CN109134218A - Ingredient 4- oxo-trans- 2- hexenoic aldehyde synthetic method is lured in a kind of fleahopper sex pheromone - Google Patents
Ingredient 4- oxo-trans- 2- hexenoic aldehyde synthetic method is lured in a kind of fleahopper sex pheromone Download PDFInfo
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- CN109134218A CN109134218A CN201810921420.1A CN201810921420A CN109134218A CN 109134218 A CN109134218 A CN 109134218A CN 201810921420 A CN201810921420 A CN 201810921420A CN 109134218 A CN109134218 A CN 109134218A
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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
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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
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
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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
- C07C29/44—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon double or triple bond
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Abstract
The invention discloses ingredient 4- oxo-trans- 2- hexenoic aldehyde synthetic method is lured in a kind of fleahopper sex pheromone, comprising the following steps: (1) in the presence of alkali, substitution reaction occurs for propargyl alcohol and acetaldehyde, obtains 1- methyl-1,4- butynediols；(2) under the action of reducing agent, reduction reaction occurs for the 1- methyl-1 that step (2) obtains, 4- butynediols, obtains 1- methyl-1,4- butylene glycol；(3) the 1- methyl-1 that step (2) obtains, 4- butylene glycol occur oxidation reaction under the action of oxidant, obtain the 4- oxo-trans- 2- hexenoic aldehyde after post treatment after 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 lure ingredient 4- oxo-trans- 2- in a kind of fleahopper sex pheromone
The synthetic method of hexenoic aldehyde.
Background technique
Fleahopper is the important pests of China Yellow River basin and Yangtze river basin cotton production areas, green blind in addition to endangering cotton
Stinkbug endangers also extremely serious on other crops such as jujube, grape, cherry, peach, apple, tea tree, poplar seedlings and potato.Meanwhile
Green plant bug drug resistance is very serious, endangers serious area and needs to spray every year more than chemical pesticide time.Pesticide is largely used, is being killed
While natural enemy, potential hazard is caused to environment and human health.
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 main fleahopper type sex pheromone such as green plant bug, black striped plant bug is extracted from nature, yield is lower,
Meanwhile higher cost, be unfavorable for applying, research shows that 4- oxo-trans- 2- hexenoic aldehyde (structure is shown in formula I) be green plant bug, in
The main component of the main fleahopper type sex pheromone such as black fleahopper, if it is possible to which this artificial synthesized substance, can have
Important meaning.
Summary of the invention
It, should the present invention provides ingredient 4- oxo-trans- 2- hexenoic aldehyde synthetic method is lured in a kind of fleahopper sex pheromone
The raw material that synthetic method uses is cheap and easily-available, meanwhile, obtained product yield high.
Ingredient 4- oxo-trans- 2- hexenoic aldehyde synthetic method is lured in a kind of fleahopper sex pheromone, comprising the following steps:
(1) in the presence of alkali, necleophilic reaction occurs for propargyl alcohol and acetaldehyde, obtains 1- methyl-1,4- butynediols；
(2) under the action of reducing agent, reduction reaction occurs for the 1- methyl-1 that step (2) obtains, 4- butynediols, obtains
1- methyl-1,4- butylene glycol；
(3) under the action of oxidant oxidation reaction, reaction occur for the 1- methyl-1 that step (2) obtains, 4- butylene glycol
After obtain the 4- oxo-trans- 2- hexenoic aldehyde after post treatment；
Reaction equation is as follows:
Preferably, the alkali is n-BuLi in step (1).
In step (1), reaction temperature is room temperature.
In step (1), the solvent for reacting used is ether solvent, preferably tetrahydrofuran or Isosorbide-5-Nitrae-dioxane.
Preferably, the reducing agent is metallic sodium in step (2), reaction carries out in ethanol.
In step (2), metallic sodium first is mixed to be back to by when reaction with ethyl alcohol to be completely dissolved, and adds 1- methyl-1,4-
Butynediols carries out reduction reaction.
Preferably, the oxidant is PCC in step (3), and when using PCC as oxidant, the yield of reaction
With selective height.
In step (3), reaction dissolvent is methylene chloride, chloroform, toluene or dimethylbenzene, preferably methylene chloride.
In step (3), reaction temperature is room temperature.
Compared with the existing technology, the beneficial effects of the present invention are embodied in:
(1) raw material propargyl alcohol and acetaldehyde price used in synthetic method of the invention are lower, cheap and easily-available, can be effectively
Reduce the cost of synthesis；
(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
Propargyl alcohol (5.6g, 0.1mol) is added in 500mL three-necked flask, vacuumizes, inflated with nitrogen three times, is then added dry
Dry tetrahydrofuran 50mL, stirring and dissolving are cooled to -20 DEG C, then be added dropwise n-BuLi pentane solution (2.5M, 80mL,
0.2mol), continue to stir half an hour.Then the tetrahydrofuran (50mL) that acetaldehyde (4.8g, 0.11mol) is added dropwise into reaction solution is molten
Liquid after being added dropwise to complete, prior to -20 DEG C two hours of reaction, is then stirred at room temperature 12 hours, and TLC shows fully reacting, to reaction
The aqueous solution that the ammonium chloride of saturation is added dropwise in liquid is quenched, and ethyl acetate is then added and is extracted, with brine It two
It is secondary, it obtains organic phase and is dried with anhydrous magnesium sulfate, filtered, remove solvent, carry out column and chromatograph to obtain 1- methyl-1,4- butine
Glycol product 9.1g, yield 90.9%.
Embodiment 2
Ethyl alcohol 50mL is added in 250mL round-bottomed flask, metallic sodium (1.3g, 56mmol) then is added in batches, reflux
To whole dissolutions, the 1- methyl-1 that step (1) obtains then is added, 4- butynediols (5g, 50mmol) continues back flow reaction 12
Hour, TLC shows fully reacting, and the aqueous solution that the ammonium chloride of saturation is added is quenched.Then ethyl acetate is added to be extracted
It takes, twice with brine It, obtains organic phase and be dried with anhydrous magnesium sulfate, filter, remove solvent, carry out column and chromatograph
To 1- methyl-1,4- butylene glycol product 4.5g, yield 88.2%.
Embodiment 3
Under stiring, by CrO3(100g, 1mol) is quickly adding into hydrochloric acid (184ml, 6mol/L), will be homogeneous after 5min
System is cooled to 0 degree Celsius, and 79.1g1mol pyridine is carefully added at least 10min.Reaction system is cooled to 0 DEG C again,
Orange/yellow solid is obtained, filtering is dried in vacuo 1h, obtains PCC 180.8g.
PCC (17.2g, 0.08mol) is dissolved in 50ml methylene chloride, at room temperature, is instilled 1- methyl-1,4-
In the 30ml dichloromethane solution of butylene glycol (2.1g, 20mmol), stir 2 hours, black mixture is dilute with 175ml ether
It releases, filters, solid is washed with ether, and filtrate is washed with saturated common salt, and sodium sulphate is dry, and concentration is separated, second with silica gel column chromatography
Acetoacetic ester-petroleum ether elution, obtains 4- oxo-trans- 2- hexenoic aldehyde 1.8g, yield 89.2%, and HPLC purity is 99.1%.
Characterization of The Products data are as follows
1H NMR(400MHz,CDCl3) δ 9.77 (d, 1H, J=7.1Hz), 6.83 (d, 1H, J=16.3Hz), 6.72 (dd,
1H, J=16.3,7.0Hz), 2.40 (s, 3H)；13C NMR(100MHz,CDCl3)δ198.1,193.7,145.5,138.3,
28.1.
Embodiment 4
Dai Si-Martin's oxidant (33.9g, 0.08mol) is dissolved in 50ml methylene chloride, at room temperature, is dripped
Enter 1- methyl-1, in the 30ml dichloromethane solution of 4- butylene glycol (2.1g, 20mmol), stirs 2 hours, black mixture is used
The dilution of 175ml ether, filtering, solid are washed with ether, and filtrate is washed with saturated common salt, and sodium sulphate is dry, and silicagel column is used in concentration
Chromatography, ethyl acetate-light petrol elution, obtains 4- oxo-trans- 2- hexenoic aldehyde 1.7g, yield 84.3%, HPLC purity is
97.8%.
Claims (8)
1. luring ingredient 4- oxo-trans- 2- hexenoic aldehyde synthetic method in a kind of fleahopper sex pheromone, which is characterized in that including
Following steps:
(1) in the presence of alkali, necleophilic reaction occurs for propargyl alcohol and acetaldehyde, obtains 1- methyl-1,4- butynediols；
(2) under the action of reducing agent, reduction reaction occurs for the 1- methyl-1 that step (2) obtains, 4- butynediols, obtains 1- first
Base -1,4- butylene glycol；
(3) under the action of oxidant oxidation reaction occurs for the 1- methyl-1 that step (2) obtains, 4- butylene glycol, and reaction terminates
Obtain the 4- oxo-trans- 2- hexenoic aldehyde after post treatment afterwards；
Reaction equation is as follows:
2. ingredient 4- oxo-trans- 2- hexenoic aldehyde synthetic method is lured in fleahopper sex pheromone according to claim 1,
It is characterized in that, the alkali is n-BuLi in step (1).
3. ingredient 4- oxo-trans- 2- hexenoic aldehyde synthetic method is lured in fleahopper sex pheromone according to claim 1,
It is characterized in that, the solvent for reacting used is ether solvent in step (1).
4. ingredient 4- oxo-trans- 2- hexenoic aldehyde synthetic method is lured in fleahopper sex pheromone according to claim 1,
It is characterized in that, the ether solvent is tetrahydrofuran or Isosorbide-5-Nitrae-dioxane.
5. ingredient 4- oxo-trans- 2- hexenoic aldehyde synthetic method is lured in fleahopper sex pheromone according to claim 1,
It is characterized in that, the reducing agent is metallic sodium in step (2), reaction carries out in ethanol.
6. ingredient 4- oxo-trans- 2- hexenoic aldehyde synthetic method is lured in fleahopper sex pheromone according to claim 1,
It is characterized in that, in step (2), metallic sodium first is mixed to be back to by when reaction with ethyl alcohol to be completely dissolved, and adds 1- methyl-1,
4- butynediols carries out reduction reaction.
7. ingredient 4- oxo-trans- 2- hexenoic aldehyde synthetic method is lured in fleahopper sex pheromone according to claim 1,
It is characterized in that, the oxidant is PCC or Dai Si-Martin's oxidant in step (3).
8. ingredient 4- oxo-trans- 2- hexenoic aldehyde synthetic method is lured in fleahopper sex pheromone according to claim 1,
It is characterized in that, reaction dissolvent is methylene chloride, chloroform, toluene or dimethylbenzene in step (3).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810921420.1A CN109134218A (en) | 2018-08-14 | 2018-08-14 | Ingredient 4- oxo-trans- 2- hexenoic aldehyde synthetic method is lured in a kind of fleahopper sex pheromone |
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| CN201810921420.1A CN109134218A (en) | 2018-08-14 | 2018-08-14 | Ingredient 4- oxo-trans- 2- hexenoic aldehyde synthetic method is lured in a kind of fleahopper sex pheromone |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111747837A (en) * | 2020-06-12 | 2020-10-09 | 苏州华道生物药业股份有限公司 | Synthesis method of trans-4-oxo-2-hexenal |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103478127A (en) * | 2013-09-23 | 2014-01-01 | 中国农业科学院植物保护研究所 | Sex attractant for adelphocoris fasciaticollis reuters and application of sex attractant |
-
2018
- 2018-08-14 CN CN201810921420.1A patent/CN109134218A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103478127A (en) * | 2013-09-23 | 2014-01-01 | 中国农业科学院植物保护研究所 | Sex attractant for adelphocoris fasciaticollis reuters and application of sex attractant |
Non-Patent Citations (3)
| Title |
|---|
| SAUERS,RONALD R.等: "A Thio-Staudinger Reaction: Thermolysis of a Vinyl Azide in the Presence of t-Butyl Mercaptan", 《PHOSPHORUS, SULFUR AND SILICON AND THE RELATED ELEMENTS(2003)》 * |
| SAUERS,RONALD R.等: "γ-Hydroxyalkynyl Ketones as Useful Scaffolds for the Preparation of Combinatorial Libraries of Furans, Isoxazoles and Pyrazoles", 《JOURNAL OF COMBINATORIAL CHEMISTRY(2004)》 * |
| SKATTEBOEL,LARS等: "Preparation of two aggression controlling substances in bees", 《ACTA CHEMICA SCANDINAVICA(1995)》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111747837A (en) * | 2020-06-12 | 2020-10-09 | 苏州华道生物药业股份有限公司 | Synthesis method of trans-4-oxo-2-hexenal |
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Application publication date: 20190104 |