CN101550117A - Fall webworm sex pheromone synthesizing method - Google Patents
Fall webworm sex pheromone synthesizing method Download PDFInfo
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Abstract
The invention provides a fall webworm sex pheromone synthesizing method, which relates to an epoxypropane coumpound. The method takes (Z)-2-acetylene tetradecanol synthesized by cheap and easy obtained 2-propargyl alcohol as raw materials, to synthesize fall webworm sex pheromone 3 [(9S, 10R) -9,10 - epoxy - (3Z, 6Z) -3,6-heneidecadienol] and 4 [(9S, 10R) -9,10 - epoxy - (3Z, 6Z) -1,3 ,6-heneidecatrienol] with high efficiency, high enantioselectivity and high yield. Step 6, 25% of the total yield is synthesized into (9S, 10R) -3; 6-step, 21% of the total yield is synthesized into (9S, 10R)-4; and the antipode excess e. e is more than 99%. The separation of the various steps of the invention is simple; the used reagent are all common reagents, cheap and easy to get; the invention has high yield and a shorter route, and is suitable for requirement o f the industrial production.
Description
Technical field
The present invention relates to a kind of propylene oxide compound, especially an end is a saturated carbon chains, and an end is the synthetic method of unsaturated carbon chains propylene oxide compound, especially a kind of synthetic fall webworm sex pheromone III[(9S, 10R)-9, the 10-epoxy-(3Z, 6Z)-3,6-21 carbon diene] and IV[(9S, 10R)-9, the 10-epoxy-(3Z, 6Z)-1,3,6-21 carbon triolefin] method.
Background technology
Fall webworms have another name called autumn curtain caterpillar, belong to worldwide quarantine pest insect, broad-leaved such as main harm fruit tree, shade tree and ornamental trees and farm crop etc.This worm originates in the North America, imports China in 1979 into, give farming, production of forestry and the urban afforestation of China bring huge harm (1, Ni Jing, Bai Guoyi, Cao Lin, Zhang Fangli; The study on the synthesis of fall webworm sex pheromone is explored; Chemical propellant and macromolecular material; 2002,6,14-16), nineteen ninety is classified as one of seven fully stocked wood insects by Ministry of Forestry.At 2008 Beijing Olympic Games opening eve, so the insect pest of North China's big area outburst fall webworms is to monitoring, the quarantine of fall webworms and prevent and treat extremely urgent.
With respect to using traditional agricultural chemicals kill pests, adopt the fall webworm sex pheromone of synthetic, can trap fall webworms very effectively, reach the purpose that reduces the fall webworms insect pest.1976, Russia and the U.S. two countries begin the cooperation, in nineteen eighty-two successfully identify fall webworm sex pheromone three kinds of component I [(9Z, 12Z)-diene-18 aldehyde], II[(9Z, 12Z, 15Z)-triolefin-18 aldehyde], III.But three kinds of components of this of synthetic are failed to demonstrate and are significantly lured the worm activity.Hungary Toth in 1989 etc. utilize modern separate analytical technique to find two new component I V and V[(9S again, 10R)-9, and the 10-epoxy-(3Z, 6Z)-1,3,6-20 carbon triolefin].Late 1980s, states such as Japan, China, Hungary, Italy cooperate, and 5 components identifying are carried out woodland give birth to survey and screening, have confirmed that the woodland of synthetic sex attractant lures the worm activity.
Since nineteen eighty-two Hill has reported the structure of fall webworm sex pheromone, the organic chemist studies the complete synthesis of fall webworm sex pheromone, for preceding two olefine aldehydr compounds, from the natural compounds linolenic and linoleic carry out first esterification then partial reduction get final product.The synthetic difficult point concentrates on the compound of back 3 propylene oxide that contain chirality, and the main synthetic method of having reported is as follows:
Initial Kovalev adopts parallel synthetic strategy for the needs of identifying have synthesized III, utilizes uncommon (Wittig) reaction of loving and respect one's elder brother Wei, for synthetic method is thereafter established basic ideas.
The shortcoming of this method is that yield is low, stereoselectivity is bad.Compound is write a Chinese character in simplified form NH
3Be liquefied ammonia, Na is a sodium Metal 99.5.
The eighties in 20th century, the K.Mori of Tokyo Univ Japan has successively finished the synthetic of 5 kinds of components of fall webworm sex pheromone according to the structure of American-European scholar's report.To synthesizing of compound III, omnidistance productive rate reaches 7%, and to synthesizing of compound IV, omnidistance productive rate reaches 1.5%.Its synthetic route is as follows:
The route of this method is oversize, and productive rate is low, and the intermediate product of polyyne is very unstable, easily isomerization or oxidation.It is the ethyl Grignard reagent that compound is write a Chinese character in simplified form EtMgBr, Cu
2Cl
2Be cuprous chloride, THF is a tetrahydrofuran (THF), PBr
3Be phosphorus tribromide, C
5H
5N is a pyridine, and THP is the tetrahydropyrans protecting group, and KOH is a potassium hydroxide, and EtOH is an ethanol, and PPTS is the tosic acid pyridinium salt, and MeOH is a methyl alcohol, (n-C
10H
21)
2CuLi is an organic copper lithium reagent, Et
2O is an ether.
1993, woods Guoqiang etc. were raw material with two ethene methyl alcohol, through 10 steps reactions such as Sharpless asymmetric Epoxidation, had synthesized fall webworm sex pheromone III, overall yield 16.8% (the superfluous e.e.=98% of enantiomorph).It is L-(+)-tartrate diisopropyl ester that compound is write a Chinese character in simplified form L-(+)-DIPT, Ti (Oi-Pr)
4Be tetra isopropyl oxygen titanium, t-BuO
2H is a peroxy tert-butyl alcohol, CH
2Cl
2Be methylene dichloride, TMSCl is a trimethylchlorosilane, Et
3N is a triethylamine, and TsOH is a tosic acid, and HBr is a hydrogen bromide, and HOAc is an acetate, and PDC is a pyridinium dichromate, and n-BuLi is a n-Butyl Lithium, and HMPA is a hexamethylphosphoramide.
Bell in 1988, Yadav in 1998, Zhang in 1999 etc. are by key intermediate 1, and 2-epoxy-3-sulphonate is at boron trifluoride diethyl etherate (BF
3Et
2O) exist following and the synthetic fall webworm sex pheromone III of lithium reagent coupling, IV.Compound writes a Chinese character in simplified form 1, and 4-heptadiyne-Li is 1,4-two heptyne lithiums, K
2CO
3Be salt of wormwood, BaSO
4Be barium sulfate, quinoline is a quinoline, and pentane is a Skellysolve A, and 1-hexyne is the 1-hexin, Ac
2O is a diacetyl oxide, and DMAP is a Dimethylamino pyridine, and ozonolysis refers to that ozone decomposes, and NHMDS is a sodium hexamethyldisilazide.
K.Mori in 2005 is raw material with the cis-butenediol, has determined the three-dimensional arrangement of epoxy by enzymatic chiral separation, introduces saturated alkyl and polyenoid fragment respectively by linked reaction then.Synthetic route is as follows, obtains III through 10 overall yields that go on foot with 12%, obtains IV (the superfluous e.e. of enantiomorph＞99%) through 12 overall yields that go on foot with 8.6%.
Compound is write a Chinese character in simplified form Tf
2O is a Trifluoromethanesulfonic anhydride, Pd/CaCO
3/ Pb
2+Be Lin Dela (Lindlar) catalyzer, cyclohexane is a hexanaphthene, and TBAF is a tetrabutyl ammonium fluoride, and TsCl is a Tosyl chloride, and TMS is trimethyl silicon based, and t-BuOK is a potassium tert.-butoxide, and 18-crown-6 is 18 hats 6, and hexane is a hexane.
To letter, gradually to high-level efficiency, the high purity direction develops above synthetic method from numerous.Because the unsaturated alkane of polyyne is very unstable, the preparation difficulty costs an arm and a leg, reported first introducing saturated carbon chains from Bell in 1988, synthetic important intermediate 1,2-epoxy-3-sulphonate, introduce the method for unsaturated carbon chains again, the similar synthetic route of the many employings of the scholar of back.By above introduction, be not difficult to find out that pheromone molecule I V and V's is synthetic than the III complexity, productive rate is low; Existent method, the whole piece route can only synthesize individual molecule, and efficient is low.
Summary of the invention
It is raw material with 2-propargyl alcohol (1) synthetic (Z) cheap and easy to get-2-alkynes ten four carbon alcohols (2) that purpose of the present invention aims to provide a kind of, the synthetic method of the fall webworm sex pheromone that efficient, enantioselectivity and productive rate are higher.
Described fall webworm sex pheromone is III[(9S, 10R)-9, and the 10-epoxy-(3Z, 6Z)-3,6-21 carbon diene] and IV[(9S, 10R)-9, the 10-epoxy-(3Z, 6Z)-1,3,6-21 carbon triolefin].
Synthetic route of the present invention is:
In following statement, specific synthetic product is according to the numbering in the structural formula, represents that with Arabic numerals R or S represent the absolute configuration of compound.
Step of the present invention is as follows:
1) under-40～0 ℃, the Sharpless epoxidation reaction takes place in compound 2 under catalyzer and oxygenant effect in a kind of halogenated hydrocarbon solvent, through extraction, dry, concentrate, obtain white solid 3 behind the purifying;
2) under-80～0 ℃, compound 3 in a kind of halohydrocarbon or ether solvent, under the organic bases effect, with the reaction of a kind of sulphonic acid anhydride, through extraction, dry, concentrate, obtain colourless liquid 4 behind the purifying;
3) under-100～0 ℃, compound 4 is in a kind of ether solvent, under catalyst action with 3, the alkynes negative ion generation linked reaction of the trimethyl silicon based ether of 6-diine enanthol, after water treatment, extraction, concentrate, in alkali alcosol, remove silica-based protection, through extraction, dry, concentrate, obtain white solid 5 behind the purifying;
4) under 0～25 ℃, catalytic hydrogenation reaction takes place in compound 5 under the Lindlar catalyst action in a kind of lower boiling alkane solvent saturated by hydrogen, through filtering, concentrate, obtaining white solid 6 behind the purifying;
5) under-10～30 ℃, compound 6 reacts with carbon tetrabromide and triphenyl phosphorus in a kind of halogenated hydrocarbon solvent, through extraction, dry, concentrate, obtain colourless liquid 7 behind the purifying;
6) under 60～80 ℃, compound 7 reacts under the effect of catalyzer in the saturated alcoholic solution of a kind of ammonium chloride, through filtration, concentrate, obtain behind the purifying colourless liquid (9S, 10R)-III;
7) under-40～0 ℃, compound 7 take place to be eliminated reaction under the effect of catalyzer and a kind of alkali in a kind of lower boiling alkane solvent, through extraction, dry, concentrate, obtain behind the purifying colourless liquid (9S, 10R)-IV.
In step 1), described halogenated hydrocarbon solvent can be selected from C
1～C
4Halohydrocarbon etc., particularly methylene dichloride or trichloromethane etc.; Described catalyzer can be selected tetra isopropyl oxygen titanium, L-tartrate diisopropyl ester, L-tartrate diethyl ester, 4 for use
Molecular sieve, 3
Molecular sieve, 300～400 purpose silica gel or hydrolith etc.; Described oxygenant is the nonane solution of tertbutanol peroxide etc.
In step 2) in, described halogenated hydrocarbon solvent is selected from C
1～C
4Halohydrocarbon etc., particularly methylene dichloride or trichloromethane etc.; Described ether solvent is selected from C
2～C
4Aliphatic ether or alicyclic ether etc., particularly ether or tetrahydrofuran (THF) etc.; Described organic bases can be selected tertiary amine etc., particularly imidazoles, pyridine or triethylamine etc. for use; Described sulphonic acid anhydride can be selected Trifluoromethanesulfonic anhydride etc. for use.
In step 3), described ether solvent can be selected from C
2～C
4Aliphatic ether or alicyclic ether etc., particularly ether or tetrahydrofuran (THF) etc.; Described catalyzer can be hexamethylphosphoramide etc.; 3, the alkynes negative ion of the trimethyl silicon based ether of 6-diine enanthol is by 3, and trimethyl silicon based ether of 6-diine enanthol and highly basic effect make, and highly basic is n-Butyl Lithium; Alkali is carbonate, particularly salt of wormwood or yellow soda ash etc.; Alcohol can be selected from C
1～C
6Fatty Alcohol(C12-C14 and C12-C18) etc., particularly methyl alcohol or ethanol etc.
In step 4), described lower boiling alkane solvent can be selected from C
5～C
6Aliphatics saturated alkane etc., particularly hexanaphthene or normal hexane etc.; The Lindlar catalyzer can be selected from that metallic lead is poisoned or the lime carbonate of the palladium metal that quinoline is poisoned or barium sulfate carrier etc.; But doping in the Lindlar catalyzer, described additive can be selected from rare or cyclohexadiene of alkene etc., particularly hexamethylene etc.
In step 5), described halogenated hydrocarbon solvent can be selected from C
1～C
4Halohydrocarbon etc., particularly methylene dichloride or trichloromethane etc.
In step 6), described alcohol can be selected from C
1～C
6Fatty Alcohol(C12-C14 and C12-C18) etc., particularly methyl alcohol or ethanol etc.; Described catalyzer can be platina etc.
In step 7), described lower boiling alkane solvent can be selected from C
5～C
6Aliphatics saturated alkane etc., particularly Skellysolve A or normal hexane etc.; Described catalyzer can be selected from crown ether etc., particularly 18 is preced with 6 or 15 hats 5 etc.; Described alkali can be selected from the metal-salt etc. of alcohol, particularly potassium tert.-butoxide or ethanol and receive etc.
The present invention is a raw material with (Z)-2-alkynes ten four carbon alcohols (2) cheap and easy to get, efficient, high enantioselectivity, high productivity synthesized fall webworm sex pheromone (9S, 10R)-III and (9S, 10R)-IV.Each step operation of the present invention separates simple, and productive rate is higher, and used reagent is common agents, and is cheap and easy to get, and route is shorter.6 steps, overall yield 25% synthesized (9S, 10R)-III; 6 steps, overall yield 21% synthesized (9S, 10R)-IV; Enantioselectivity height (the superfluous e.e. of enantiomorph＞99%).
Embodiment
The present invention is further illustrated below by embodiment.
Embodiment 1
Step 1 synthetic (2S, 3R)-2,3-epoxy-1-14 carbon alcohol (3)
Under the argon atmospher protection, 200mg silica gel mixes the 150mg hydrolith, injects 280mL exsiccant dichloromethane solvent, injects 10.9mL (35.8mmol) tetra isopropyl oxygen titanium, and-35 ℃ are stirred 20min.(-35 ℃ are stirred 20min for 9825mg, methylene dichloride 41.1mmol) (15mL) solution slowly to inject L-(+)-tartrate diisopropyl ester.(-35 ℃ are stirred 20min for 6.6g, methylene dichloride 31.13mmol) (15mL) solution slowly to inject (Z)-2-alkynes ten four carbon alcohols 2.Slowly inject nonane (12.5mL) solution of tertbutanol peroxide (68.49mmol) ,-30 ℃ were stirred 3 days.Add 80mL 10% tartaric aqueous solution cancellation reaction, slowly heat up, separatory, water dichloromethane extraction, (3 * 20mL) washings three times of organic layer saturated aqueous common salt.Anhydrous sodium sulfate drying concentrates, and obtains white solid 3 (4.7g, 65%) behind the purifying.R
f0.25(ethyl?acetate∶petroleum?ether＝1∶5)；mp?69-70℃；[α]
D 28-4.26(c?1.01，CHCl
3)；IR(film)v
max：3301(br)，2954，2914，2849，1470，1035，891，843，716cm
-1；
1H-NMR(400MHz，CDCl
3)δ：0.88(t，J＝6.8Hz，3H，CH
3)，1.20-1.62(m，20H，C
10H
20CH
3)，2.12(dd，J＝4.6，7.5Hz，1H，OH)，3.01-3.06(m，1H，C(3)-H)，3.16(ddd，J＝3.9，4.3，7.0Hz，1H，C(2)-H)，3.67(ddd，J＝4.6，7.0，11.9Hz，1H，CH
2OH)，3.86(ddd，J＝3.9，7.5，11.9Hz，1H，CH
2OH)ppm；
13C-NMR(100MHz，CDCl
3)δ：14.1，22.7，26.6，27.9，29.3，29.4，29.48，29.5，29.58，29.59，31.9，56.9，57.3，60.9ppm；MS(ESI)m/z?251.2(M+Na
+，100％)；Anal.Calcd?for?C
14H
28O
2：C，73.63；H，12.36.Found：C，73.66；H，12.36.
Step 2 synthetic (2S, 3R)-2,3-epoxy-ten four carbon alcohols trifluoromethayl sulfonic acid ester (4)
Argon atmospher protection down ,-78 ℃ to compound 3 (502mg, (1.1mL, 7.9mmol), (1.1mL 6.6mmol), slowly is warming up to the solution clarification to Trifluoromethanesulfonic anhydride to add triethylamine in methylene dichloride 2.2mmol) (146mL) solution.30mL saturated ammonium chloride solution cancellation reaction, separatory, water dichloromethane extraction, organic layer saturated aqueous common salt (2 * 10mL) washed twice.Anhydrous sodium sulfate drying concentrates, and gets colourless liquid 4 (775mg, 98%) behind the purifying.R
f?0.33(ethyl?acetate∶petroleum?ether＝1∶40).
Step 3 synthetic (9S, 10R)-9,10-epoxy-3,6-diine-1-21 carbon alcohol (5)
Argon atmospher protection down ,-78 ℃ to 3 of new system, the trimethyl silicon based ether of 6-diine enanthol (900mg, add in ether 5.0mmol) (23mL) solution n-Butyl Lithium (2.9M in hexane, 1.6mL, 4.6mmol) ,-78 ℃ of reaction 30min.Slowly add compound (2S, 3R)-4 (900mg, the hexamethylphosphoramide of (2mL) solution of ether 2.5mmol) and 0.9mL ,-78 ℃ of reaction 40min.20mL methyl alcohol cancellation reaction, (690mg 5mmol), stirs 1h under the room temperature to add Anhydrous potassium carbonate.Concentrate, washing, extracted with diethyl ether, anhydrous sodium sulfate drying concentrates, and gets white solid (9S, 10R)-5 (680mg, 85%) behind the purifying.R
f0.25(ethyl?acetate∶petroleum?ether＝1∶4)；mp?72-73℃；[α]
D 28+32.45(c?1.02，CHCl
3)；IR(film)v
max：3311(br)，3171，2954，2916，2849，1470，1318，1049，843cm
-1；
1H-NMR(400MHz，CDCl
3)δ：0.88(t，J＝6.8Hz，3H，CH
3)，1.20-1.55(m，20H，C
10H
20CH
3)，1.72(t，J＝6.3Hz，1H，OH)，2.28(ddt，J＝17.0，7.0，2.4Hz，1H，C(8)-H)，2.45(tt，J＝6.2，2.4Hz，2H，C(2)-H)，2.55(ddt，J＝17.0，5.7，2.4Hz，1H，C(8)-H)，2.96(dt，J＝4.2，5.9Hz，1H，C(10)-H)，3.12(ddd，J＝4.2，5.7，7.0Hz，1H，C(9)-H)，3.16(ddt，J＝2.4，2.4，2.4Hz，2H，C(5)-H)，3.71(dt，J＝6.3，6.2Hz，2H，CH
2OH)ppm；
13C-NMR(100MHz，CDCl
3)δ：9.8，14.1，18.7，22.6，23.0，26.4，27.5，29.3，29.4，29.5，29.59，29.6，31.9，55.0，57.1，61.0，75.7，76.22，76.23，77.1ppm；MS(ESI)m/z?341.3(M+Na
+，100％)，357.3(M+K
+，70％)；Anal.Calcd?for?C
21H
34O
2：C，79.19；H，10.76.Found：C，78.95；H，11.03.
Step 4 synthetic (9S, 10R)-9, the 10-epoxy-(3Z, 6Z)-3,6-diene-1-21 carbon alcohol (6)
Under the nitrogen atmosphere, 0 ℃ to Lindlar catalyzer (Pd/CaCO
3/ Pb
2+, 50mg) (0～20 ℃ of about 30min of reaction filters middle adding compound 5, concentrates, and gets white solid (9S, 10R)-6 (330mg, 60%) behind the purifying for 550mg, normal hexane 1.73mmol) (10mL) solution.R
f0.29(ethyl?acetate∶petroleum?ether＝1∶4)；mp?46-47℃；[α]
D 28-2.64(c?1.10，CHCl
3)；IR(film)v
max：3234(br)，2954，2914，2848，1650(w，C＝C)，1469，1450，1080，1057，1030，828，720cm
-1；
1H-NMR(400MHz，CDCl
3)δ：0.88(t，J＝6.8Hz，3H，CH
3)，1.20-1.55(m，20H，C
10H
20CH
3)，1.45(t，J＝5.8Hz，1H，OH)，2.24(dt，J＝14.6，5.7Hz，1H，C(8)-H)，2.32-2.44(m，3H，C(8)-H，C(2)-H)，2.86(m，2H，C(5)-H)，2.91-2.98(m，2H，C(9)-H，C(10)-H)，3.66(dt，J＝5.8，6.4Hz，2H，CH
2OH)，5.38-5.60(m，4H，C(3)-H，C(4)-H，C(6)-H，C(7)-H)ppm；
13C-NMR(100MHz，CDCl
3)δ：14.1，22.7，25.9，26.3，26.6，27.8，29.3，29.5，29.6，29.61，30.8，31.9，56.4，57.2，62.1，124.6，126.0，130.2，130.6ppm；MS(ESI)m/z345.4(M+Na
+，100％)；Anal.Calcd?for?C
21H
38O
2：C，78.20；H，11.88.Found：C，77.94；H，12.16.
Step 5 synthesize the 1-bromo-(9S, 10R)-9, the 10-epoxy-(3Z, 6Z)-3,6-21 carbon diene (7)
Argon atmospher protection down, 0 ℃ to compound (9S, 10R)-6 (613mg, add in methylene dichloride 1.9mmol) (19mL) solution carbon tetrabromide (756mg, 2.28mmol) and triphenyl phosphorus (598mg 2.28mmol), rises to the about 1h of room temperature reaction.The Skellysolve A dilution is filtered, and concentrates, and gets colourless liquid (9S, 10R)-7 (635mg, 87%) behind the purifying.R
f0.30(ethyl?acetate∶petroleumether＝1∶40)；[α]
D 28+1.10(c?1.18，CHCl
3)；IR(film)v
max：3014，2955，2924，2854，1648(w，C＝C)，1465，1380，1307，1267，1208，1034，969，898，826，721cm
-1；
1H-NMR(400MHz，CDCl
3)δ：0.88(t，J＝6.8Hz，3H，CH
3)，1.20-1.60(m，20H，C
10H
20CH
3)，2.23(dt，J＝15.1，6.1Hz，1H，C(8)-H)，2.38(dt，J＝15.1，6.1Hz，1H，C(8)-H)，2.65(dt，J＝7.0，7.0Hz，2H，C(2)-H)，2.83(t，J＝6.1Hz，2H，C(5)-H)，2.94(m，2H，C(9)-H，C(10)-H)，3.38(t，J＝7.0Hz，2H，CH
2Br)，5.36-5.58(m，4H，C(3)-H，C(4)-H，C(6)-H，C(7)-H)ppm；
13C-NMR(100MHz，CDCl
3)δ：14.1，22.7，26.0，26.3，26.6，27.8，29.3，29.5，29.61，29.62，30.8，31.9，32.3，56.3，57.2，124.9，126.6，129.9，130.5ppm；MS(ESI)m/z407.2，409.1(M+Na
+，both?100％)；Anal.Calcd?for?C
21H
37BrO：C，65.44；H，9.68.Found：C，65.55；H，9.89。
Step 6 synthetic (9S, 10R)-9, the 10-epoxy-(3Z, 6Z)-3,6-21 carbon diene (III)
In the aqueous solution (20mL) of copper sulfate (400mg), add zinc powder (3.0g) under the room temperature, leave standstill behind the stirred for several min, filter alloy water and methanol wash.The platina of new system places and is chlorinated the saturated methyl alcohol of ammonium (15mL), the adding compound (9S, and 10R)-7 (77mg, 0.20mmol), the about 40min of mixture temperature rising reflux.Filter, filter cake washs with ether, concentrate, behind the purifying colourless liquid (9S, 10R)-III (56mg, 92%).R
f0.35(ethyl?acetate∶petroleum?ether＝1∶50)；[α]
D 28+3.93(c?1.83，CHCl
3)；IR(film)v
max：3012，2960，2925，2854，1648，1463，1381，1069，1026，720cm
-1；
1H-NMR(400MHz，CDCl
3)δ：0.88(t，J＝6.8Hz，3H，C
10H
20CH
3)，0.98(t，J＝7.5Hz，3H，C(1)-H)，1.20-1.60(m，20H，C
10H
20CH
3)，2.08(dq，J＝7.2，7.5Hz，2H，C(2)-H)，2.22(dt，J＝15.1，6.4Hz，1H，C(8)-H)，2.40(dt，J＝15.1，6.2Hz，1H，C(8)-H)，2.81(t，J＝7.0Hz，2H，C(5)-H)，2.90-2.97(m，2H，C(9)-H，C(10)-H)，5.26-5.56(m，4H，C(3)-H，C(4)-H，C(6)-H，C(7)-H)ppm；
13C-NMR(100MHz，CDCl
3)δ：14.1，14.2，20.5，22.7，25.7，26.2，26.6，27.8，29.3，29.5，29.6，29.61，31.9，56.4，57.2，124.2，126.7，130.7，132.2ppm；MS(ESI)m/z?329.2(M+Na
+，100％)；Anal.Calcd?for?C
21H
38O：C，82.28；H，12.50.Found：C，82.54；H，12.13.
Step 7 synthetic (9S, 10R)-9, the 10-epoxy-(3Z, 6Z)-1,3,6-21 carbon triolefin (IV)
Argon atmospher protection down ,-40 ℃ to compound (9S, 10R)-7 (116mg, add in normal hexane 0.30mmol) (3mL) solution potassium tert.-butoxide (51mg, 0.45mmol) and 18 hats 6 (8mg 0.03mmol), is warming up to-20 ℃ of about 3h of reaction.1mL saturated ammonium chloride solution cancellation reaction, separatory, the water extracted with diethyl ether, organic layer washs with saturated aqueous common salt (1mL).Anhydrous sodium sulfate drying concentrates, behind the purifying colourless liquid (9S, 10R)-IV (68mg, 75%).R
f0.35(ethyl?acetate∶petroleumether＝1∶50)；[α]
D 28-0.88(c?1.94，CHCl
3)；IR(film)v
max：2924，2854，1635，1466，1429，1379，1080，1051，1035，1018，996，903cm
-1；
1H-NMR(400MHz，CDCl
3)δ：0.88(t，J＝6.8Hz，3H，CH
3)，1.20-1.57(m，20H，C
10H
20CH
3)，2.24(dt，J＝14.5，6.4Hz，1H，C(8)-H)，2.40(dt，J＝14.5，6.4Hz，1H，C(8)-H)，2.90-3.00(m，4H，C(5)-H，C(9)-H，C(10)-H)，5.13(d，J＝10.1Hz，1H，C(1)-H)，5.22(d，J＝16.8Hz，1H，C(1)-H)，5.41(dt，J＝10.5，8.0Hz，1H，C(4)-H)，5.45-5.58(m，2H，C(6)-H，C(7)-H)，6.03(dd，J＝10.9，10.5Hz，1H，C(3)-H)，6.65(ddd，J＝16.8，10.9，10.1Hz，1H，C(2)-H)ppm；
13C-NMR(100MHz，CDCl
3)δ：14.1，22.7，26.25，26.28，26.6，27.8，29.3，29.55，29.63，31.9，56.3，57.2，117.7，124.9，129.5，129.83，129.88，131.8ppm；MS(ESI)m/z?327.2(M+Na
+，100％)；Anal.Calcd?for?C
21H
36O：C，82.83；H，11.92.Found：C，82.94；H，11.63.
Embodiment 2
Step 1 synthetic (2S, 3R)-2,3-epoxy-1-14 carbon alcohol (3)
Under the argon atmospher protection, activatory 3
Molecular sieve powder 300mg injects 280mL exsiccant dichloromethane solvent, injects 1.09mL (3.58mmol) tetra isopropyl oxygen titanium, and-35 ℃ are stirred 20min.(-35 ℃ are stirred 20min for 983mg, methylene dichloride 4.11mmol) (5mL) solution slowly to inject L-(+)-tartrate diisopropyl ester.(-35 ℃ are stirred 20min for 6.6g, methylene dichloride 31.13mmol) (15mL) solution slowly to inject (Z)-2-alkynes ten four carbon alcohols 2.Slowly inject nonane (12.5mL) solution of tertbutanol peroxide (68.49mmol) ,-30 ℃ were stirred 3 days.Add 50mL 10% tartaric aqueous solution cancellation reaction, slowly heat up separatory, water CH
2Cl
2Extraction, (3 * 20mL) wash three times organic layer with saturated aqueous common salt.Anhydrous sodium sulfate drying concentrates, and obtains white solid 3 (4415mg, 62%) behind the purifying.
Step 2 synthetic (2S, 3R)-2,3-epoxy-ten four carbon alcohols trifluoromethayl sulfonic acid ester (4)
The operation of compound 4 is identical with the operation among the embodiment 1, and the solvent of reaction is used trichloromethane instead, and alkali is used pyridine instead, the yield basal ration.
Step 3 synthetic (9S, 10R)-9,10-epoxy-3,6-diine-1-21 carbon alcohol (5)
Argon atmospher protection down ,-78 ℃ to 3 of new system, adds n-Butyl Lithium (2.9M in hexane) in the tetrahydrofuran solution of the trimethyl silicon based ether of 6-diine enanthol ,-78 ℃ of reaction 30min.Slowly add compound (2S, tetrahydrofuran solution 3R)-4 and hexamethylphosphoramide ,-78 ℃ of reaction 40min.Methyl alcohol cancellation reaction adds anhydrous sodium carbonate, stirs 1h under the room temperature.Concentrate, washing, extracted with diethyl ether, anhydrous sodium sulfate drying concentrates, behind the purifying white solid (9S, 10R)-5 (88%).
Step 4 synthetic (9S, 10R)-9, the 10-epoxy-(3Z, 6Z)-3,6-diene-1-21 carbon alcohol (6)
Under the nitrogen atmosphere, 0 ℃ to Lindlar catalyzer (Pd/CaCO
3/ Pb
2+, add in 35mg) compound 5 (540mg, hexanaphthene 1.7mmol) (10mL) solution adds the 0.5mL tetrahydrobenzene again, 10～20 ℃ of about 30min of reaction filter, and concentrate, and get white solid (9S, 10R)-6 (340mg, 63%) behind the thick purifying products.
Step 5 synthesize the 1-bromo-(9S, 10R)-9, the 10-epoxy-(3Z, 6Z)-3,6-21 carbon diene (7)
The operation of compound 7 is identical with the operation among the embodiment 1, and the solvent of reaction is used trichloromethane instead, and yield is 85%.
Step 6 synthetic (9S, 10R)-9, the 10-epoxy-(3Z, 6Z)-3,6-21 carbon diene (III)
The operation of compound III is identical with the operation among the embodiment 1, and the solvent of reaction is used ethanol instead, and yield is 90%.
Step 7 synthetic (9S, 10R)-9, the 10-epoxy-(3Z, 6Z)-1,3,6-21 carbon triolefin (IV)
Argon atmospher protection down ,-40～-30 ℃ to compound (9S adds in Skellysolve A solution 10R)-7 that ethanol is received and 15 hats 5, is warming up to-20 ℃ of about 3h of reaction.Saturated ammonium chloride solution cancellation reaction, separatory, water extracted with diethyl ether, organic layer saturated common salt water washing.Anhydrous sodium sulfate drying concentrates, behind the purifying colourless liquid (9S, 10R)-IV (68%).
Embodiment 3
Step 1 synthetic (2S, 3R)-2,3-epoxy-1-14 carbon alcohol (3)
Under the argon atmospher protection, 200mg silica gel mixes the 150mg hydrolith, injects 280mL exsiccant dichloromethane solvent, injects 10.9mL (35.8mmol) tetra isopropyl oxygen titanium, and-35 ℃ are stirred 20min.(-35 ℃ are stirred 20min for 8650mg, methylene dichloride 41.1mmol) (15mL) solution slowly to inject L-(+)-tartrate diethyl ester.(-35 ℃ are stirred 20min for 6.6g, methylene dichloride 31.13mmol) (15mL) solution slowly to inject (Z)-2-alkynes ten four carbon alcohols 2.Slowly inject nonane (12.5mL) solution of tertbutanol peroxide (68.49mmol) ,-30 ℃ were stirred 3 days.Add 80mL 10% tartaric aqueous solution cancellation reaction, slowly heat up, separatory, water dichloromethane extraction, (3 * 20mL) washings three times of organic layer saturated aqueous common salt.Anhydrous sodium sulfate drying concentrates, and obtains white solid 3 (4915mg, 68%) behind the thick purifying products.
Step 2 synthetic (2S, 3R)-2,3-epoxy-ten four carbon alcohols trifluoromethayl sulfonic acid ester (4)
The operation of compound 4 is identical with the operation among the embodiment 1, and alkali is used imidazoles instead, the yield basal ration.
Step 3 synthetic (9S, 10R)-9,10-epoxy-3,6-diine-1-21 carbon alcohol (5)
Argon atmospher protection down ,-100 ℃ to 3 of new system, adds n-Butyl Lithium (2.9M in hexane) in the diethyl ether solution of the trimethyl silicon based ether of 6-diine enanthol ,-100 ℃ of reaction 1h.Slowly add compound (2S, diethyl ether solution 3R)-4 and hexamethylphosphoramide ,-100 ℃ of reaction 2h.Ethanol cancellation reaction adds Anhydrous potassium carbonate, stirs 1h under the room temperature.Concentrate, washing, extracted with diethyl ether, anhydrous sodium sulfate drying concentrates, behind the thick purifying products white solid (9S, 10R)-5 (92%).
Step 4 synthetic (9S, 10R)-9, the 10-epoxy-(3Z, 6Z)-3,6-diene-1-21 carbon alcohol (6)
Under the nitrogen atmosphere, 0 ℃ to Lindlar catalyzer (Pd, 5wt%on BaSO
4) in add the hexane solution of compound 5, add an amount of quinoline again, 10～25 ℃ of about 40min of reaction filter, and get white solid (9S, 10R)-6 (55%) behind the thick purifying products.
Step 5 synthesize the 1-bromo-(9S, 10R)-9, the 10-epoxy-(3Z, 6Z)-3,6-21 carbon diene (7)
The operation of compound 7 is identical with the operation among the embodiment 1, and 0 ℃ is stirred 2h, and yield is 88%.
Step 6 synthetic (9S, 10R)-9, the 10-epoxy-(3Z, 6Z)-3,6-21 carbon diene (III)
In the aqueous solution (5mL) of copper sulfate (100mg), add zinc powder (0.75mg) under the room temperature, leave standstill behind the stirred for several min, filter alloy water and methanol wash.The platina of new system places and is chlorinated the saturated methyl alcohol of ammonium (10mL), the adding compound (9S, and 10R)-7 (77mg, 0.20mmol), the about 40min of mixture temperature rising reflux.Filter, the filter cake methanol wash concentrates, must colourless liquid behind the thick purifying products (9S, 10R)-III (58mg, 95%).
Step 7 synthetic (9S, 10R)-9, the 10-epoxy-(3Z, 6Z)-1,3,6-21 carbon triolefin (IV)
Argon atmospher protection down ,-40～-20 ℃ to compound (9S adds potassium tert.-butoxide and 18 hats 6 in cyclohexane solution 10R)-7, be warming up to-20 ℃ of about 5h of reaction.Saturated ammonium chloride solution cancellation reaction, separatory, water extracted with diethyl ether, organic layer saturated common salt water washing.Anhydrous sodium sulfate drying concentrates, behind the thick purifying products colourless liquid (9S, 10R)-IV (78%).
Claims (10)
1. the synthetic method of fall webworm sex pheromone is characterized in that described fall webworm sex pheromone is III[(9S, 10R)-9, and 10-epoxy-(3Z, 6Z)-3,6-21 carbon diene] and IV[(9S, 10R)-9,10-epoxy-(3Z, 6Z)-1,3,6-21 carbon triolefin], its synthetic route is:
Specific synthetic product is according to the numbering in the structural formula, represents that with Arabic numerals R or S represent the absolute configuration of compound.
2. the synthetic method of fall webworm sex pheromone as claimed in claim 1 is characterized in that may further comprise the steps:
1) under-40～0 ℃, the Sharpless epoxidation reaction takes place in compound 2 under catalyzer and oxygenant effect in a kind of halogenated hydrocarbon solvent, through extraction, dry, concentrate, obtain white solid 3 behind the purifying;
2) under-80～0 ℃, compound 3 in a kind of halohydrocarbon or ether solvent, under the organic bases effect, with the reaction of a kind of sulphonic acid anhydride, through extraction, dry, concentrate, obtain colourless liquid 4 behind the purifying;
3) under-100～0 ℃, compound 4 is in a kind of ether solvent, under catalyst action with 3, the alkynes negative ion generation linked reaction of the trimethyl silicon based ether of 6-diine enanthol, after water treatment, extraction, concentrate, in alkali alcosol, remove silica-based protection, through extraction, dry, concentrate, obtain white solid 5 behind the purifying;
4) under 0～25 ℃, catalytic hydrogenation reaction takes place in compound 5 under the Lindlar catalyst action in a kind of lower boiling alkane solvent saturated by hydrogen, through filtering, concentrate, obtaining white solid 6 behind the purifying;
5) under-10～30 ℃, compound 6 reacts with carbon tetrabromide and triphenyl phosphorus in a kind of halogenated hydrocarbon solvent, through extraction, dry, concentrate, obtain colourless liquid 7 behind the purifying;
6) under 60～80 ℃, compound 7 reacts under the effect of catalyzer in the saturated alcoholic solution of a kind of ammonium chloride, through filtration, concentrate, obtain behind the purifying colourless liquid (9S, 10R)-III;
7) under-40～0 ℃, compound 7 take place to be eliminated reaction under the effect of catalyzer and a kind of alkali in a kind of lower boiling alkane solvent, through extraction, dry, concentrate, obtain behind the purifying colourless liquid (9S, 10R)-IV.
3. the synthetic method of fall webworm sex pheromone as claimed in claim 2 is characterized in that in step 1), and described halogenated hydrocarbon solvent is selected from C
1～C
4Halohydrocarbon; Described catalyzer be selected from tetra isopropyl oxygen titanium, L-tartrate diisopropyl ester, L-tartrate diethyl ester,
Molecular sieve,
Molecular sieve, 300～400 purpose silica gel or hydroliths; Described oxygenant is the nonane solution of tertbutanol peroxide.
4. the synthetic method of fall webworm sex pheromone as claimed in claim 2 is characterized in that in step 2) in, described halogenated hydrocarbon solvent is selected from C
1～C
4Halohydrocarbon; Described ether solvent is selected from C
2～C
4Aliphatic ether or alicyclic ether; Described organic bases is a tertiary amine; Described sulphonic acid anhydride is a Trifluoromethanesulfonic anhydride.
5. the synthetic method of fall webworm sex pheromone as claimed in claim 2 is characterized in that in step 3), and described ether solvent is selected from C
2～C
4Aliphatic ether or alicyclic ether; Described catalyzer is a hexamethylphosphoramide.
6. the synthetic method of fall webworm sex pheromone as claimed in claim 2, it is characterized in that in step 3) described 3, the alkynes negative ion of the trimethyl silicon based ether of 6-diine enanthol is by 3, trimethyl silicon based ether of 6-diine enanthol and highly basic effect make, and highly basic is n-Butyl Lithium; Alkali is carbonate; Alcohol is selected from C
1～C
6Fatty Alcohol(C12-C14 and C12-C18).
7. the synthetic method of fall webworm sex pheromone as claimed in claim 2 is characterized in that in step 4), and described lower boiling alkane solvent is selected from C
5～C
6The aliphatics saturated alkane; Described Lindlar catalyzer is selected from the lime carbonate or the barium sulfate carrier of the palladium metal of metallic lead poisoning or quinoline poisoning.
8. the synthetic method of fall webworm sex pheromone as claimed in claim 2 is characterized in that in step 5), and described halogenated hydrocarbon solvent is selected from C
1～C
4Halohydrocarbon.
9. the synthetic method of fall webworm sex pheromone as claimed in claim 2 is characterized in that in step 6), and described alcohol is selected from C
1～C
6Fatty Alcohol(C12-C14 and C12-C18); Described catalyzer is a platina.
10. the synthetic method of fall webworm sex pheromone as claimed in claim 2 is characterized in that in step 7), and described lower boiling alkane solvent is selected from C
5～C
6The aliphatics saturated alkane; Described catalyzer is a crown ether; Described alkali is the metal-salt of alcohol.
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| CN101798293A (en) * | 2010-03-15 | 2010-08-11 | 厦门大学 | Simple stereoselective synthesis method of sex pheromones of hyphantria cunea |
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| CN107556150A (en) * | 2016-06-30 | 2018-01-09 | 上海有德化工科技有限公司 | A kind of synthetic method of fall webworm sex pheromone |
| CN109369573A (en) * | 2018-12-11 | 2019-02-22 | 苏州华道生物药业股份有限公司 | The preparation method of fall webworm sex pheromone intermediate |
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| CN101798293B (en) * | 2010-03-15 | 2012-05-23 | 厦门大学 | Simple stereoselective synthesis method of sex pheromones of hyphantria cunea |
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| CN109369573A (en) * | 2018-12-11 | 2019-02-22 | 苏州华道生物药业股份有限公司 | The preparation method of fall webworm sex pheromone intermediate |
| CN109369573B (en) * | 2018-12-11 | 2022-03-01 | 苏州华道生物药业股份有限公司 | Preparation method of sex pheromone intermediate of fall webworm |
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