CN108997100A - Lure ingredient suitable in a kind of pine moth pheromone, the synthetic method of trans- 12 carbon diene derivative of 5,7- - Google Patents
Lure ingredient suitable in a kind of pine moth pheromone, the synthetic method of trans- 12 carbon diene derivative of 5,7- Download PDFInfo
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- CN108997100A CN108997100A CN201810921472.9A CN201810921472A CN108997100A CN 108997100 A CN108997100 A CN 108997100A CN 201810921472 A CN201810921472 A CN 201810921472A CN 108997100 A CN108997100 A CN 108997100A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
- A01N31/02—Acyclic compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
- A01N35/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aliphatically bound aldehyde or keto groups, or thio analogues thereof; Derivatives thereof, e.g. acetals
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/02—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D309/10—Oxygen atoms
- C07D309/12—Oxygen atoms only hydrogen atoms and one oxygen atom directly attached to ring carbon atoms, e.g. tetrahydropyranyl ethers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Abstract
The invention discloses lure ingredient suitable in a kind of pine moth pheromone; trans- 5; the synthetic method of 12 carbon diene derivative of 7-; the synthetic method is with 5- hexin -1- pure and mild 3; 4- dihydro -2H- pyrans is starting material; successively suitable, trans- 5,7-, 12 carbon diene derivative is obtained by addition reaction, condensation reaction, elimination reaction, hydrogenation reaction, deprotection reaction and derivative reaction.The synthetic method route is shorter, meanwhile, each step reaction yield is higher, and it is easy to operate, it is convenient for mass production.
Description
Technical field
The invention belongs to organic synthesis fields, and in particular to and lure ingredient suitable in a kind of pine moth pheromone, trans- 5,7-
The synthetic method of 12 carbon diene derivatives.
Background technique
Pine moth Dendrolimus is the general designation of Lepidoptera Lasiocampidae Dendrolimus insect.Also known as caterpillar, fiery caterpillar,
Gu claims loose silkworm, shares more than 30, China is distributed with 27 kinds, is the most abundant country of pine moth type.Pine moth can be to conifer, cypress
The important species such as class, China fir class generate food evil.The earliest record of China sees Guangdong " Longchuan's county annals " in 1530: " 9 years bright Jiajin Year,
Occur year after year when great drought, hair is black, and thirty years of age to the greatest extent of food pine needle withered, spins on pine branch, being of winter end is to the greatest extent." so far, pine moth is still forest
The Main Forest Insect Pests that occurrence quantity is big in pest, harm is wide.It sprays insecticide currently, the control method of pine moth mainly passes through
Mode killed, one side cost is larger, and biggish pollution on the other hand can be caused to environment.
Sex pheromone is the animal for carrying out two sexual lifves, and the substance released to identify mutually can by such substance
Make female, male close.General is mostly that passively female secretion distributes sex pheromone, and the male for drawing active is lured to generate sexual excitement, but
Have by the type of male secretion.Pest control is used for using sex pheromone and its similar compound, the influence to environment is smaller, together
When, killing efficiency is also higher.
If the sex pheromone of pine moth is extracted from nature, yield is lower, meanwhile, higher cost is unfavorable for
Using research shows that suitable as shown in structure (I)~(III), trans- 5,7-, 12 carbon diene derivative is pine moth pheromones
Main component, if it is possible to which this artificial synthesized substance, can have great importance.
Summary of the invention
The present invention provides the synthetic method for luring ingredient in a kind of pine moth pheromone, the original which uses
Expect it is cheap and easily-available, meanwhile, obtained product yield high.
Lure ingredient suitable in a kind of pine moth pheromone, the synthetic method of trans- 5,7-, 12 carbon diene derivative, including
Following steps:
(1) 5- hexin -1- alcohol and 3,4- dihydro -2H- pyrans occur addition reaction, obtain oxinane -2- base alkynes hexyl
Ether；
(2) in the presence of alkali, condensation reaction occurs for the oxinane -2- base alkynes hexyl ether and hexanal that step (1) obtains,
Obtain condensation intermediate；
(3) elimination reaction occurs for the condensation intermediate that step (2) obtains, and obtains eliminating intermediate；
(4) under the action of hydrogenation catalyst, hydrogenation reaction occurs for the cancellation intermediate that step (3) obtains, and obtains adding hydrogen
Intermediate；
(5) what step (4) obtained adds hydrogen intermediate to slough protecting group by hydrolysis, before obtaining pine moth pheromone
Body；
(6) the pine moth pheromone precursor that step (5) obtains passes through derivatization, obtains suitable, trans- 5, the 7- 12
Carbon diene derivative；
The derivatization includes oxidation, esterification or propylated；
Preferably, the addition reaction carries out under the action of acid catalyst in step (1).As further
It is preferred that the acid catalyst is solid acid catalyst, preferably phosphotungstic acid.
Preferably, the alkali is n-BuLi in step (2), reaction carries out in tetrahydrofuran.
Preferably, the elimination reaction carries out under the action of thionyl chloride and pyridine in step (3).
Preferably, the hydrogenation catalyst is lindlar catalyst in step (4).
Preferably, the hydrolysis carries out under the action of HCl in step (5).
Preferably, the derivative turns to oxidation reaction, oxidant PCC in step (6).
Preferably, the derivative turns to ethyl esterified reaction in step (6), the effect in chloroacetic chloride and pyridine is reacted
Lower progress.
Preferably, the derivative turns to propylated reaction in step (6), reaction carries out under the action of potassium carbonate.
Compared with the existing technology, the beneficial effects of the present invention are embodied in:
(1) pure and mild 3, the 4- dihydro -2H- pyrans price of raw material 5- hexin -1- used in synthetic method of the invention is lower, just
It is preferably easy to get, the cost of synthesis can be effectively reduced；
(2) shorter using the entire reaction step of preparation method of the invention, yield is higher, and obtained product purity is higher,
It is convenient for producing in enormous quantities.
Specific embodiment
Embodiment 1
5- hexin -1- alcohol (11.8g, 0.12mol) and 3 is added into reaction flask, 4- dihydro -2H- pyrans (8.4g,
0.1mol), 1g solid acid catalyst phosphotungstic acid (H is then added3PW12O40), 100mL1,2- dichloroethanes carries out at room temperature
Reaction, after reaction 12 hours, TLC shows fully reacting.It filters, be concentrated to get crude product oxinane -2- base alkynes hexyl ether, produce
Product weight is 17.5g, and yield 96%, GC purity is 95.4%, directly progress next step reaction.
Embodiment 2
5- hexin -1- alcohol (11.8g, 0.12mol) and 3 is added into reaction flask, 4- dihydro -2H- pyrans (8.4g,
0.1mol), 1g solid acid catalyst ZSM-5 zeolite, 100mL 1 is then added, 2- dichloroethanes is reacted at room temperature,
After reaction 12 hours, TLC shows fully reacting.It filters, be concentrated to get crude product oxinane -2- base alkynes hexyl ether, product weight
Amount is 17.2g, and GC purity is 81.2%.
Embodiment 3
Be added in reaction flask obtain according to 1 method of embodiment oxinane -2- base alkynes hexyl ether (18.2g,
0.1mol), it vacuumizes, three times, dry tetrahydrofuran 50mL is then added in inflated with nitrogen, and stirring and dissolving is cooled to -20 DEG C, so
The pentane solution (2.5M, 80mL, 0.2mol) of n-BuLi is added dropwise afterwards, continues to stir half an hour.Then it is added dropwise into reaction solution
Tetrahydrofuran (50mL) solution of hexanal (11g, 0.11mol), after being added dropwise to complete, prior to -20 DEG C two hours of reaction, then room
Temperature stirring 12 hours, TLC shows fully reacting, and the aqueous solution that the ammonium chloride of saturation is added dropwise into reaction solution is quenched, then
Ethyl acetate is added to be extracted, twice with brine It, obtains organic phase and is dried with anhydrous magnesium sulfate, filters, removes
Solvent is removed, rectification under vacuum obtains condensation intermediate, product weight 25.9g, yield 91.8%, GC purity 97.1%.
Embodiment 4
The condensation intermediate (28.2g, 0.1mol) and pyridine obtained according to the method for embodiment 3 is added in reaction flask
(50mL) after being sufficiently stirred, is added dropwise thionyl chloride (23.8g, 0.2mol), is then reacted at 70 DEG C, react 12 hours
Vacuum distillation removes pyridine afterwards, and rectification under vacuum obtains eliminating intermediate, product weight 23.5g, yield 89%, GC purity
98.7%.
Embodiment 5
The condensation intermediate (28.2g, 0.1mol) and the concentrated sulfuric acid obtained according to the method for embodiment 3 is added in reaction flask
(100mL) after being sufficiently stirred, is heated to 170 DEG C and is reacted, and after reaction 3 hours, sampling analysis, raw material decomposes are serious, secondary anti-
It answers more, is not post-processed.
Embodiment 6
Cancellation intermediate (26.4g, 0.1mol), the Lin Dela obtained according to 4 method of embodiment is added in reaction flask to urge
Agent (5wt%) and methanol (50mL), are successively replaced three times with nitrogen and hydrogen respectively, then in the presence of the hydrogen of 1atm,
It is reacted 12 hours in 25 DEG C, TLC monitoring reaction filters after reaction, is spin-dried for solvent, and then progress column, which chromatographs to obtain, adds in hydrogen
Mesosome, product weight 25.8g, yield 97%, HPLC purity 96.4%.
Embodiment 7
Obtaining according to 6 method of embodiment plus hydrogen intermediate (26.6g, 0.1mol), HCL aqueous solution are added in reaction flask
(1N, 0.2mol) reacts 12 hours in 25 DEG C, and TLC monitoring reaction filters after reaction, is spin-dried for solvent, obtaining product weight is
17.8g, yield 98%, HPLC purity 96.1%.
Embodiment 8
4.3g (0.02mol) PCC is dissolved in 25ml methylene chloride, at room temperature, is instilled hydrolysate
In the 15ml dichloromethane solution of (1.8g, 0.01mol), stirring 2 hours, black mixture is diluted with 175ml ether, filtering,
Solid is washed with ether, and filtrate is washed with saturated common salt, and sodium sulphate is dry, and concentration is separated, ethyl acetate-with silica gel column chromatography
Petroleum ether (1:5) elution, obtains product 1 (1.5g), yield 83%, HPLC purity 98.1%.
The structural formula of product 1 is as follows:
Characterize data is as follows:
1H NMR(300MHz,CDCl3)δ9.40(t,1H),6.03(t,1H),5.95(t,1H),5.63(m,1H)5.48
(m,1H)2.43(dr,2H),2.38(dr,2H),2.07(m,2H),1.70(m,2H),1.30(m,4H),0.93(t,3H)
Embodiment 9
In reaction flask, hydrolysate (1.8g, 0.01mol), chloroacetic chloride (0.02mol) and pyridine 15ml, room temperature is added
Under be stirred overnight, then vacuum distillation remove pyridine, separated with silica gel column chromatography, ethyl acetate-light petrol elution, obtain product 2
(2.1g), yield 93%, HPLC purity 99.1%.
The structure of product 2 is as follows:
Characterize data is as follows:
1H NMR(300MHz,CDCl3)δ6.05(t,1H),5.96(t,1H),5.64(m,1H)5.49(m,1H),4.18
(t,2H),2.48(dr,2H),2.39(dr,2H),2.11(s,3H),2.07(m,2H),1.70(m,2H),1.30(m,6H),
0.93(t,3H)
Embodiment 10
In reaction flask, hydrolysate (1.8g, 0.01mol), N-Propyl Bromide (0.02mol), potassium carbonate (0.02mol) is added
With DMF 20ml, 60 DEG C are stirred overnight, and then plus water quenching reaction, the extraction of addition methylene chloride three times, successively use water and saturation
Brine It, anhydrous sodium sulfate is dry, is separated with silica gel column chromatography, and ethyl acetate-light petrol elution obtains product 3 (2.0g),
Yield 89%, HPLC purity 98.5%.
The structure of product 3 is as follows:
Characterize data is as follows:
1H NMR(300MHz,CDCl3)δ6.03(t,1H),5.92(t,1H),5.63(m,1H)5.47(m,1H),3.39
(t,2H),3.32(t,2H),2.48(dr,2H),2.39(dr,2H),2.07(m,2H),1.70(m,2H),1.43(m,2H),
1.29(m,6H),0.94(t,3H),0.91(t,3H)。
Claims (8)
1. lure ingredient suitable in a kind of pine moth pheromone, the synthetic method of trans- 5,7-, 12 carbon diene derivative, feature
It is, comprising the following steps:
(1) 5- hexin -1- alcohol and 3,4- dihydro -2H- pyrans occur addition reaction, obtain oxinane -2- base alkynes hexyl ether；
(2) in the presence of alkali, condensation reaction occurs for the oxinane -2- base alkynes hexyl ether and hexanal that step (1) obtains, and obtains
It is condensed intermediate；
(3) elimination reaction occurs for the condensation intermediate that step (2) obtains, and obtains eliminating intermediate；
(4) under the action of hydrogenation catalyst, hydrogenation reaction occurs for the cancellation intermediate that step (3) obtains, and obtains adding among hydrogen
Body；
(5) what step (4) obtained adds hydrogen intermediate to slough protecting group by hydrolysis, obtains pine moth pheromone precursor；
(6) the pine moth pheromone precursor that step (5) obtains passes through derivatization, obtains suitable, trans- 5,7-, 12 carbon pair
Ene derivative；
The derivatization includes oxidation, esterification or propylated；
Reaction equation is as follows:
2. lure ingredient suitable in pine moth pheromone according to claim 1, trans- 12 carbon diene derivative of 5,7-
Synthetic method, which is characterized in that in step (2), the alkali is n-BuLi, and reaction carries out in tetrahydrofuran.
3. lure ingredient suitable in pine moth pheromone according to claim 1, trans- 12 carbon diene derivative of 5,7-
Synthetic method, which is characterized in that in step (3), the elimination reaction carries out under the action of thionyl chloride and pyridine.
4. lure ingredient suitable in pine moth pheromone according to claim 1, trans- 12 carbon diene derivative of 5,7-
Synthetic method, which is characterized in that in step (4), the hydrogenation catalyst is lindlar catalyst.
5. lure ingredient suitable in pine moth pheromone according to claim 1, trans- 12 carbon diene derivative of 5,7-
Synthetic method, which is characterized in that in step (5), the hydrolysis carries out under the action of HCl.
6. lure ingredient suitable in pine moth pheromone according to claim 1, trans- 12 carbon diene derivative of 5,7-
Synthetic method, which is characterized in that in step (6), the derivative turns to oxidation reaction, oxidant PCC.
7. lure ingredient suitable in pine moth pheromone according to claim 1, trans- 12 carbon diene derivative of 5,7-
Synthetic method, which is characterized in that in step (6), the derivative turns to ethyl esterified reaction, reacts the work in chloroacetic chloride and pyridine
With under carry out.
8. lure ingredient suitable in pine moth pheromone according to claim 1, trans- 12 carbon diene derivative of 5,7-
Synthetic method, which is characterized in that in step (6), the derivative turn to propylated reaction, reaction under the action of potassium carbonate into
Row.
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| CN201810921472.9A CN108997100A (en) | 2018-08-14 | 2018-08-14 | Lure ingredient suitable in a kind of pine moth pheromone, the synthetic method of trans- 12 carbon diene derivative of 5,7- |
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| CN201810921472.9A CN108997100A (en) | 2018-08-14 | 2018-08-14 | Lure ingredient suitable in a kind of pine moth pheromone, the synthetic method of trans- 12 carbon diene derivative of 5,7- |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101801933A (en) * | 2007-09-26 | 2010-08-11 | 安斯泰来制药株式会社 | quinolone derivative |
| CN102613177A (en) * | 2011-01-27 | 2012-08-01 | 温州医学院 | Process for synthesizing sex pheromone of pine caterpillar |
| CN107207555A (en) * | 2015-01-21 | 2017-09-26 | 味之素株式会社 | Precipitation promoter and use its intermediate processing |
-
2018
- 2018-08-14 CN CN201810921472.9A patent/CN108997100A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101801933A (en) * | 2007-09-26 | 2010-08-11 | 安斯泰来制药株式会社 | quinolone derivative |
| CN102613177A (en) * | 2011-01-27 | 2012-08-01 | 温州医学院 | Process for synthesizing sex pheromone of pine caterpillar |
| CN107207555A (en) * | 2015-01-21 | 2017-09-26 | 味之素株式会社 | Precipitation promoter and use its intermediate processing |
Non-Patent Citations (5)
| Title |
|---|
| BERNARD L. FLYNN 等: "A Concise Approach to the Polycyclic Scaffold of Frondosin D", 《J. ORG. CHEM.》 * |
| LARRY E. OVERMAN 等: "Total Synthesis of (-)-Sarain A", 《J. AM. CHEM. SOC.》 * |
| TAYEBEE, REZA: "Mild and Efficient Catalytic Protocol for Tetrahydropyranylation of Alcohols Using Acidic Keggin and Wells-Dawson Structures", 《CHINESE JOURNAL OF CHEMISTRY》 * |
| 王礼琛: "《有机化学》", 31 December 2004, 东南大学出版社 * |
| 赵成华: "马尾松毛虫性外激素的新成分:化学结构鉴定和田间试验", 《昆虫学报》 * |
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