CN101486721A - Use of lithium diisopropyl amido in 1-methyl cyclopropene preparation - Google Patents
Use of lithium diisopropyl amido in 1-methyl cyclopropene preparation Download PDFInfo
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- CN101486721A CN101486721A CNA2009100961671A CN200910096167A CN101486721A CN 101486721 A CN101486721 A CN 101486721A CN A2009100961671 A CNA2009100961671 A CN A2009100961671A CN 200910096167 A CN200910096167 A CN 200910096167A CN 101486721 A CN101486721 A CN 101486721A
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- diisopropylamine
- lithium
- methylcyclopropene
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- lithium diisopropylamine
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Abstract
The invention relates to the application of lithium diisopropylamide which is an organic alkali in preparing 1-methylcyclopropene; the application of the lithium diisopropylamide as a catalyst to prepare the 1-methylcyclopropene well solves the technical problem that the production course of the 1-methylcyclopropene has high energy consumption, low content and high cost, simplifies the production processes, reduces the production costs and realizes high yield of 1-methylcyclopropene.
Description
Technical field
The present invention relates to the application of a kind of organic alkali in preparation 1-methylcyclopropene, relate in particular to the application of a kind of organic alkali lithium diisopropyl amido in preparation 1-methylcyclopropene; Belong to technical field of chemical synthesis.
Background technology
1-methylcyclopropene (1-MCP) is the plant-growth regulator of a kind of novelty of recently finding, can restrain the effect to plant of endogenous and exogenous ethylene effectively, and it is old and feeble and come off to delay ethene inductive plant organ.Because its is nontoxic, low amount, advantage such as efficient, can block the physiological effect of endogenous ethylene consumingly, therefore in the preservation and freshness of fruit, vast potential for future development is arranged.
Synthetic for 1-methylcyclopropene, existing processing method mainly are to be basic material with the 2-methylallyl chloride, prepare 1-MCP by ring-closure reaction under organic alkali catalysis such as n-Butyl Lithium or phenyl lithium.
Reaction formula is as follows:
Wherein: X refers to Cl
-, Br
-
The alkali that cyclization is used is n-Butyl Lithium, and n-Butyl Lithium is generally by halogen butane and metallic lithium reaction, and the working condition harshness, need make one times n-Butyl Lithium with 2 times metallic lithium, and price is relatively expensive.There is bibliographical information also can use phenyl lithium to finish this reaction, comes, can improve production cost greatly but phenyl lithium is also transformed by butyllithium.
Lithium diisopropylamine (LDA), skeleton symbol ((CH
3)
2CH)
2N-Li, English name: Lithium diisopropylamide, density is to be 0.812g/ml under 25 ℃ the condition in temperature.Lithium diisopropylamine (LDA) belongs to non-nucleophilicity highly basic, is used to the deprotonation hydrocarbon polymer as alkali usually.As the application in preparation benzyl isoeugenol, thiophene macrocyclic compound and derivative thereof, 3-amino-2-alkene imines, beta-amino nitrile compounds, but prior art was never reported the application of lithium diisopropylamine in preparation 1-methylcyclopropene.
Summary of the invention
The object of the present invention is to provide the new purposes of lithium diisopropylamine, i.e. application in preparation 1-methylcyclopropene.
Lithium diisopropylamine (LDA) can play the deprotonation effect to the carbonyl compound (comprising carboxylic acid, ester, aldehyde and ketone) of the most pure and mild α of containing-hydrogen.In tetrahydrofuran solution, lithium diisopropylamine (LDA) mainly exists with dimeric form, and can resolve into monomer when other materials of its deprotonation in advance.The present invention utilizes the character of lithium diisopropylamine (LDA), and it can be made 2-methylallyl chloride self cyclization as catalyzer, obtains the 1-methylcyclopropene.
In above-mentioned application process, the preparation process of described lithium diisopropylamine is: with Diisopropylamine, metallic lithium is raw material, add in the solvent earlier, be to drip auxiliary agent under 0 ℃～40 ℃ the condition in temperature, being warming up to 40～60 ℃ reacts, when the color of question response system becomes a kind of in grey, black, blueness, the mazarine, be cooled to continue under 0～40 ℃ the condition reaction 0.5～10 hour lithium diisopropylamine; The weight ratio of wherein said Diisopropylamine and metallic lithium is 5～20:1; The weight ratio of described Diisopropylamine and solvent is 1:1～5; The weight ratio of described Diisopropylamine and auxiliary agent is 1～3:1.Adopt Diisopropylamine in the presence of auxiliary agent, to make lithium diisopropylamine (LDA),, reduced a large amount of energy consumptions like this because this step has relatively mild reaction conditions; The metallic lithium consumption is less in the reaction, can reduce the generation of lithium salts like this, can reduce simultaneously the consumption of solvent, and because the existence of auxiliary agent is arranged, and reaction can stable carrying out, and side reaction is few.
In above-mentioned application process, described solvent is one or more in ether, 2-methyltetrahydrofuran, tetrahydrofuran (THF), benzene, hexanaphthene, the methyl tertiary butyl ether, and described auxiliary agent is one or more in vinylbenzene, Tetramethyl Ethylene Diamine, hexamethylphosphoramide, the toluene.As preferably, described solvent is a kind of in ether, 2-methyltetrahydrofuran, the tetrahydrofuran (THF); Described auxiliary agent is a vinylbenzene.
In above-mentioned application process, as preferably, the temperature that drips auxiliary agent is 35～38 ℃, is warming up to 55～58 ℃, is cooled to 35～38 ℃.
In above-mentioned application process, the application process of described lithium diisopropylamine is: the application process of described lithium diisopropylamine is: be under 20 ℃～30 ℃ the condition in temperature, drip the 2-methylallyl chloride in the solvent of lithium diisopropylamine or in its reaction system, dropwising the back continues to stir 1～2 hour, add entry, collect gas and obtain the 1-methylcyclopropene, wherein the mol ratio of lithium diisopropylamine and 2-methylallyl chloride is 0.5～2:1; Lithium diisopropylamine and water mol ratio are 1:1～3.The present invention generates after 1-MCP with the cyclization of lithium diisopropylamine (LDA) catalysis 2-methylallyl chloride, available distillatory method reclaims materials such as solvent, Diisopropylamine, auxiliary agent, carry out recycled, residuum is the chlorination lithium salts substantially, thereby reduced the discharging of waste liquid pollution on the environment, meet the cleaner production requirement, cost is reduced significantly.
In above-mentioned application process, as preferably, the temperature the during application process of lithium diisopropylamine is 25 ℃～28 ℃.
The reaction equation that the preparation of lithium diisopropylamine of the present invention and application lithium diisopropylamine catalysis 2-methylallyl chloride generate the 1-methylcyclopropene is as follows:
In sum, the present invention has the following advantages:
Application in preparation 1-methylcyclopropene preferably resolves that to produce in the 1-methylcyclopropene process of producing product energy consumption big as catalyzer with lithium diisopropylamine in the present invention, content is low, the technical barrier that cost is high, simplified production technique, reduced production cost, 1-methylcyclopropene yield height.
Description of drawings
Fig. 1 is that the present invention prepares lithium diisopropylamine and uses the process flow sheet that lithium diisopropylamine catalysis 2-methylallyl chloride generates the 1-methylcyclopropene.
Embodiment
Below by specific embodiment also in conjunction with the accompanying drawings, technical scheme of the present invention is described in further detail; But the present invention is not limited to these embodiment.
Embodiment 1: the preparation lithium diisopropylamine
With Diisopropylamine 170g, metallic lithium 12g adds in the 300ml tetrahydrofuran (THF), and under 37 ℃, beginning slowly drips 95g vinylbenzene, constantly carry out along with dripping, reaction system begins to heat up, and is warmed up to 56 ℃, and this moment, reaction system was a grey, begin cooling later on, keep 37 ℃ constant, continue to stir, react and generate lithium diisopropylamine after 6 hours.
Application Example 1
In the reaction system of embodiment 1,, slowly drip the 1mol2-methylallyl chloride by the frozen water cooling, this moment, temperature of reaction was 26 ℃, continued to stir, and solution is creamy white, after dropwising, continue to stir, solution is oyster white, react after 1.5 hours, add 2mol water, have a large amount of bubbles to emerge, collect the 1-methylcyclopropene gas, yield is more than 50%, and the entire reaction schema as shown in Figure 1.
Embodiment 2: the preparation lithium diisopropylamine
With Diisopropylamine 170g, metallic lithium 12g adds in the 300ml anhydrous diethyl ether, and under 37 ℃, beginning slowly drips the 95g Tetramethyl Ethylene Diamine, constantly carry out along with dripping, reaction system begins to heat up, and is warmed up to 56 ℃, and this moment, reaction system was a grey, begin cooling later on, keep 37 ℃ constant, continue to stir, react and generate lithium diisopropylamine after 4 hours.
Application Example 2
In the reaction system of embodiment 2,, slowly drip the 1mol2-methylallyl chloride by the frozen water cooling, this moment, temperature of reaction was 26 ℃, continued to stir, and solution is creamy white, after dropwising, continue to stir, solution is oyster white, reacts after 1.5 hours, add 2mol water, have a large amount of bubbles to emerge, collect the 1-methylcyclopropene gas, yield is more than 50%.
Embodiment 3: the preparation lithium diisopropylamine
With Diisopropylamine 180g, metallic lithium 10g adds in the 350ml tetrahydrofuran (THF), and under 20 ℃, beginning slowly drips 105g vinylbenzene, constantly carry out along with dripping, reaction system begins to heat up, and is warmed up to 45 ℃, and this moment, reaction system was a grey, begin cooling later on, keep 20 ℃ constant, continue to stir, react and generate lithium diisopropylamine after 8 hours.
Application Example 3
In the reaction system of embodiment 3,, slowly drip the 1.5mol2-methylallyl chloride by the frozen water cooling, this moment, temperature of reaction was 25 ℃, continued to stir, and solution is creamy white, after dropwising, continue to stir, solution is oyster white, reacts after 2 hours, add 3mol water, have a large amount of bubbles to emerge, collect the 1-methylcyclopropene gas, yield is more than 50%.
Embodiment 4: the preparation lithium diisopropylamine
With Diisopropylamine 200g, metallic lithium 15g adds in the 400ml tetrahydrofuran (THF), and under 10 ℃, beginning slowly drips 110g vinylbenzene, constantly carry out along with dripping, reaction system begins to heat up, and is warmed up to 58 ℃, and this moment, reaction system was a grey, begin cooling later on, keep 10 ℃ constant, continue to stir, react and generate lithium diisopropylamine after 10 hours.
Application Example 4
In the reaction system of embodiment 4,, slowly drip the 1mol2-methylallyl chloride by the frozen water cooling, this moment, temperature of reaction was 28 ℃, continued to stir, and solution is creamy white, after dropwising, continue to stir, solution is oyster white, reacts after 1 hour, add 1.5mol water, have a large amount of bubbles to emerge, collect the 1-methylcyclopropene gas, yield is more than 50%.
Embodiment 5
With Diisopropylamine 170g, metallic lithium 12g adds in the 300ml2-methyltetrahydrofuran, and under 37 ℃, beginning slowly drips 95g vinylbenzene, constantly carry out along with dripping, reaction system begins to heat up, and is warmed up to 56 ℃, and this moment, reaction system was a grey, begin cooling later on, keep 37 ℃ constant, continue to stir, react and generate lithium diisopropylamine after 2 hours.
Application Example 5
In the reaction system of embodiment 5,, slowly drip the 1mol2-methylallyl chloride by the frozen water cooling, this moment, temperature of reaction was 26 ℃, continued to stir, and solution is creamy white, after dropwising, continue to stir, solution is oyster white, reacts after 1.5 hours, add 2mol water, have a large amount of bubbles to emerge, collect the 1-methylcyclopropene gas, yield is more than 50%.
Comparative example 1
Under nitrogen protection; earlier metallic lithium 14.3g is dropped in the 200ml anhydrous diethyl ether of-15 degree; slowly drip ready n-propylcarbinyl chloride (92.5g then; the dilution of 200ml anhydrous diethyl ether); after adding, be incubated-10 ℃ of half an hour, be warmed up to 0～5 ℃ then and stirred 2 hours; under the last nitrogen protection, suction filtration is removed the solid lithium chloride.Get the diethyl ether solution of n-Butyl Lithium, yield 85%.
Use comparative example 1
The n-Butyl Lithium diethyl ether solution frozen water that filtration obtains is lowered the temperature, slowly drip the 76.5g2-methylallyl chloride, control reaction temperature is no more than 26 ℃, after dropwising, continues to stir, solution is creamy white, behind the question response 1.5 hours, add 36g water, have a large amount of bubbles to emerge, collect the 1-methylcyclopropene gas, 1-methylcyclopropene gas reaction yield is lower than 40%.
Comparative example 2
Under nitrogen protection; earlier in the 200ml anhydrous diethyl ether (solvent) with-15 ℃ of metallic lithium 14.3g inputs; slowly drip ready n-propylcarbinyl chloride (92.5g then; the dilution of 200ml anhydrous diethyl ether); after adding, be incubated-10 ℃ of half an hour, be warmed up to 0 ~ 5 ℃ of stirring then and obtained n-Butyl Lithium in 2 hours; this solution is desalination not, directly prepares to carry out next step reaction.
Use comparative example 2
The diethyl ether solution frozen water of above-mentioned n-Butyl Lithium is cooled, slowly drip the 76.5g2-methylallyl chloride, control reaction temperature is no more than 26 ℃, after dropwising, carefully add 36g water, have a large amount of bubbles to emerge, collect the 1-methylcyclopropene gas, 1-methylcyclopropene yield only is 20%.
Specific embodiment described in the present invention only is that the present invention's spirit is illustrated.The technician of the technical field of the invention can make various modifications or replenishes or adopt similar mode to substitute described specific embodiment, but can't depart from spirit of the present invention or surmount the defined scope of appended claims.
Although the present invention has been made detailed explanation and has quoted some specific embodiments as proof, to those skilled in the art, only otherwise leave that the spirit and scope of the present invention can be done various variations or correction is obvious.
Claims (6)
1, the application of lithium diisopropylamine in preparation 1-methylcyclopropene.
2, application according to claim 1, it is characterized in that: the preparation process of described lithium diisopropylamine is: with Diisopropylamine, metallic lithium is raw material, add in the solvent earlier, be to drip auxiliary agent under 0 ℃～40 ℃ the condition in temperature, being warming up to 40～60 ℃ reacts, when the color of question response system becomes a kind of in grey, black, blueness, the mazarine, be cooled to continue under 0～40 ℃ the condition reaction 0.5～10 hour lithium diisopropylamine; The weight ratio of wherein said Diisopropylamine and metallic lithium is 5～20:1; The weight ratio of described Diisopropylamine and solvent is 1:1～5; The weight ratio of described Diisopropylamine and auxiliary agent is 1～3:1.
3, application according to claim 2, it is characterized in that: described solvent is one or more in ether, 2-methyltetrahydrofuran, tetrahydrofuran (THF), benzene, hexanaphthene, the methyl tertiary butyl ether, and described auxiliary agent is one or more in vinylbenzene, Tetramethyl Ethylene Diamine, hexamethylphosphoramide, the toluene.
4, application according to claim 2 is characterized in that: the temperature that drips auxiliary agent is 35～38 ℃, is warming up to 55～58 ℃, is cooled to 35～38 ℃.
5, according to any described application of claim 1～4, it is characterized in that: the application process of described lithium diisopropylamine is: be under 20 ℃～30 ℃ the condition in temperature, drip the 2-methylallyl chloride in the solvent of lithium diisopropylamine or in its reaction system, dropwising the back continues to stir 1～2 hour, add entry, collect gas and obtain the 1-methylcyclopropene, wherein the mol ratio of lithium diisopropylamine and 2-methylallyl chloride is 0.5～2:1; Lithium diisopropylamine and water mol ratio are 1:1～3.
6, application according to claim 5 is characterized in that: the temperature the during application process of lithium diisopropylamine is 25 ℃～28 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009100961671A CN101486721B (en) | 2009-02-17 | 2009-02-17 | Use of lithium diisopropyl amido in 1-methyl cyclopropene preparation |
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| CN2009100961671A CN101486721B (en) | 2009-02-17 | 2009-02-17 | Use of lithium diisopropyl amido in 1-methyl cyclopropene preparation |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167653A (en) * | 2010-02-26 | 2011-08-31 | 青岛绿诺新能源有限公司 | Method for preparing 1-methylcyclopropene |
| CN102964615A (en) * | 2012-10-09 | 2013-03-13 | 新疆农业科学院农产品贮藏加工研究所 | Preparation method of cyclopropene preservative paper |
| CN103360413A (en) * | 2010-02-26 | 2013-10-23 | 青岛绿诺新能源有限公司 | Storage method of 1-methylcyclopropene lithium |
| CN106928015A (en) * | 2017-04-18 | 2017-07-07 | 常州茂尔盛生态农业科技有限公司 | The preparation method of 1 methyl cyclopropene |
| CN108727413A (en) * | 2017-04-13 | 2018-11-02 | 中国科学院青岛生物能源与过程研究所 | A kind of thiazole bioxindol class compound and preparation method thereof |
| CN112430197A (en) * | 2020-11-30 | 2021-03-02 | 江苏阿尔法药业有限公司 | Synthesis method of tert-butyl 3-oxo-5-hydroxy-6-cyanohexanoate |
| JP2021530490A (en) * | 2018-07-11 | 2021-11-11 | アルベマール・ジャーマニー・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング | Stable alkaline amide solution and its preparation method |
| CN114230627A (en) * | 2021-12-31 | 2022-03-25 | 湖南新合新生物医药有限公司 | Preparation method of betamethasone epoxy hydrolysate intermediate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4595779A (en) * | 1984-12-24 | 1986-06-17 | Lithium Corporation Of America, Inc. | Stable lithium diisopropylamide and method of preparation |
-
2009
- 2009-02-17 CN CN2009100961671A patent/CN101486721B/en active Active
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167653A (en) * | 2010-02-26 | 2011-08-31 | 青岛绿诺新能源有限公司 | Method for preparing 1-methylcyclopropene |
| CN103360413A (en) * | 2010-02-26 | 2013-10-23 | 青岛绿诺新能源有限公司 | Storage method of 1-methylcyclopropene lithium |
| CN102964615A (en) * | 2012-10-09 | 2013-03-13 | 新疆农业科学院农产品贮藏加工研究所 | Preparation method of cyclopropene preservative paper |
| CN102964615B (en) * | 2012-10-09 | 2017-09-22 | 新疆农业科学院农产品贮藏加工研究所 | A kind of preparation method of cyclopropene preservative paper |
| CN108727413A (en) * | 2017-04-13 | 2018-11-02 | 中国科学院青岛生物能源与过程研究所 | A kind of thiazole bioxindol class compound and preparation method thereof |
| CN106928015A (en) * | 2017-04-18 | 2017-07-07 | 常州茂尔盛生态农业科技有限公司 | The preparation method of 1 methyl cyclopropene |
| JP2021530490A (en) * | 2018-07-11 | 2021-11-11 | アルベマール・ジャーマニー・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング | Stable alkaline amide solution and its preparation method |
| JP7423593B2 (en) | 2018-07-11 | 2024-01-29 | アルベマール・ジャーマニー・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング | Stable alkaline amide solution and its preparation method |
| CN112430197A (en) * | 2020-11-30 | 2021-03-02 | 江苏阿尔法药业有限公司 | Synthesis method of tert-butyl 3-oxo-5-hydroxy-6-cyanohexanoate |
| CN112430197B (en) * | 2020-11-30 | 2023-05-05 | 江苏阿尔法药业股份有限公司 | Synthesis method of 3-oxo-5-hydroxy-6-cyano tert-butyl caproate |
| CN114230627A (en) * | 2021-12-31 | 2022-03-25 | 湖南新合新生物医药有限公司 | Preparation method of betamethasone epoxy hydrolysate intermediate |
| CN114230627B (en) * | 2021-12-31 | 2023-09-15 | 湖南新合新生物医药有限公司 | Preparation method of betamethasone epoxy hydrolysate intermediate |
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Address after: Jia Zhi Jiaojiang District of Taizhou City, Zhejiang Province, three village 318013 Patentee after: Liansheng Chemical Group Co Ltd Address before: Jia Zhi Jiaojiang District of Taizhou City, Zhejiang Province, three village 318013 Patentee before: Zhejiang Realsun Chemical Industry Co., Ltd. |
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