses to production of forestry and improvement of the ecological environment.
Utilizing the aggregation pheromone compound to lure collection blastophagus piniperda adult to carry out insect pest and observe and predict, take accordingly corresponding prophylactico-therapeutic measures, is one of main direction of world today's bark beetle comprehensive regulation.In recent years, at the western loose bark beetle (DedroDedroctonus breviscomis) of North America, dendroctonus frontalis (D.frontalis), the red wing bark beetle of dragon spruce (D.pseudotsugae) and Tomicus piniperda (Tomicuspiniperda) utilize verbenone (4, 6, 6-trimethylammonium dicyclo [3.1.1]-3-hepten-2-one) (verbenone), cis verbenol (4, 6, 6-trimethylammonium dicyclo [3.1.1]-3-heptene-2-alcohol) (cis-verbenol) or trans verbenol 4, 6, 6-trimethylammonium dicyclo [3.1.1]-3-heptene-2-alcohol) (trans-verbenol) etc. as the bark beetle pheromone compound, in monitoring, forecast, the trapping moth, control is harmed and is conserved forests and has a significant effect.
Generate in the reaction of alcohol ketone at the alkene catalytic air oxidation, often use cobalt salt as catalyzer.The employing resin acid cobalts such as Yin Caixia are catalyzer, oxygen is oxygenant, the productive rate that α-pinene generates verbenol, verbenone through catalyzed oxidation is respectively 13.6% and 35.6%, overall selectivity is 35% (Yin Caixia, Xiao Han, Zhang Fengmei etc. bark beetle pheromone verbenol and verbenone study on the synthesis. chemistry and biotechnology .2005,9 (22), 25-27.Yin Caixia etc. have carried out the synthetic and biological activity determination of bark beetle pheromone α-pinene containing oxygen derivative. (Yin Caixia, high bamboo grove, Zhou Nan, Liu Fuchu, Qiao Ying Yunnan University journal (natural science edition), 2001,23 (2), 132-134).Chen Qiu carries out selective catalytic oxidation with different cobalt salts to α-pinene, synthetic verbenol and verbenone, the highest transformation efficiency can reach 57.46% (Chen Qiu. cobalt salt catalysis α-pinene selective oxidation. Journal of Kunming Metallurgy College .2009,25 (3), 74-77.).
Platinum, palladium, ruthenium, rhodium and iridium that Kuznetsova will load on carbon are catalyzer, take oxygen as oxygenant, and the transformation efficiency of α-pinene is 20%～40%, and the selectivity of verbenone is less than 50% (Kuznetsov, L.I.; Kuznetsov, N.I.; Lisitsyn, A.S.Beck, I.E.; Likholobov, V.A.; Ancel, J.E.Liquid-phase oxidation of α-pinene with oxygen catalyzed by carbon-supported platinum metals.Kinet.Catal.2007,48,38-44.).Casuscelli be take titanium-containing mesoporous material as heterogeneous catalyst, and with hydrogen peroxide Oxygen in Liquid α-pinene, the α-pinene transformation efficiency is 12%～16%, and primary product is verbenol and verbenone (Casuscelli, S.G.; Eimer, G.A.; Canepa, A.; Heredia, A.C.; Poncio, C.E.; Crivello, M.E.; Perez, C.F.; Aguilar, A.; Herrero, E.R.Ti-MCM-41 as catalyst for α-pinene oxidation:Study of the effect of Ti content and H
2o
2addition on activity and selectivity.Catal.Today2008,133,678-683.).It is catalyzer that Maksimchuk etc. be take Ti-MMM-2 and Fe-MMM-2 equimolecular sieve, hydrogen oxide oxidation α-pinene, the α-pinene transformation efficiency is only 8%～15%, and it is main (both total contents are 80%～82%) (Maksimchuk, N.V. that product be take verbenol and verbenone; Melgunov, M.S.
, J.; Jarzebski, A.B.; Kholdeeva, O.A.H
2o
2-based allylic oxidation of α-pinene over different singlesite catalysts.J.Catal.2005,235,175-183.).
Aforesaid method, on the whole, the transformation efficiency of α-pinene transformation efficiency is not high, and total selectivity is also undesirable, and, the mixture that mostly is verbenone and verbenol obtained.This especially embodies more obvious for separating and purifying and bring certain difficulty when the verbenone for preparing optical purity and verbenol.Therefore, develop a kind of transformation efficiency is high and selectivity is high synthetic verbenol and the method for verbenone and remain the important research topic of this technical field.
summary of the invention
In order to solve the shortcoming of prior art, the invention provides the containing oxygen derivative bark beetle pheromone verbenone that relates to a kind of α-pinene and the synthetic method of verbenol.It is a kind of method of transformation efficiency high and pure body verbenone and verbenol.
The containing oxygen derivative bark beetle pheromone verbenone of a kind of α-pinene provided by the invention and the synthetic method of verbenol, its step and condition are as follows:
(1) synthesizing of (-)-verbenone
According to (-)-α-pinene: CrO
3mol than for 1:1, by (-)-α-pinene and CrO
3in the mixed solution that the volume ratio that is dissolved in acetone and water is 25:4, under stirring, 25 ℃ of reactions, after 10 hours, are filtered, and steam except acetone, and the gained mixture is dissolved in CH
2cl
2in, this organic phase is used respectively to saturated NaCO
3with use anhydrous Na after the NaCl solution washing
2sO
4drying, filter, and steaming desolventizes, and the gained crude product is through column chromatography, and condition is ethyl acetate: sherwood oil=1:5 wash-out obtains weak yellow liquid (-)-verbenone.
(2) synthesizing of (+)-verbenone
According to (+)-α-pinene: CrO
3mol than for 1:1, by (+)-α-pinene and CrO
3in the mixed solution that the volume ratio that is dissolved in acetone and water is 75:6, under stirring, 25 ℃ of reactions, after 10 hours, are filtered, and steam except acetone, and the gained mixture is dissolved in CH
2cl
2in, use respectively saturated NaCO
3with the NaCl solution washing, use anhydrous Na
2sO
4dry; Filter, steaming desolventizes, and the gained crude product is through column chromatography, and condition is ethyl acetate: sherwood oil=1:5 wash-out obtains weak yellow liquid (+)-verbenone.
(3) synthesizing of (-)-cis verbenol
According to NaBH
4: the mol of (-)-verbenone is than being 1:1, first NaBH
4in the solution that the volume ratio that is dissolved in 2-the third alcohol and water is 5:1, under-20 ℃, under stirring, then drip (-)-verbenone in described solution, after the thin-layer chromatography monitoring reaction finishes, excessive NaBH
4the hydrochloric acid soln that is 6% with mass percent concentration neutralization, use extracted with diethyl ether three times after the reaction mixture thin up, merge organic phase, and organic phase is through saturated NaCl solution washing, anhydrous MgSO
4drying, filter and revolve and boil off solvent, obtains light yellow solid, and this crude product obtains white crystal (-)-cis verbenol after the normal hexane recrystallization.
(4) synthesizing of (+)-cis verbenol
According to NaBH
4: the mol of (+)-verbenone is than being 1:1, first NaBH
4in the solution that the volume ratio that is dissolved in 2-the third alcohol and water is 5: 1, at-20 ℃, under stirring, then drip (+)-verbenone in described solution, after the thin-layer chromatography monitoring reaction finishes, excessive NaBH
4the hydrochloric acid soln that is 6% with mass percent concentration neutralization, use extracted with diethyl ether three times after the reaction mixture thin up, merge organic phase, and organic phase is through saturated NaCl solution washing, anhydrous MgSO
4drying, filter and revolve and boil off solvent, obtains light yellow solid, and this crude product obtains white crystal (+)-cis verbenol after the normal hexane recrystallization.
(5) synthesizing of (-)-trans verbenol
According to (-)-α-pinene: Pb (OAc)
4the mol ratio be 1: 11, (-)-α-pinene is dissolved in benzene, be heated to 65 ℃, then by Pb (OAc)
4join in above-mentioned system, the thin-layer chromatography monitoring reaction, after reaction finishes, after filtering, gained filtrate is used respectively H
2o and saturated NaCl solution washing, use anhydrous Na
2sO
4drying, filter, and steams solvent, and the gained crude product is dissolved in acetic acid, uses n-hexane extraction three times after this mixture dilute with water; Merge organic phase, organic phase is used respectively H successively
2the NaHCO that O, mass concentration are 5%
3with saturated NaCl solution washing, anhydrous Na SO
4drying, filter, and steaming desolventizes, and the gained crude product is 0.05mmHg at pressure, 65-67 ℃ of underpressure distillation, obtains (-)-trans verbenene alcohol acetic ester crude product;
By (-) of above-mentioned preparation-verbenene alcohol acetic ester crude product, place again 48h in refrigerator after the mixed solution of the KOH aqueous solution that to be dissolved in methyl alcohol and mass concentration be 25%, in this mixed solution, methyl alcohol and KOH mass ratio are 4: 1, saturated NaCl solution washing for above-mentioned mixed solution, use anhydrous Na
2sO
4drying, filter and steam solvent, obtains (-)-trans verbenol colourless liquid.
(6) synthesizing of (+)-trans verbenol
According to (+)-α-pinene: Pb (OAc)
4the mol ratio be 1: 1.1, (+)-α-pinene is dissolved in benzene, be heated to 65 ℃, then by Pb (OAc)
4join in above-mentioned system, the thin-layer chromatography monitoring reaction, after reaction finishes, after filtering, gained filtrate is used respectively H
2o and saturated NaCl solution washing, use anhydrous Na
2sO
4drying, filter and steam solvent, and the gained crude product is dissolved in acetic acid, uses n-hexane extraction three times after this mixture dilute with water; 2 merge organic phase, and organic phase is used respectively H
2o, the NaHCO that mass concentration is 5%
3with saturated NaCl solution washing, anhydrous Na SO
4drying, filter and steam and desolventize, and in vacuum tightness, is 0.05mmHg, and temperature is 65-67 ℃ of underpressure distillation, obtains (+)-trans verbenene alcohol acetic ester crude product;
Place again 48h in refrigerator after (+) of above-mentioned preparation-trans verbenene alcohol acetic ester crude product being dissolved in to the mixed solution of the KOH aqueous solution that methyl alcohol and mass concentration are 25%, in this mixed solution, methyl alcohol and KOH mass ratio are 4: 1, above-mentioned mixed solution thin up, by extracted with diethyl ether three times, merge organic phase, organic phase is used respectively H
2o and saturated NaCl solution washing, use anhydrous Na
2sO
4drying, filter and steam solvent, obtains (+)-trans verbenol colourless liquid.
Beneficial effect: the invention provides a kind of containing oxygen derivative bark beetle pheromone verbenone of α-pinene and the synthetic method of verbenol.It is that a kind of transformation efficiency is high, selectivity is high and the method for pure body verbenone and verbenol, and wherein the α-pinene transformation efficiency is almost 100%; The yield of (-)-verbenone is 57%, the yield of (+)-verbenone is 60%, the yield of (-)-cis verbenol is 89%, the yield of (+)-cis verbenol is 79%, the yield of (-)-trans verbenol is 51%, and the yield of (+)-trans verbenol is 49%.The containing oxygen derivative bark beetle pheromone verbenone of the product α-pinene that the present invention obtains and verbenol can be for preventing and treating the pinaceae plant insect pest.
Embodiment:
Synthesizing of embodiment 1 (-)-verbenone
By 25g, be that 184mmol (-)-α-pinene is dissolved in the mixed solution of 500mL acetone and 80mL water, under stirring, adding 18.4g is 184mmol CrO
3, 25 ℃ are reacted 10 hours.Filter, steam except acetone, the gained mixture is dissolved in CH
2cl
2in, this organic phase is used respectively to saturated NaCO
3, use anhydrous Na after the NaCl solution washing
2sO
4drying, filtration, steaming desolventize, and the gained crude product, through column chromatography, is used ethyl acetate: sherwood oil=carry out wash-out at 1: 5, obtain weak yellow liquid (-)-verbenone 157g, yield is 57%.
1HNMR(300MHz，CDCl
3)：δ＝1.01[s，3H，C(6)-CH
3]，1.50[s，3H，C(6)-CH
3]，2.01[s，3H，C(4)-CH
3]，2.06[d，1H，
3J
H，H＝9.6Hz，C(7)-H]，2.42[1H，C(7)-H]，2.64[1H，C(1)-H]，2.81[1H，C(5)-H]，5.71[1H，C(3)-H].
Synthesizing of embodiment 2 (+)-verbenone
15.6g (+)-α-pinene 114mmol is dissolved in the mixed solution of 300mL acetone and 48mL water, under stirring, adds CrO
311.4g (114mmol), 25 ℃ are reacted 10 hours.Will be after filtration, steam except acetone, the gained mixture is dissolved in CH
2cl
2in, and it is used respectively to saturated NaCO
3, the NaCl solution washing, use anhydrous Na
2sO
4dry; Filtration, steaming desolventize, and the gained crude product, through column chromatography, is used ethyl acetate: sherwood oil=wash-out after obtain weak yellow liquid (+)-verbenone 9g at 1: 5, yield is 60%.
1H?NMR(300MHz，CDCl
3)：δ＝0.95[s，3H，C(6)-CH
3]，1.44[s，3H，C(6)-CH
3]，1.96[3H，C(4)-CH
3]，2.02[d，1H，
3JH，H＝9.1Hz，C(7)-H]，237[1H，C(7)-H]，2.58[1H，C(1)-H]，2.75[1H，C(5)-H]，5.67[1H，C(3)-H].
13C?NMR(75MHz，CDCl
3)：δ＝21.9，23.4，26.4，40.7，49.5，539，57.4，121.0，170.0，203.8.
Synthesizing of embodiment 3 (-)-cis verbenol
Under-20 ℃, to the 0.56g that contains stirred, be 1.5mmol NaBH
4the mixed solution and dripping 22g of 60mL volume ratio third alcohol and water that is 5: 12 be 1.5mmol (-)-verbenone, after thin-layer chromatography TLC monitoring reaction finishes, the hydrochloric acid soln that excessive NaBH4 is 6% with mass percent neutralizes.Use 10mL extracted with diethyl ether three times after the reaction mixture thin up, merge organic phase, organic phase is through saturated NaCl solution washing, anhydrous MgSO
4drying, filter, revolve to boil off solvent and obtain light yellow solid, this crude product after the normal hexane recrystallization white crystal (-)-cis verbenol 1.97g, yield is 89%.
1H?NMR(300MHz，CDCl
3)：δ＝1.08[s，3H，C(6)-CH
3]，1.29[1H，C(7)-H]，1.35[3H，C(6)-CH
3]，1.61[1H，CHO
H]，1.73[3H，C(4)-CH
3]，1.97[1H，C(1)-H]，2.29[1H，C(5)-H]，2.44[1H，C(7)-H]，445[1H，C
HOH]，5.36[1H，C(3)-H].
Synthesizing of embodiment 4 (+)-cis verbenol
Under-20 ℃, to the 1.26g that contains stirred, be 33mmol NaBH
4the mixing solutions of 90mL volume ratio 2-the third alcohol and water that is 5: 1 in, dripping 5g is 3.3mmol (+)-verbenone; After thin-layer chromatography TLC monitoring reaction finishes, excessive NaBH
4hydrochloric acid soln neutralization by mass percent 6%; Use 10mL extracted with diethyl ether three times after the reaction mixture thin up, merge organic phase; Organic phase is through saturated NaCl solution washing, anhydrous MgSO
4drying, filter, revolve to boil off solvent and obtain light yellow solid, this crude product after the normal hexane recrystallization white crystal (+)-cis verbenol 397g, yield is 79%.
1HNMR(300MHz，CDCl
3)：δ＝1.06[s，3H，C(6)-CH
3]，1.28[1H，C(7)-H]，1.33[3H，C(6)-CH
3]，1.65[1H，CHO
H]，1.71[3H，C(4)-CH
3]，1.96[1H，C(1)-H]，2.27[1H，C(5)-H]，2.42[1H，C(7)-H]，4.45[1H，C
HOH]，5.35[1H，C(3)-H].
13C?NMR(75MHz，CDCl
3)：δ＝22.6，26.8，35.4，38.9，47.6，48.1，74.4，119.2，147.3.
Synthesizing of embodiment 5 (-)-trans verbenol
Be that 54.5mmol (-)-α-pinene is dissolved in benzene by 7.42g, be heated to 65 ℃; By 26.5g, be the Pb (OAc) of 59.8mmol
4join in above-mentioned system thin-layer chromatography TLC monitoring reaction.After reaction finishes, after filtering, gained filtrate is used respectively H
2o, saturated NaCl solution washing, use anhydrous Na
2sO
4drying, filter, steam solvent, and the gained crude product is dissolved in 30mL acetic acid, uses 10mL n-hexane extraction three times after this mixture dilute with water; Merge organic phase, organic phase is used respectively H
2o, the NaHCO that mass concentration is 5%
3, saturated NaCl solution washing, anhydrous Na SO
4drying, filter, and steams to desolventize to obtain crude product; Crude product is that 0.05mmHg and temperature are to carry out underpressure distillation under 65-67 ℃ in vacuum tightness, obtains (-)-trans verbenene alcohol acetic ester crude product.
Place again 48h in refrigerator after (-) of above-mentioned preparation-verbenene alcohol acetic ester being dissolved in to the mixed solution of the KOH aqueous solution that methyl alcohol and mass concentration are 25%, in this mixed solution, methyl alcohol and KOH mass ratio are 4: 1, above-mentioned mixed solution thin up, 5mL extracted with diethyl ether three times, merge organic phase; Organic phase is used respectively H
2o, saturated NaCl solution washing, use anhydrous Na
2sO
4drying, filter, steam solvent, obtains colourless liquid (-)-trans verbenol colourless liquid 4.23g, and yield is 51%.
1H?NMR(300MHz，CDCl
3)：δ＝0.87[s，3H，C(6)-CH
3]，1.30[1H，C(7)-H]，1.33[3H，C(6)-CH
3]，1.57[1H，CHOH]，1.72[3H，C(4)-CH
3]，2.04[1H，C(1)-H]，2.17[1H，C(5)-H]，2.29[1H，?C(7)-H]，4.27[1H，C
HOH]，5.34[1H，C(3)-H].
Synthesizing of embodiment 6 (+)-trans verbenol
Be that 54.5mmol (+)-α-pinene is dissolved in benzene by 7.42g, be heated to 65 ℃; By 26.5g, be 59.8mmol Pb (OAc)
4join in above-mentioned system thin-layer chromatography TLC monitoring reaction.After reaction finishes, after filtering, gained filtrate is used respectively H
2o, saturated NaCl solution washing, use anhydrous Na
2sO
4drying, filter, steam solvent, and the gained crude product is dissolved in 30mL acetic acid, uses 10mL n-hexane extraction three times after this mixture dilute with water; Merge organic phase, organic phase is used respectively H
2the NaHCO that O, mass concentration are 5%
3, saturated NaCl solution washing, anhydrous Na SO
4drying, filter, and steams to desolventize to obtain crude product; Crude product is 0.05mmHg in vacuum tightness, and temperature 65-67 ℃ is carried out underpressure distillation, obtains (+)-trans verbenene alcohol acetic ester crude product.
Place again 48h in refrigerator after (+) of above-mentioned preparation-trans verbenene alcohol acetic ester crude product being dissolved in to the mixed solution of the KOH aqueous solution that methyl alcohol and mass concentration are 25%, in this mixed solution, methyl alcohol and KOH mass ratio are 4: 1, above-mentioned mixed solution thin up, by 5mL extracted with diethyl ether three times, merge organic phase; Organic phase is used respectively H
2o, saturated NaCl solution washing, use anhydrous Na
2sO
4drying, filter, steam solvent, obtains colourless liquid 4.06g, and yield is 49%.
1H?NMR(300MHz，CDCl
3)：δ＝0.86[s，3H，C(6)-CH
3]，1.32[3H，C(6)-CH
3]，1.44[1H，C(7)-H]，1.74[3H，C(4)-CH
3]，2.94-2.29[4H]，4.27[1H，C
HOH]，5.34[1H，C(3)-H].
Claims (6)
1. the synthetic method of the containing oxygen derivative bark beetle pheromone verbenone of a α-pinene, is characterized in that, its step and condition are as follows:
Synthesizing of (-)-verbenone
According to (-)-α-pinene: CrO
3mol than for 1:1, by (-)-α-pinene and CrO
3in the mixed solution that the volume ratio that is dissolved in acetone and water is 25:4, under stirring, 25 ℃ of reactions, after 10 hours, are filtered, and steam except acetone, and the gained mixture is dissolved in CH
2cl
2in, this organic phase is used respectively to saturated NaCO
3with use anhydrous Na after the NaCl solution washing
2sO
4drying, filter, and steaming desolventizes, and the gained crude product is through column chromatography, and condition is ethyl acetate: sherwood oil=1:5 wash-out obtains weak yellow liquid (-)-verbenone.
2. the synthetic method of the containing oxygen derivative bark beetle pheromone verbenone of a α-pinene, is characterized in that, its step and condition are as follows:
Synthesizing of (+)-verbenone
According to (+)-α-pinene: CrO
3mol than for 1:1, by (+)-α-pinene and CrO
3in the mixed solution that the volume ratio that is dissolved in acetone and water is 75:6, under stirring, 25 ℃ of reactions, after 10 hours, are filtered, and steam except acetone, and the gained mixture is dissolved in CH
2cl
2in, use respectively saturated NaCO
3with the NaCl solution washing, use anhydrous Na
2sO
4dry; Filter, steaming desolventizes, and the gained crude product is through column chromatography, and condition is ethyl acetate: sherwood oil=1:5 wash-out obtains weak yellow liquid (+)-verbenone.
3. the synthetic method of the containing oxygen derivative bark beetle pheromone verbenol of a α-pinene, is characterized in that, its step and condition are as follows:
Synthesizing of (-)-cis verbenol
According to NaBH
4: the mol of (-)-verbenone is than being 1:1, first NaBH
4in the solution that the volume ratio that is dissolved in 2-the third alcohol and water is 5:1, under-20 ℃, under stirring, then drip (-)-verbenone in described solution, after the thin-layer chromatography monitoring reaction finishes, excessive NaBH
4the hydrochloric acid soln that is 6% with mass percent concentration neutralization, use extracted with diethyl ether three times after the reaction mixture thin up, merge organic phase, and organic phase is through saturated NaCl solution washing, anhydrous MgSO
4drying, filter and revolve and boil off solvent, obtains light yellow solid, and this crude product obtains white crystal (-)-cis verbenol after the normal hexane recrystallization.
4. the synthetic method of the containing oxygen derivative bark beetle pheromone verbenol of a α-pinene, is characterized in that, its step and condition are as follows:
Synthesizing of (+)-cis verbenol
According to NaBH
4: the mol of (+)-verbenone is than being 1:1, first NaBH
4in the solution that the volume ratio that is dissolved in 2-the third alcohol and water is 5:1, at-20 ℃, under stirring, then drip (+)-verbenone in described solution, after the thin-layer chromatography monitoring reaction finishes, excessive NaBH
4the hydrochloric acid soln that is 6% with mass percent concentration neutralization, use extracted with diethyl ether three times after the reaction mixture thin up, merge organic phase, and organic phase is through saturated NaCl solution washing, anhydrous MgSO
4drying, filter and revolve and boil off solvent, obtains light yellow solid, and this crude product obtains white crystal (+)-cis verbenol after the normal hexane recrystallization.
5. the synthetic method of the containing oxygen derivative bark beetle pheromone verbenol of a α-pinene, is characterized in that, its step and condition are as follows:
Synthesizing of (-)-trans verbenol
According to (-)-α-pinene: Pb (OAc)
4mol than for 1:1.1, (-)-α-pinene is dissolved in benzene, be heated to 65 ℃, then by Pb (OAc)
4join in above-mentioned system, the thin-layer chromatography monitoring reaction, after reaction finishes, after filtering, gained filtrate is used respectively H
2o and saturated NaCl solution washing, use anhydrous Na
2sO
4drying, filter, and steams solvent, and the gained crude product is dissolved in acetic acid, uses n-hexane extraction three times after this mixture dilute with water; Merge organic phase, organic phase is used respectively H successively
2the NaHCO that O, mass concentration are 5%
3with saturated NaCl solution washing, anhydrous Na SO
4drying, filter, and steaming desolventizes, and the gained crude product is 0.05mmHg at pressure, 65-67 ℃ of underpressure distillation, obtains (-)-trans verbenene alcohol acetic ester crude product;
By (-) of above-mentioned preparation-verbenene alcohol acetic ester crude product, place again 48h in refrigerator after the mixed solution of the KOH aqueous solution that to be dissolved in methyl alcohol and mass concentration be 25%, in this mixed solution, methyl alcohol and KOH mass ratio are 4:1, saturated NaCl solution washing for above-mentioned mixed solution, use anhydrous Na
2sO
4drying, filter and steam solvent, obtains (-)-trans verbenol colourless liquid.
6. the synthetic method of the containing oxygen derivative bark beetle pheromone verbenol of a α-pinene, is characterized in that, its step and condition are as follows:
Synthesizing of (+)-trans verbenol
According to (+)-α-pinene: Pb (OAc)
4mol than for 1:1.1, (+)-α-pinene is dissolved in benzene, be heated to 65 ℃, then by Pb (OAc)
4join in above-mentioned system, the thin-layer chromatography monitoring reaction, after reaction finishes, after filtering, gained filtrate is used respectively H
2o and saturated NaCl solution washing, use anhydrous Na
2sO
4drying, filter and steam solvent, and the gained crude product is dissolved in acetic acid, uses n-hexane extraction three times after this mixture dilute with water; Merge organic phase, organic phase is used respectively H
2o, the NaHCO that mass concentration is 5%
3with saturated NaCl solution washing, anhydrous Na SO
4drying, filter and steam and desolventize, and in vacuum tightness, is 0.05mmHg, and temperature is 65-67 ℃ of underpressure distillation, obtains (+)-trans verbenene alcohol acetic ester crude product;
Place again 48h in refrigerator after (+) of above-mentioned preparation-trans verbenene alcohol acetic ester crude product being dissolved in to the mixed solution of the KOH aqueous solution that methyl alcohol and mass concentration are 25%, in this mixed solution, methyl alcohol and KOH mass ratio are 4:1, above-mentioned mixed solution thin up, by extracted with diethyl ether three times, merge organic phase, organic phase is used respectively H
2o and saturated NaCl solution washing, use anhydrous Na
2sO
4drying, filter and steam solvent, obtains (+)-trans verbenol colourless liquid.
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| CN104970016B (en) * | 2014-04-03 | 2017-04-12 | 中国林业科学研究院森林生态环境与保护研究所 | Attractant of tomicus yunnanensis |
| CN104970017B (en) * | 2014-04-03 | 2017-04-12 | 中国林业科学研究院森林生态环境与保护研究所 | Components and formula of attractant of tomicus minor hartig |
| CN104814009B (en) * | 2015-03-25 | 2018-10-19 | 中国林业科学研究院森林生态环境与保护研究所 | Larch bark bcetle worm repellant and lure and preparation method thereof |
| CN104855376A (en) * | 2015-04-08 | 2015-08-26 | 海南大学 | Formula for trapping agent of bark beetles in rubber |
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