CN110818576A - Secondary amine derivative synthesized by rare earth catalysis and preparation method thereof - Google Patents
Secondary amine derivative synthesized by rare earth catalysis and preparation method thereof Download PDFInfo
- Publication number
- CN110818576A CN110818576A CN201911014908.7A CN201911014908A CN110818576A CN 110818576 A CN110818576 A CN 110818576A CN 201911014908 A CN201911014908 A CN 201911014908A CN 110818576 A CN110818576 A CN 110818576A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- secondary amine
- amine derivative
- reaction
- amide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a secondary amine derivative synthesized by rare earth catalysis and a preparation method thereof, wherein the secondary amine derivative is prepared by taking secondary amide and pinacolborane as reactants; a rare earth catalyst of bis-trimethylsilyl amino yttrium is also added; the reaction temperature is 100-140 ℃, and the reaction time is 20-25 hours; the whole reaction is carried out under normal pressure, the reaction condition is mild, and the method is easy to achieve and safe. The method has simple and convenient operation and strong reaction selectivity, can directly synthesize the target product, does not need to separate intermediate products, can obtain the target product only by reacting under normal pressure, has simple reaction process and highest yield of 90 percent, greatly simplifies process engineering, reduces energy consumption and has the advantage of high yield; the reaction raw materials are stable and easy to store; the method has strong substrate universality, thereby providing good guarantee for developing related substances of the secondary amine derivatives and being suitable for large-scale popularization and application.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a secondary amine derivative synthesized by rare earth catalysis and a preparation method thereof.
Background
The secondary amine derivative is an important organic compound and widely exists in molecular frameworks of biological medicines, foods, cosmetics, pesticides and natural products, so that the efficient synthesis method of the secondary amine derivative has great application value and wide application prospect.
Efficient synthesis of secondary amine derivatives has been one of the continuing goals of organic chemistry workers, where the synthesis of secondary amines by reduction of substrate molecules containing carbon-nitrogen unsaturated functional groups, such as imines, nitriles, oximes, amides, etc., has been an important technological approach; the reducing agent commonly used at present is NaBH4，LiAlH4，B2H6These reducing agents can easily and directly reduce compounds such as imines, nitriles, oximes, amides, etc. to the corresponding secondary amines. However, there are problems, firstly the amount of reducing agent, which usually needs to be in large excess; secondly, a lot of metal salt wastes are generated after the reaction is finished, and the atom economy is poor; finally, the post-reaction treatment is cumbersome. These disadvantages limit NaBH to some extent4，LiAlH4，B2H6The use of classical reducing agents (chem. soc. rev.1998,27,395). In recent years, the hydrogen transfer reduction reaction of amide is favored by more and more chemical workers (chem. eur. j.2011,17,12186; chem. Commun.2013,49, 9758-9760), and compared with the amide reduction by catalytic hydrogenation of hydrogen directly, the hydrogen transfer reduction reaction avoids the use of hydrogen and is safer. The most commonly used hydrogen transfer reduction reagent is an organosilicon reagent, but most organosilicon substances are very sensitive to air, are easy to react with oxygen in the air to damage the structure, and are not easy to expose in the air for a long time, so that the preparation method has certain limitation in actual production, and cannot be really popularized and used in a large scale.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a secondary amine derivative synthesized by rare earth catalysis and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme: a secondary amine derivative synthesized by rare earth catalysis has a structural formula
wherein-R1Is any one of methyl, ethyl, benzyl, cyclohexyl and phenyl;
-R is aryl or alkyl.
As a further improvement of the invention, the alkyl is any one of methyl, benzyl and tert-butyl; the aryl is phenyl with 0-3 substituents on the phenyl ring.
As a further improvement of the present invention, the substituent is any one of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen, a nitro group and a trifluoromethyl group.
As a further improvement of the invention, the secondary amine derivative is formed by reacting a secondary amide with pinacolborane;
the secondary amide has the structural formula
The pinacol borane has a structural formula of
Which is of the formula
wherein-R in secondary amide and secondary amine derivatives1The same is any one of methyl, ethyl, benzyl, cyclohexyl and phenyl;
the secondary amide is also the same as-R in the secondary amine derivative, and is an alkyl or aryl group;
wherein the alkyl is any one of methyl, benzyl and tert-butyl;
aryl is phenyl with 0-3 substituents on the phenyl ring; the substituent is any one of alkyl with 1-4 carbon numbers, alkoxy with 1-4 carbon numbers, halogen, nitro and trifluoromethyl.
As a further development of the invention, the reaction of the secondary amide with pinacolborane is carried out in a solvent which is toluene or xylene.
As a further improvement of the invention, when the secondary amide and the pinacol borane react in the solvent, a rare earth catalyst is also added into the solvent, and the rare earth catalyst is bistrimethylsilyl amino yttrium.
As a further improvement of the invention, the preparation method of the secondary amine derivative synthesized by rare earth catalysis comprises the following steps: under the protection of nitrogen, adding secondary amide, pinacolborane, a rare earth catalyst and a solvent into a reaction vessel, and stirring and mixing; after being mixed evenly, the mixture reacts for 20 to 25 hours at the temperature of 100 ℃ and 140 ℃ to prepare the secondary amine derivative.
As a further development of the invention, the substances of secondary amide and pinacolborane are added to the reaction vessel in a ratio of the amounts of 1: 5-8.
As a further improvement of the invention, the ratio of the amounts of the substances of secondary amide and rare earth catalyst added to the reaction vessel is 1: 0.08-0.15.
The invention has the beneficial effects that: the raw materials are easy to obtain, wide in source, low in cost, stable in property, easy to store, low in toxicity and not easy to influence human health; the preparation method is simple and convenient to operate, has strong reaction selectivity, can directly synthesize a target product, does not need to separate intermediate products, can obtain the target product only by reacting under normal pressure, has simple reaction process and highest yield of 90 percent, greatly simplifies process engineering, reduces energy consumption and has the advantage of high yield; the reaction raw materials are stable and easy to store, and the catalyst can be directly purchased commercially, so that the catalyst has a good application prospect; meanwhile, in the reaction process, the waste solution is less, and other polluted gases and liquid are not discharged, so that the method reduces the discharge of the waste solution, and has the advantages of protecting the environment and ensuring the health of operators; the toxicity of the substances used in the invention is low, thus ensuring the health of operators; in addition, a series of secondary amine derivatives can be prepared, and the method has strong substrate universality, thereby providing better guarantee for developing related substances related to the secondary amine derivatives and being suitable for large-scale popularization and application.
Drawings
FIG. 1 is a diagram of the reaction mechanism of the present invention;
Detailed Description
Example 1
Under the protection of nitrogen, raw materials of N-benzyl benzamide (0.5mmol), pinacol borane (3.0mmol), a rare earth catalyst of bis (trimethylsilyl) amino yttrium (10 mol%) and a solvent of toluene (3ml) are added into a reaction vessel for stirring and mixing; after being uniformly mixed, the mixture reacts for 24 hours at the temperature of 120 ℃ to prepare dibenzylamine; the final product yield was 90%.
Characterization data:1H NMR(CDCl3,500MHz,ppm):δ7.43-7.38(m,8H),7.35-7.31(m,2H),3.88(s,4H),1.75(brs,1H).13C NMR(CDCl3,125MHz,ppm):δ140.5,128.5,128.2,127.0,53.5.
dibenzylamine has the following structural formula:
which is of the formula
Example 2
Under the protection of nitrogen, raw materials of N-benzyl-4-methoxybenzamide (0.5mmol), pinacol borane (3.5mmol), a rare earth catalyst of bis (trimethylsilyl) amino yttrium (9 mol%) and a solvent of toluene (3ml) are added into a reaction vessel for stirring and mixing; after being uniformly mixed, the mixture reacts for 25 hours at the temperature of 110 ℃ to prepare N-benzyl-4-methoxyphenyl methylamine; the final product yield was 89%.
Characterization data:1H NMR(CDCl3,500MHz,ppm):δ7.37-7.34(m,4H),7.30-7.28(m,3H),6.92-6.89(m,2H),3.82(s,5H),3.78(s,2H),1.85(brs,1H).13C NMR(CDCl3,125MHz,ppm):δ158.8,140.5,132.6,129.4,128.5,128.2,127.0,113.9,55.3,53.2,52.7.
the structural formula of the N-benzyl-4-methoxyphenyl methylamine is
Which is of the formula
Example 3
Under the protection of nitrogen, raw materials of N-benzyl-2-furancarboxamide (0.5mmol), pinacolborane (2.5mmol), a rare earth catalyst of bis (trimethylsilyl) amino yttrium (12 mol%) and a solvent of toluene (3ml) are added into a reaction vessel for stirring and mixing; after being mixed evenly, the mixture reacts for 22 hours at the temperature of 100 ℃ to prepare N-benzyl-1- (2-furan) -methylamine; the final product yield was 85%.
Characterization data:1H NMR(CDCl3,500MHz,ppm):δ7.39-7.38(m,1H),7.35-7.34(m,4H),7.29-7.26(m,1H),6.34(dd,J＝1.9Hz,J＝3.1Hz,1H),6.20(d,J＝3.1Hz,1H),3.80(s,4H),1.97(brs,1H).13C NMR(CDCl3,125MHz,ppm):δ154.0,141.9,140.0,128.5,128.3,127.1,110.2,107.1,52.9,45.5.
the structural formula of N-benzyl-1- (2-furan) -methylamine is as follows:
which is of the formula
Example 4
Under the protection of nitrogen, raw materials of N-benzyl-4-bromobenzamide (0.5mmol), pinacol borane (3.0mmol), a rare earth catalyst of bistrimethylsilyl amino yttrium (10 mol%) and a solvent of toluene (3ml) are added into a reaction vessel for stirring and mixing; after being mixed evenly, the mixture reacts for 25 hours at the temperature of 130 ℃ to prepare N-benzyl-4-bromophenyl methylamine; the final product yield was 86%.
Characterization data:1H NMR(CDCl3,500MHz,ppm):δ7.42(d,J＝8.3Hz,2H),7.34-7.29(m,4H),7.27-7.23(m,1H),7.20(d,J＝8.3Hz,2H),3.76(s,2H),3.72(s,2H),1.70(brs,1H).13CNMR(CDCl3,125MHz,ppm):δ140.3,139.5,131.6,130.0,128.5,128.2,127.1,120.8,53.2,525.5.
the structural formula of the N-benzyl-4-bromophenyl methylamine is as follows:
which is of the formula
Example 5
Under the protection of nitrogen, raw materials of N-benzyl-4-trifluoromethyl benzamide (0.5mmol), pinacol borane (4.0mmol), a rare earth catalyst of bis (trimethylsilyl) amino yttrium (13 mol%) and a solvent of toluene (3ml) are added into a reaction vessel for stirring and mixing; after being uniformly mixed, the mixture reacts for 23 hours at the temperature of 120 ℃ to prepare N-benzyl-4-trifluoromethyl phenyl methylamine; the final product yield was 83%.
Characterization data:1H NMR(CDCl3,500MHz,ppm):δ7.61(d,J＝8.0Hz,2H),7.49(d,J＝8.0Hz,2H),7.39-7.34(m,4H),7.33-7.27(m,1H),3.88(s,2H),3.83(s,2H),1.75(brs,1H).13C NMR(CDCl3125MHz, ppm): δ 144.7,140.2,129.4(q, J ═ 32.3Hz),128.6,128.4,128.3,127.2,125.4(q, J ═ 3.8Hz),124.5(q, J ═ 271.9Hz),53.4,52.7. the structural formula of N-benzyl-4-trifluoromethylphenylmethylamine is as follows:
which is of the formula
Example 6
Under the protection of nitrogen, adding N-phenyl benzamide (0.5mmol), pinacol borane (3.0mmol), a rare earth catalyst bis (trimethylsilyl) amino yttrium (10 mol%) and a solvent toluene (3ml) into a reaction vessel, and stirring and mixing; after being uniformly mixed, the mixture reacts for 22 hours at the temperature of 120 ℃ to prepare the N-benzyl aniline; the final product yield was 87%.
Characterization data:1H NMR(CDCl3,500MHz,ppm):δ7.41-7.35(m,4H),7.32-7.29(m,1H),7.23-7.19(m,2H),6.75(t,J＝7.3Hz,1H),6.67(d,J＝7.8Hz,2H),4.36(s,2H),4.12(brs,1H).13C NMR(CDCl3,125MHz,ppm):δ148.3,139.6,129.4,128.8,127.7,127.4,117.8,113.1,48.5.
the structural formula of the N-benzylaniline is as follows:
which is of the formula
Example 7
Under the protection of nitrogen, adding N-cyclohexyl benzamide (0.5mmol), pinacol borane (3.0mmol), a rare earth catalyst bis (trimethylsilyl) amino yttrium (15 mol%) and a solvent toluene (3ml) into a reaction vessel, and stirring and mixing; after being uniformly mixed, the mixture reacts for 21 hours at the temperature of 140 ℃ to prepare N-benzyl cyclohexyl amine; the final product yield was 82%.
Characterization data:1H NMR(CDCl3,500MHz,ppm):δ7.33-7.32(m,4H),7.25-7.22(m,1H),3.81(s,2H),2.53-2.46(m,1H),1.94-1.91(m,2H),1.76-1.72(m,2H),1.63-1.60(m,2H),1.31-1.08(m,5H).13C NMR(CDCl3,125MHz,ppm):δ141.0,128.5,128.3,126.9,56.3,51.1,33.7,26.3,25.2.
the structural formula of the N-benzylcyclohexylamine is as follows:
which is of the formula
Example 8
Under the protection of nitrogen, adding N-cyclohexyl-4-methylbenzamide (0.5mmol), pinacolborane (3.5mmol), a rare earth catalyst bis (trimethylsilyl) amino yttrium (13 mol%) and a solvent toluene (3ml) into a reaction vessel, and stirring and mixing; after being uniformly mixed, the mixture reacts for 24 hours at the temperature of 130 ℃ to prepare N- (4-methylbenzyl) cyclohexylamine; the final product yield was 87%.
Characterization data:1H NMR(CDCl3,500MHz,ppm):δ7.21(d,J＝7.9Hz,2H),7.13(d,J＝7.9Hz,2H),3.77(s,2H),2.52-2.45(m,1H),2.33(s,3H),1.93-1.90(m,2H),1.75-1.60(m,4H),1.30-1.08(m,5H).13C NMR(CDCl3,125MHz,ppm):δ137.9,136.5,129.2,128.2,56.2,50.8,33.6,26.3,25.2,21.2.
the structural formula of the N- (4-methylbenzyl) cyclohexylamine is as follows:
which is of the formula
Example 9
Under the protection of nitrogen, adding N-benzyl cyclopropyl amide (0.5mmol), pinacolborane (3.0mmol), a rare earth catalyst bis (trimethylsilyl) amino yttrium (12 mol%) and a solvent toluene (3ml) into a reaction vessel, and stirring and mixing; after being uniformly mixed, the mixture reacts for 20 hours at the temperature of 140 ℃ to prepare N-benzyl cyclopropyl methylamine; the final product yield was 88%.
Characterization data:1H NMR(CDCl3,500MHz,ppm):δ7.33-7.32(m,4H),7.28-7.22(m,1H),3.82(s,2H),2.49(d,J＝6.9Hz,2H),1.77(brs,1H),1.04-0.94(m,1H),0.50-0.46(m,2H),0.12-0.08(m,2H).13C NMR(CDCl3,125MHz,ppm):δ140.6,128.5,128.2,127.0,54.5,53.9,11.4,3.5.
the structural formula of the N-benzyl cyclopropyl methylamine is as follows:
which is of the formula
Example 10
Under the protection of nitrogen, adding N-benzyl tert-butyl amide (0.5mmol), pinacolborane (3.0mmol), a rare earth catalyst bis (trimethylsilyl) amino yttrium (11 mol%) and a solvent toluene (3ml) into a reaction vessel, and stirring and mixing; after being uniformly mixed, the mixture reacts for 24 hours at the temperature of 120 ℃ to prepare N-benzyl tert-butyl methylamine; the final product yield was 88%.
Characterization data:1H NMR(CDCl3,500MHz,ppm):δ7.36-7.31(m,4H),7.27-7.24(m,1H),3.83(s,2H),2.37(s,2H),1.49(brs,1H),0.93(s,9H).13C NMR(CDCl3,125MHz,ppm):δ141.1,128.4,128.1,126.9,61.8,54.8,31.7,27.9.
the structural formula of the N-benzyl tert-butyl methylamine is as follows:
which is of the formula
FIG. 1 is a reaction scheme of the present invention, as can be seen from FIG. 1: firstly, reacting a rare earth catalyst with pinacol borane to generate a rare earth hydride intermediate A, inserting a rare earth-hydrogen bond into acyl to form an intermediate B, further reacting the borane with the intermediate B to obtain a borate intermediate C, and generating the intermediate A. Intermediate C is then converted to iminium cation intermediate D. D reacts with pinacolborane to generate imine E, and hydrogen and boron ester are released. And further adding imine and rare earth hydride to obtain an intermediate F, reacting F with pinacol borane to obtain a boron-amine compound G and rare earth hydride to complete catalytic cycle. And G is hydrolyzed to obtain the target product amine.
The invention relates to a secondary amine derivative synthesized by rare earth catalysis and a preparation method thereof, which are prepared by taking secondary amide and pinacolborane as reactants for reaction; wherein the secondary amide has the formulawherein-R1Is any one of methyl, ethyl, benzyl, cyclohexyl and phenyl; -R is aryl or alkyl; wherein the alkyl group is any of methyl, benzyl and tert-butylThe method is as follows; aryl is phenyl with 0-3 substituents on the phenyl ring; the substituent is any one of alkyl with 1-4 carbon numbers, alkoxy with 1-4 carbon numbers, halogen, nitro and trifluoromethyl.
And the pinacolborane has the structural formula
The reactant raw materials are easy to obtain, wide in source, low in cost, stable in property, easy to store, low in toxicity and not easy to influence human health; the reaction of the invention is carried out in a solvent, wherein the solvent is toluene or xylene; during reaction, a rare earth catalyst is also added into the solvent; the amount of the added substances of the rare earth catalyst is 8 to 15 percent of the secondary amide of the raw material; the rare earth catalyst used in the invention is bis-trimethylsilyl amino yttrium; under the catalytic action of the catalyst, the reaction rate can be greatly accelerated, and the reaction is shortened, so that the reaction cost is reduced; the reaction temperature of the invention is 100-140 ℃, the reaction time is 20-25 hours, the whole reaction is carried out under normal pressure, the reaction condition is mild, easy to achieve and safe.
The method has simple and convenient operation and strong reaction selectivity, can directly synthesize the target product, does not need to separate intermediate products, can obtain the target product only by reacting under normal pressure, has simple reaction process and highest yield of 90 percent, greatly simplifies process engineering, reduces energy consumption and has the advantage of high yield; the reaction raw materials are stable and easy to store, and the catalyst can be directly purchased commercially, so that the catalyst has a good application prospect; meanwhile, in the reaction process, the waste solution is less, and other polluted gases and liquid are not discharged, so that the method reduces the discharge of the waste solution, and has the advantages of protecting the environment and ensuring the health of operators; the toxicity of the substances used in the invention is low, thus ensuring the health of operators; in addition, a series of secondary amine derivatives can be prepared, and the method has strong substrate universality, thereby providing better guarantee for developing related substances related to the secondary amine derivatives and being suitable for large-scale popularization and application.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (9)
1. A secondary amine derivative synthesized by rare earth catalysis is characterized in that: the secondary amine derivative has the structural formula
wherein-R1Is any one of methyl, ethyl, benzyl, cyclohexyl and phenyl;
-R is aryl or alkyl.
2. A rare earth catalytically synthesized secondary amine derivative according to claim 1, wherein: the alkyl is any one of methyl, benzyl and tert-butyl;
the aryl is phenyl with 0-3 substituents on the phenyl ring.
3. A rare earth catalytically synthesized secondary amine derivative according to claim 2, wherein: the substituent is any one of alkyl with 1-4 carbon numbers, alkoxy with 1-4 carbon numbers, halogen, nitro and trifluoromethyl.
4. A rare earth catalytically synthesized secondary amine derivative according to claim 3, wherein: the secondary amine derivative is prepared from a secondary amide and
pinacol borane is reacted;
the secondary amide has the structural formula
The pinacol borane has a structural formula of
Which is of the formula
wherein-R in secondary amide and secondary amine derivatives1The same is any one of methyl, ethyl, benzyl, cyclohexyl and phenyl;
the secondary amide is also the same as-R in the secondary amine derivative, and is an alkyl or aryl group;
wherein the alkyl is any one of methyl, benzyl and tert-butyl;
aryl is phenyl with 0-3 substituents on the phenyl ring; the substituent is any one of alkyl with 1-4 carbon numbers, alkoxy with 1-4 carbon numbers, halogen, nitro and trifluoromethyl.
5. A rare earth catalyzed synthetic secondary amine derivative according to claim 4, wherein: the reaction of the secondary amide and pinacolborane is carried out in a solvent which is toluene or xylene.
6. A rare earth catalyzed synthetic secondary amine derivative according to claim 5, wherein: when the secondary amide and the pinacol borane react in the solvent, a rare earth catalyst is also added into the solvent, and the rare earth catalyst is bis (trimethylsilyl) amino yttrium.
7. The method for preparing a secondary amine derivative through rare earth catalytic synthesis according to claim 6, wherein: under the protection of nitrogen, adding secondary amide, pinacolborane, a rare earth catalyst and a solvent into a reaction vessel, and stirring and mixing; after being mixed evenly, the mixture reacts for 20 to 25 hours at the temperature of 100 ℃ and 140 ℃ to prepare the secondary amine derivative.
8. The method for preparing a secondary amine derivative through rare earth catalytic synthesis according to claim 7, wherein the method comprises the following steps: the ratio of the amounts of the substance of secondary amide and pinacolborane added to the reaction vessel was 1: 5-8.
9. The method for preparing a secondary amine derivative through rare earth catalytic synthesis according to claim 8, wherein: the ratio of the amounts of the substances of secondary amide and rare earth catalyst added to the reaction vessel is 1: 0.08-0.15.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911014908.7A CN110818576B (en) | 2019-10-24 | 2019-10-24 | Secondary amine derivative synthesized by rare earth catalysis and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911014908.7A CN110818576B (en) | 2019-10-24 | 2019-10-24 | Secondary amine derivative synthesized by rare earth catalysis and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110818576A true CN110818576A (en) | 2020-02-21 |
| CN110818576B CN110818576B (en) | 2023-02-24 |
Family
ID=69550490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911014908.7A Active CN110818576B (en) | 2019-10-24 | 2019-10-24 | Secondary amine derivative synthesized by rare earth catalysis and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110818576B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778344A (en) * | 2021-01-08 | 2021-05-11 | 温州大学新材料与产业技术研究院 | Synthesis method of alkenyl borate |
| CN113426482A (en) * | 2021-07-27 | 2021-09-24 | 北京理工大学 | Application method of sodium triethylborohydride, organic amine compound and preparation method thereof |
| CN113549099A (en) * | 2021-09-18 | 2021-10-26 | 苏州源展材料科技有限公司 | Preparation method of tri [ N, N-bis (trimethylsilyl) amino ] yttrium |
-
2019
- 2019-10-24 CN CN201911014908.7A patent/CN110818576B/en active Active
Non-Patent Citations (4)
| Title |
|---|
| CHRISTOPHER J. BARGER等: "La[N(SiMe3)2]3-Catalyzed Ester Reductions with Pinacolborane: Scope and Mechanism of Ester Cleavage", 《ACS CATAL.》 * |
| GUOQI ZHANG等: "Redox-Noninnocent Ligand-Supported Vanadium Catalysts for the Chemoselective Reduction of C=X (X=O, N) Functionalities", 《J. AM. CHEM. SOC.》 * |
| 无: "无", 《STN REGISTRY数据库》 * |
| 武振杰: "硅胺稀土配合物催化醛、酮以及亚胺的硼氢化反应的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778344A (en) * | 2021-01-08 | 2021-05-11 | 温州大学新材料与产业技术研究院 | Synthesis method of alkenyl borate |
| CN113426482A (en) * | 2021-07-27 | 2021-09-24 | 北京理工大学 | Application method of sodium triethylborohydride, organic amine compound and preparation method thereof |
| CN113549099A (en) * | 2021-09-18 | 2021-10-26 | 苏州源展材料科技有限公司 | Preparation method of tri [ N, N-bis (trimethylsilyl) amino ] yttrium |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110818576B (en) | 2023-02-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110818576B (en) | Secondary amine derivative synthesized by rare earth catalysis and preparation method thereof | |
| Wang et al. | The ortho-substituent on 2, 4-bis (trifluoromethyl) phenylboronic acid catalyzed dehydrative condensation between carboxylic acids and amines | |
| Hu | Nucleophilic ring opening of aziridines | |
| Ramazani et al. | Three‐Component Reaction of Isocyanides and 2‐Formylbenzoic Acid with Dibenzylamine Catalyzed by Silica Nanoparticles under Solvent‐Free Conditions | |
| Michon et al. | Inter‐and Intramolecular Hydroamination of Unactivated Alkenes Catalysed by a Combination of Copper and Silver Salts: The Unveiling of a Brønstedt Acid Catalysis | |
| Mita et al. | One‐Step Synthesis of Racemic α‐Amino Acids from Aldehydes, Amine Components, and Gaseous CO2 by the Aid of a Bismetal Reagent | |
| CN109331872B (en) | Application of n-butyl lithium in catalyzing imine and borane hydroboration reaction | |
| CN110803995B (en) | Method for synthesizing tertiary amine derivative through hydroboration reaction of tertiary amide under catalysis of rare earth | |
| Wang et al. | Copper-catalyzed coupling of amines with carbazates: An approach to carbamates | |
| WO2009037307A2 (en) | Accelerated reduction of organic substances with boranes | |
| Li et al. | Straightforward approach toward multifunctionalized aziridines via catalyst-free three-component reactions of α-diazoesters, nitrosoarenes, and alkynes | |
| Baishya et al. | Catalyst free C–N bond formation by the reaction of amines with diimides: bulky guanidines | |
| Singh et al. | New energetic polynitro cyclic esters: ammonium, hydrazinium, and hydroxylammonim salts of polynitramines | |
| Cossy et al. | Lithium bistrifluoromethanesulfonimidate-mediated regioselective ring opening of aziridines by amines | |
| Nagao et al. | MONITORED AMINOLYSIS OF 3-ACYLTHIAZOLIDINE-2-THI0NE: A NEW SYNTHESIS OF MACROCYCLIC AMIDES | |
| CN107235845B (en) | Novel method for nonmetal-catalyzed bidirectional selective reduction of tertiary aromatic amide | |
| Nayak et al. | Organoaluminum Catalyzed Guanylation and Hydroboration Reactions of Carbodiimides | |
| Timmons et al. | The combination of TsNH2 and NCS as nitrogen and chlorine sources for direct diamination of enones | |
| Tanaka et al. | Catalytic dehydrogenative N-((triisopropylsilyl) oxy) carbonyl (Tsoc) protection of amines using iPr 3 SiH and CO 2 | |
| JP7525112B2 (en) | Method for producing urea derivatives | |
| JP2015513562A (en) | Reaction product of hydrazine derivative and carbon dioxide | |
| CN111116420B (en) | Preparation method of symmetrical urea compound | |
| CN109289914B (en) | Application of o-methyl aniline lithium in catalyzing imine and borane hydroboration reaction | |
| Baruah et al. | An atom economic acid catalyzed synthetic method for aromatic imines | |
| WO2012040853A1 (en) | Group 5 metal complexes useful for amine functionalization and synthetic process for manufacture thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |