CN108727167B - Preparation method of anoplophora chinensis gathering pheromone - Google Patents
Preparation method of anoplophora chinensis gathering pheromone Download PDFInfo
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- CN108727167B CN108727167B CN201810390288.6A CN201810390288A CN108727167B CN 108727167 B CN108727167 B CN 108727167B CN 201810390288 A CN201810390288 A CN 201810390288A CN 108727167 B CN108727167 B CN 108727167B
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
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- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
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Abstract
The invention discloses a preparation method of anoplophora chinensis gathering pheromone, which comprises the following steps of carrying out substitution reaction under the alkaline condition and the action of a first catalyst to obtain a compound; and carrying out deprotection reaction on the compound in ionic liquid under the action of a second catalyst to obtain the final compound. The synthetic method has the advantages of excellent yield of target products and simple and convenient reaction operation; compared with the prior art, the adopted raw materials have convenient sources, low price and lower production material cost; the ionic liquid is used as a solvent in the reaction, so that reactants can be well dissolved, the phase transfer catalyst function is realized, the reaction can be promoted to be rapidly and smoothly carried out, and the method is novel; after the reaction is finished, the ionic liquid can be repeatedly used after being washed and dried, and the process is environment-friendly and safe and is suitable for industrial production.
Description
Technical Field
The invention relates to the field of compound preparation, in particular to a preparation method of longicorn aggregation pheromone.
Background
The anoplophora chinensis is a kind of trunk-boring pests with great harmfulness in the forest industry, the distribution is very wide, the distribution range recorded earlier comprises Hebei, beijing, shandong, jiangsu, zhejiang, shanxi, shaanxi, gansu, hubei, hunan, sichuan, guizhou, fujian, guangdong, hong Kong, hainan and Guangxi, and the distribution records recorded later comprise Yunnan, jiangxi, jilin, liaoning, taiwan and Heilongjiang. The hosts of anoplophora chinensis are very wide, at least 36 families are included, and the acer truncatum belongs to Acer (Sapindaceae), citrus (Rutaceae), lagerstroemia (Lythraceae), poplar (willow), rosaceous rose (Rosaceae), salix (Salicaceae) and ulmaceae mainly cause serious harm to citrus parks and shelter belts in the south of China.
Because the sex of the larva of the anoplophora chinensis is strong, the host range is large, the prevention difficulty of the larva of the anoplophora chinensis is increased, and the green, high-efficiency and pollution-free ecological prevention and control technology is favored by people more and more along with the improvement of the requirements of people on environment and food safety. The method for trapping the longicorn by using the aggregation pheromone is a most efficient control method developed in recent years, and the artificially synthesized longicorn aggregation pheromone can be used for trapping and killing the longicorn in a trap, so that the population density of the longicorn is reduced, and the method is one of the most effective measures for comprehensively controlling the longicorn.
For anoplophora chinensis gathering pheromone 4- (n-heptyloxy) -1-butanol, only one method has been reported so far:
dissolving 1,4-butanediol serving as a reaction raw material in a large amount of DMF solvent, adding sodium hydrogen to prepare sodium alkoxide, and then dropwise adding 1-bromoheptane to perform an ether forming reaction to synthesize 4- (n-heptyloxy) -1-butanol [ A.Zhang et al.Z.Naturforsch.57c,553-558 (2002) ]; the sodium hydrogen used in the synthesis method is inflammable and explosive, and a large amount of hydrogen can be generated in the reaction, so that the method is extremely dangerous; meanwhile, a large amount of DMF is used as a solvent in the reaction, so that a large amount of water is required to extract the product, the product yield is low, the waste water amount is large, and the environmental influence is high.
Due to the good market prospect of the anoplophora chinensis gathering pheromone 4- (n-heptyloxy) -1-butanol, the development of a novel synthetic method for realizing the industrial production of the anoplophora chinensis gathering pheromone is very significant.
Disclosure of Invention
In view of this, the invention provides a preparation method of anoplophora chinensis gathering pheromone 4- (n-heptyloxy) -1-butanol, which has the advantages of simple and convenient operation, safety, reliability and lower production cost,
in order to solve the technical problems, the technical scheme of the invention is to adopt a preparation method of anoplophora chinensis aggregation pheromone, which comprises the following steps: mixing a compound shown in a formula I and a compound shown in a formula II in ionic liquid, and carrying out substitution reaction under the action of a first catalyst under an alkaline condition to obtain a compound shown in a formula III; carrying out deprotection reaction on the compound shown in the formula III in ionic liquid under the action of a second catalyst to obtain a compound shown in a formula IV;
preferably, the ionic liquid is selected from one or more of the following compounds: 1-n-hexyl-3-methylimidazolium chloride, 1-n-hexyl-3-methylimidazolium bromide, 1-n-hexyl-3-methylimidazolium iodide, 1-n-hexyl-3-methylimidazolium tetrafluoroborate, 1-n-hexyl-3-methylimidazolium hexafluorophosphate, 1-n-hexyl-3-ethylimidazolium chloride, 1-n-hexyl-3-ethylimidazolium bromide, 1-n-hexyl-3-ethylimidazolium iodide, 1-n-hexyl-3-ethylimidazolium tetrafluoroborate, 1-n-hexyl-3-ethylimidazolium hexafluorophosphate.
Preferably, the ionic liquid is selected from one or more of the following compounds: 1-n-hexyl-3-methylimidazole chlorine salt, 1-n-hexyl-3-methylimidazole iodine salt and 1-n-hexyl-3-ethylimidazole hexafluorophosphate.
Preferably, the basic conditions are provided by one or more of the following compounds: potassium tert-butoxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, cesium carbonate, lithium carbonate.
Preferably, the first catalyst is selected from one or more of the following compounds: octadeca-coronene hexa, pentadeca-coronene penta, sodium bromide, potassium bromide, sodium iodide, potassium iodide, tetrabutylammonium iodide and tetrabutylammonium bromide.
Preferably, the mass ratio of the compound of formula I, the compound providing the basic conditions, the compound of formula II and a catalyst is 1: (1.0-1.5): (1.0-1.5): (0.01-0.05).
Preferably, the concentration of the reaction system for the substitution reaction is 0.5 to 5M.
Preferably, the second catalyst employed is selected from one or more of the following compounds: trifluoroacetic acid, methanesulfonic acid, chlorosulfonic acid, concentrated hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid.
Preferably, the weight ratio of the compound represented by formula III to the second catalyst is 1.
Preferably, the concentration of the solution of the deprotection reaction system is 1 to 8M.
The invention has the advantages that: the target product of the anoplophora chinensis gathering pheromone 4- (n-heptyloxy) -1-butanol is synthesized by adopting a one-pot reaction, the yield of the target product is excellent by using the synthesis method, and the reaction operation is simple and convenient; compared with the prior art, the raw materials adopted by the invention are convenient in source, low in price and low in production material cost; the ionic liquid is used as a solvent in the reaction, so that reactants can be well dissolved, the phase transfer catalyst can be used, the reaction can be rapidly and smoothly carried out, and the method is novel; after the reaction is finished, the ionic liquid can be repeatedly used through washing and drying, and the process is environment-friendly and safe and is suitable for industrial production.
Drawings
FIG. 1 NMR spectra of compounds of formula IV prepared in example 1 of the present invention.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the present invention will be further described in detail with reference to the following embodiments.
Through research, we found that ionic liquids have a series of outstanding advantages compared with traditional organic solvents: (1) The liquid state range is wide, and the liquid state range is from lower than or close to room temperature to more than 300 ℃, so that the thermal stability and the chemical stability are high; (2) The electrolyte has the advantages that the vapor pressure is very small, the electrolyte is non-volatile, cannot be evaporated and dissipated in use and storage, can be recycled, eliminates the problem of environmental pollution caused by Volatile Organic Compounds (VOCs), has high conductivity and large electrochemical window, and can be used as the electrolyte for electrochemical research of a plurality of substances; (4) The solubility of the compound to inorganic matters, water, organic matters and polymers can be adjusted through the design of anions and cations, and the acidity of the compound can be adjusted to be superacid. (4) The product has high polarity controllability, low viscosity and high density, can form a two-phase or multi-phase system, and is suitable for being used as a separation solvent or forming a new reaction-separation coupling system; (5) Has good dissolving capacity for a large amount of inorganic and organic substances, has double functions of a solvent and a catalyst, and can be used as a solvent or a catalytic active carrier for a plurality of chemical reactions. Due to the special properties and performances of the ionic liquid, the ionic liquid is considered to form three green solvents together with supercritical CO2 and aqueous two phases, and has wide application prospect.
On the basis of systematic research on the existing main preparation method, in order to solve the existing technical problems, the preparation method of the anoplophora chinensis aggregation pheromone comprises the following steps: mixing a compound shown in a formula I and a compound shown in a formula II in ionic liquid, and carrying out substitution reaction under the action of a catalyst under an alkaline condition to obtain a compound shown in a formula III; carrying out deprotection reaction on the compound shown in the formula III in an ionic liquid under the action of a second catalyst to obtain a compound shown in a formula IV;
the specific synthetic route is as follows:
in the present invention, 4-t-butoxy-1-chlorobutane was prepared using tetrahydrofuran and methyl-t-butyl ether, which are available and inexpensive, as raw materials, according to the references [ J.org.chem.1981,46,3361-3364 and KR2017/4895 ].
According to the invention, firstly, a compound shown in a formula II and a compound shown in a formula I are used as raw materials, and substitution reaction is carried out in a proper alkali, temperature and ionic liquid as a solvent to prepare the compound shown in the formula III. The temperature range of the substitution reaction is 0-120 ℃, and the reaction temperature is more preferably 60-120 ℃. The ionic liquid is preferably selected from one or more of the following: 1-n-hexyl-3-methylimidazolium chloride salt, 1-n-hexyl-3-methylimidazolium bromide salt, 1-n-hexyl-3-methylimidazolium iodide salt, 1-n-hexyl-3-methylimidazolium tetrafluoroborate salt, 1-n-hexyl-3-methylimidazolium hexafluorophosphate salt, 1-n-hexyl-3-ethylimidazolium chloride salt, 1-n-hexyl-3-ethylimidazolium bromide salt, 1-n-hexyl-3-ethylimidazolium iodide salt, 1-n-hexyl-3-ethylimidazolium tetrafluoroborate salt, 1-n-hexyl-3-ethylimidazolium hexafluorophosphate salt; more preferably 1-n-hexyl-3-methylimidazolium chloride, 1-n-hexyl-3-methylimidazolium iodide, 1-n-hexyl-3-ethylimidazolium hexafluorophosphate. The invention adopts the ionic liquid to dissolve the reaction raw materials, can well dissolve reactants, plays a role of a phase transfer catalyst, can promote the reaction to be rapidly and smoothly carried out, and has novel method.
The basic conditions are provided by one or more of the following compounds: potassium tert-butoxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, cesium carbonate, lithium carbonate; the catalyst used is one or more of the following substances: eighteen crown hexa, fifteen crown penta, sodium bromide, potassium bromide, sodium iodide, potassium iodide, tetrabutylammonium bromide. More preferred are potassium tert-butoxide, potassium hydroxide, lithium hydroxide and cesium carbonate.
In order to promote the reaction, the invention also uses a catalyst which is potassium iodide, tetrabutylammonium iodide or octodecahexa-crown.
Preferably, the weight ratio of the compound represented by the formula I to the compound represented by the formula VII to provide the basic condition and the catalyst is 1: (1.0-1.5): (1.0-1.5): (0.01-0.05). The dosage of the ionic liquid is as follows.
After the compound shown in the formula III is obtained, under the conditions of proper acid catalyst, temperature and ionic liquid as solvent, deprotection reaction (removal of tert-butyl protecting group) is carried out to obtain the target product compound shown in the formula IV. The reaction temperature range is preferably 0-100 ℃, and more preferably 20-60 ℃; the second catalyst used is preferably one or more of the following: trifluoroacetic acid, methanesulfonic acid, chlorosulfonic acid, concentrated hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid. More preferably hydrochloric acid or trifluoroacetic acid.
According to the invention, the ionic liquid used in the solvent is preferably selected from one or more of the following: 1-n-hexyl-3-methylimidazolium chloride, 1-n-hexyl-3-methylimidazolium bromide, 1-n-hexyl-3-methylimidazolium iodide, 1-n-hexyl-3-methylimidazolium tetrafluoroborate, 1-n-hexyl-3-methylimidazolium hexafluorophosphate, 1-n-hexyl-3-ethylimidazolium chloride, 1-n-hexyl-3-ethylimidazolium bromide, 1-n-hexyl-3-ethylimidazolium iodide, 1-n-hexyl-3-ethylimidazolium tetrafluoroborate, 1-n-hexyl-3-ethylimidazolium hexafluorophosphate. More preferably: 1-n-hexyl-3-methylimidazolium chloride, 1-n-hexyl-3-methylimidazolium iodide, 1-n-hexyl-3-ethylimidazolium hexafluorophosphate;
the invention has the advantages that: the target product of the anoplophora chinensis gathering pheromone 4- (n-heptyloxy) -1-butanol is synthesized by adopting a one-pot reaction, the yield of the target product is excellent by using the synthesis method, and the reaction operation is simple and convenient; compared with the prior art, the raw materials adopted by the invention are convenient in source, low in price and low in production material cost; the ionic liquid is used as a solvent in the reaction, so that reactants can be well dissolved, the phase transfer catalyst function is realized, the reaction can be promoted to be rapidly and smoothly carried out, and the method is novel; after the reaction is finished, the ionic liquid can be repeatedly used after being washed and dried, and the process is environment-friendly and safe and is suitable for industrial production.
The following are specific examples of the present invention and illustrate the advantageous effects of the preparation method of the present invention in detail.
Example 1:
adding 100 ml of 1-n-hexyl-3-methylimidazolium chloride and 12 g of n-heptanol into a reaction bottle, heating to 60 ℃, then adding 12 g of potassium tert-butoxide in batches, and then adding 0.5 g of octadecanohexa; after 1 hour of reaction, 18 g of 4-tert-butoxy-1-chlorobutane was added dropwise thereto, and the reaction was maintained at 60 ℃ until completion (gas phase detection).
Cooling to room temperature, adding 15 ml of trifluoroacetic acid, and stirring to react completely (gas phase detection); extracting with petroleum ether for several times, combining organic phases, washing with water, drying, concentrating, and purifying the residue by column chromatography to obtain 10 g of product with 53% yield.
Example 2:
adding 80 ml of 1-n-hexyl-3-methylimidazolium tetrafluoroborate and 12 g of n-heptanol into a reaction bottle, heating to 40 ℃, then adding 6 g of potassium hydroxide and then adding 1 g of potassium iodide; after 1 hour of reaction, 18 g of 4-tert-butoxy-1-chlorobutane was added dropwise thereto, and the reaction was maintained at 40 ℃ until completion (gas phase detection).
Cooling to room temperature, adding 10 ml of concentrated hydrochloric acid, and stirring to react completely (gas phase detection); extracting with ethyl acetate for several times, combining organic phases, washing with water, drying, concentrating, and purifying the residue by column chromatography to obtain 11 g of product with the yield of 59%.
Example 3:
adding 200 ml of 1-n-hexyl-3-ethylimidazole tetrafluoroborate and 50 g of n-heptanol into a reaction bottle, heating to 60 ℃, adding 65 g of cesium carbonate and then adding 5 g of tetrabutylammonium bromide; after stirring at 60 ℃ for 1 hour, 75 g of 4-tert-butoxy-1-chlorobutane was added and the reaction was completed by heating to 100 ℃ (gas phase detection).
Cooling to 50 ℃, carrying out suction filtration while the solution is hot, adding 25 ml of 30% sulfuric acid solution into the filtrate, and heating to 80 ℃ to completely react (gas phase detection); petroleum ether is used for full extraction for a plurality of times, organic phases are combined, washed by water, dried and concentrated, and residues are distilled under reduced pressure to obtain 56 g of products with the yield of 69%.
Example 4:
50 ml of 1-hexyl-3-methylimidazolium iodide and 12 g of n-heptanol are added into a reaction flask, the mixture is heated to 50 ℃, then 6 g of sodium hydroxide are added in batches, after 1 hour of reaction, 18 g of 4-tert-butoxy-1-chlorobutane is added dropwise, and the reaction is maintained at 50 ℃ completely (gas phase detection).
Cooling to room temperature, adding 10 ml of concentrated hydrochloric acid, and stirring to react completely (gas phase detection); extracting with petroleum ether for several times, combining organic phases, washing with water, drying, concentrating, and purifying the residue by column chromatography to obtain 12 g of product with the yield of 64%.
Example 5:
adding 40 ml of 1-n-hexyl-3-ethylimidazole hexafluorophosphate and 12 g of n-heptanol into a reaction bottle, heating to 80 ℃, then adding 3 g of lithium hydroxide and then adding 0.5 g of pentadecanopentan; after 1 hour of reaction, 18 g of 4-tert-butoxy-1-chlorobutane was added dropwise thereto, and the reaction was maintained at 80 ℃ until completion (gas phase detection).
Cooling to room temperature, adding 10 ml of methanesulfonic acid, and stirring to react completely (gas phase detection); extracting with ethyl acetate for several times, combining organic phases, washing with water, drying, concentrating, and purifying residue by column chromatography to obtain 8.6 g of product with yield of 46%.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (5)
1. A preparation method of anoplophora chinensis gathering pheromone is characterized by comprising the following steps:
step one, mixing a compound shown in a formula I and a compound shown in a formula II in ionic liquid, and carrying out substitution reaction under the action of an alkaline condition and a first catalyst to obtain a compound shown in a formula III;
secondly, carrying out deprotection reaction on the compound shown in the formula III in an ionic liquid under the action of a second catalyst to obtain a compound shown in a formula IV;
the ionic liquid is independently selected from one or more of the following compounds: 1-n-hexyl-3-methylimidazolium chloride salt, 1-n-hexyl-3-methylimidazolium iodide salt, 1-n-hexyl-3-ethylimidazolium tetrafluoroborate and 1-n-hexyl-3-ethylimidazolium hexafluorophosphate; the basic conditions are provided by one or more of the following compounds: potassium tert-butoxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium carbonate; the first catalyst is selected from one or more of the following compounds: sixty-six crown, fifteen-five crown, potassium iodide and tetrabutylammonium bromide; the second catalyst used is selected from one or more of the following compounds: trifluoroacetic acid, methanesulfonic acid, concentrated hydrochloric acid and sulfuric acid.
2. The method according to claim 1, wherein the mass ratio of the compound represented by formula I, the compound providing the basic condition, the compound represented by formula II, and the first catalyst is 1: (1.0-1.5): (1.0-1.5): (0.01-0.05).
3. The method according to claim 1, wherein the concentration of the substitution reaction system is 0.5 to 5M.
4. The production method according to claim 1, wherein the mass ratio of the compound represented by formula III to the second catalyst is 1.
5. The method according to claim 1, wherein the concentration of the solution in the deprotection reaction system is 1 to 8M.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001004078A1 (en) * | 1999-07-07 | 2001-01-18 | The United States Of America, As Represented By The Secretary Of Agriculture | Aggregation pheromone for the asian longhorned beetle, anoplophora glabripennis () coleoptera: cerambycidae |
| CN107805187A (en) * | 2017-09-30 | 2018-03-16 | 苏州华道生物药业股份有限公司 | The production technology of Monochamus alternatus aggregation pheromone hendecane epoxide ethanol |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001004078A1 (en) * | 1999-07-07 | 2001-01-18 | The United States Of America, As Represented By The Secretary Of Agriculture | Aggregation pheromone for the asian longhorned beetle, anoplophora glabripennis () coleoptera: cerambycidae |
| CN107805187A (en) * | 2017-09-30 | 2018-03-16 | 苏州华道生物药业股份有限公司 | The production technology of Monochamus alternatus aggregation pheromone hendecane epoxide ethanol |
Non-Patent Citations (2)
| Title |
|---|
| Identification and Field Activity of a Male-Produced Aggregation Pheromone in the Pine Sawyer Beetle, Monochamus galloprovincialis;Juan A. Pajares等;《J Chem Ecol>;20100502;第36卷(第6期);第570-583页 * |
| Stimulatory Beetle Volatiles for the Asian Longhorned Beetle, Anoplophora glabripennis (Motschulsky);A.Zhang等;《Zeitschrift fur Naturforschung C》;20020131;第57卷;第556页右栏第1段 * |
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