CN106565501A - Method for preparing neral amine compound - Google Patents
Method for preparing neral amine compound Download PDFInfo
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- CN106565501A CN106565501A CN201610977194.XA CN201610977194A CN106565501A CN 106565501 A CN106565501 A CN 106565501A CN 201610977194 A CN201610977194 A CN 201610977194A CN 106565501 A CN106565501 A CN 106565501A
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- neral
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/52—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of imines or imino-ethers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing a neral amine compound. The method mainly solves the problems in the prior art that conventional methods for preparing neral amine compounds adopt neral and amine as reaction raw materials and are low in catalyst activity, poor in stability, long in reaction time and difficult in catalyst recovery and utilization. According to the technical scheme of the invention, neral and amine are adopted as reaction raw materials, and a solid super acid loaded by a microporous polymer PIMs is adopted as a catalyst. The catalyst is high in activity, and the reaction time lasts for 1-3 hours. The yield can reach 95.7% or more. Meanwhile, the reaction condition is relatively mild and the requirement on equipment is low. Meanwhile, the catalyst can be recycled and used for a plurality of times, so that the production cost is reduced.
Description
Technical field
The present invention relates to a kind of method for preparing neral aminated compoundss, and in particular to a kind of N- replacement-nerals amine
The preparation method of class compound.
Background technology
Neral amine has preferable effect in terms of antibacterial, sterilization.Which is generally by neral and amine under catalyst action
Reaction generates orange blossom aldimine, and then orange blossom aldimine generates neral amine in the presence of reducing agent.Catalysis wherein used
Agent is boron trifluoride diethyl etherate, zinc chloride, aluminum chloride, but the activity of these catalyst is not high, and the response time is long, while catalysis
Agent separates difficulty, is difficult to recycle, the production and application of these restriction neral amine.
The content of the invention
The technical problem to be solved is that prior art prepares neral amine as reaction raw materials with neral and amine
There is a problem of in class compound method that catalyst activity is low, stability is poor, response time length and catalyst are difficult to recycle,
A kind of new method for preparing neral aminated compoundss is provided.The method has catalyst low-temperature activity height, high income, reaction
Mild condition, be easily recycled, the advantage that environmental pollution is little.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is as follows：One kind prepares orange blossom aldehyde amines chemical combination
The method of thing, comprises the steps：（1）Neral is dissolved in into solvent, catalyst and amine is added under conditions of 5-15 DEG C, is being urged
Reaction 1-3h is carried out in the presence of agent, reaction terminates rear Filtration of catalyst, obtains N- replacement-neral imines chemical combination
Thing；（2）By step（1）N- replacement-neral the imine compounds for obtaining are dissolved in alcohol, at 0-10 DEG C add reducing agent,
In the presence of reducing agent, room temperature reaction 2-5 hours obtain N- replacement-neral aminated compoundss；Wherein used by step (1)
Catalyst is in terms of parts by weight including following components：A) 30～80 parts of carrier, carrier in the PIMs PIM-1, PIM-2,
At least one in the intrinsic microporous polymers of PIM-6；Be loaded in b thereon) 20～70 parts selected from SO4 2-、Cl-、S2O8 2-In extremely
A kind of few solid super-strong acid.
The catalyst amount is the 5%～10% of neral in mass
Described solvent is dichloromethane, one or two in thiacyclohexane.
Described amine is n-butylamine, benzylamine, cyclohexylamine, 1-Aminooctane, the one kind in aniline.Neral with the mol ratio of amine is
1:1-1.5。
Described alcohol is methanol, one or two in ethanol.The consumption of alcohol is N- replacement-orange blossom imine compound weights
20-30 times of amount.
Described reducing agent is sodium borohydride, one or two in potassium borohydride, the reducing agent and N- replacements-orange blossom
The mol ratio of aldimine is 1.5-3:1.
Step（1）Reaction temperature be 5-20 DEG C, the response time is 1-3h.
Further, catalyst is SO4 2-/PIM-1、SO4 2-/PIM-2、SO4 2-/PIM-6、Cl-/PIM-1、Cl-/PIM-2、
Cl-/PIM-6、S2O8 2-/PIM-1、S2O8 2-/PIM-2、S2O8 2-At least one in/PIM-6.Capillary copolymer material PIMs
The mol ratio of covalent ion and part in series is between 1: 5 to 5: 1
Further, step（2）Middle reaction obtains N- replacement-neral aminated compoundss crude products, processes pure by purifying crude
N- replacement-neral the aminated compoundss of change.Purifying crude is processed as using silica gel chromatography, first with n-butylamine to silicagel column
It is neutralized, then with n-hexane-ethyl acetate=1：10 (v/v) eluting, obtains corresponding purification N- replacement-orange blossom aldehyde amines
Compound.
The present invention has the advantages that：
1）With the acid of capillary copolymer material PIMs supported solid superacids as catalyst, microporous polymer PIMs carriers can make catalyst
With higher heat stability and chemical stability with very big specific surface area and while porosity, take so as to improve N-
The yield of generation-neral imine compound, the yield of N- replacement-neral imine compounds up to 97.6%, while most
The yield of end-product N- replacement-neral aminated compoundss is up to 96.1%.
2）By the present invention in that be catalyst with capillary copolymer material PIMs supported solid superacid acid, catalyst activity
Height, the response time, yield can just reach more than 95.7%, and reaction condition is relatively mild in 1-3h, the requirement to equipment compared with
It is low, while catalyst is recyclable, it is used for multiple times, reduces production cost；
3）Catalyst is separated with product simply, and catalyst is used 5 times, and its catalytic performance is not decreased obviously；
4）The purity of intermediate N replacement-neral imine compound and product N- replacement-neral aminated compoundss is high, can
Reach more than 98.0%.Therefore, achieve preferable technique effect.
Specific embodiment
Below by embodiment, the present invention is further elaborated, but the present invention is not limited to these embodiments.
Embodiment 1
The neral of 15.2g is added in 250ml flasks, and adds 100ml thiacyclohexanes, stirred, then at 10 DEG C to
1.3g catalyst SO are added wherein4 2-/ PIM-1 (mol ratio of covalent groups and part is 0.1), and by 7.3g n-butylamine Deca
To in reactant liquor, reaction 2h will be separated by filtration after reaction and obtain catalyst and reactant liquor while stirring, and reactant liquor is eaten with saturation
Salt water washing three times, and organic faciess are collected, organic faciess anhydrous sodium sulfate drying, concentrating under reduced pressure remove solvent thiacyclohexane and obtain slightly
Product, gained crude product carry out purification with silica gel column chromatography, first silicagel column are neutralized with n-butylamine, then with n-hexane-acetic acid second
Ester=2：10 (v/v) eluting, obtains corresponding purification N- normal-butyls-orange blossom aldimine, and yield is 96.8%, purity 98.5%.
Whole N- normal-butyls-orange blossom aldimines that above-mentioned steps are obtained are dissolved in 350g methanol, are added at 5 DEG C
After 0.1mol sodium borohydrides, 30min being stirred at this temperature, being then warmed to room temperature, reacted 5 hours at room temperature, adding water is carried out
Reaction is quenched, then first saturated common salt is washed to neutrality, then with anhydrous sodium sulfate drying, it is concentrated in vacuo to obtain N- normal-butyls-orange blossom
Aldehyde amines crude compound, gained crude product carry out purification with silica gel column chromatography, with n-hexane-ethyl acetate=1：10 (v/v) are washed
It is de-, corresponding purification N- normal-butyls-neral aminated compoundss are obtained, yield is 95.4%, purity 98.3%.
Embodiment 2
The neral of 15.2g is added in 250ml flasks, and adds 100ml thiacyclohexanes, stirred, then at 10 DEG C to
1.3g catalyst S are added wherein2O8 2-/ PIM-1 (covalent groups are 0.1 with the mol ratio of part), and 7.3g aniline is added drop-wise to
In reactant liquor, reaction 2.5h will be separated by filtration after reaction and obtain catalyst and reactant liquor while stirring, and reactant liquor is eaten with saturation
Salt water washing three times, and organic faciess are collected, organic faciess anhydrous sodium sulfate drying, concentrating under reduced pressure remove solvent thiacyclohexane and obtain slightly
Product, gained crude product carry out purification with silica gel column chromatography, first silicagel column are neutralized with n-butylamine, then with n-hexane-acetic acid second
Ester=2：10 (v/v) eluting, obtains corresponding purification N- phenyl-orange blossom aldimine, and yield is 96.3%, purity 98.7%.
Whole N- phenyl-orange blossom aldimines that above-mentioned steps are obtained are dissolved in 350g methanol, 0.1mol are added at 5 DEG C
After sodium borohydride, 30min being stirred at this temperature, being then warmed to room temperature, reacted 5 hours at room temperature, adding water carries out being quenched instead
Should, then first saturated common salt is washed to neutrality, then with anhydrous sodium sulfate drying, it is concentrated in vacuo to obtain N- phenyl-orange blossom aldehyde amines
Compound crude product, gained crude product carry out purification with silica gel column chromatography, with n-hexane-ethyl acetate=1：10 (v/v) eluting, obtains phase
The purification N- phenyl-neral aminated compoundss answered, yield is 95.9%, purity 98.6%.
Embodiment 3
The neral of 15.2g is added in 250ml flasks, and adds 100ml dichloromethane, stirred, then at 10 DEG C
It is added thereto to 1.3g catalyst Cl-/ PIM-2 (mol ratio of covalent groups and part is 0.1), and by 7.3g n-butylamine Deca
To in reactant liquor, reaction 2h will be separated by filtration after reaction and obtain catalyst and reactant liquor while stirring, and reactant liquor is eaten with saturation
Salt water washing three times, and organic faciess are collected, organic faciess anhydrous sodium sulfate drying, concentrating under reduced pressure remove solvent thiacyclohexane and obtain slightly
Product, gained crude product carry out purification with silica gel column chromatography, first silicagel column are neutralized with n-butylamine, then with n-hexane-acetic acid second
Ester=2：10 (v/v) eluting, obtains corresponding purification N- normal-butyls-orange blossom aldimine, and yield is 95.7%, purity 98.4%.
Whole N- normal-butyls-orange blossom aldimines that above-mentioned steps are obtained are dissolved in 350g ethanol, are added at 5 DEG C
After 0.1mol potassium borohydrides, 30min being stirred at this temperature, being then warmed to room temperature, reacted 5 hours at room temperature, adding water is carried out
Reaction is quenched, then first saturated common salt is washed to neutrality, then with anhydrous sodium sulfate drying, it is concentrated in vacuo to obtain N- normal-butyls-orange blossom
Aldehyde amines crude compound, gained crude product carry out purification with silica gel column chromatography, with n-hexane-ethyl acetate=1：10 (v/v) are washed
It is de-, corresponding purification N- normal-butyls-neral aminated compoundss are obtained, yield is 94.9%, purity 98.1%.
Embodiment 4
The neral of 15.2g is added in 250ml flasks, and adds 100ml thiacyclohexanes, stirred, then at 10 DEG C to
1.3g catalyst S are added wherein2O8 2-/ PIM-6 (mol ratio of covalent groups and part is 0.1), and by 7.3g n-butylamine Deca
To in reactant liquor, reaction 2h will be separated by filtration after reaction and obtain catalyst and reactant liquor while stirring, and reactant liquor is eaten with saturation
Salt water washing three times, and organic faciess are collected, organic faciess anhydrous sodium sulfate drying, concentrating under reduced pressure remove solvent thiacyclohexane and obtain slightly
Product, gained crude product carry out purification with silica gel column chromatography, first silicagel column are neutralized with n-butylamine, then with n-hexane-acetic acid second
Ester=2：10 (v/v) eluting, obtains corresponding purification N- normal-butyls-orange blossom aldimine, and yield is 97.6%, purity 99.0%.
Whole N- normal-butyls-orange blossom aldimines that above-mentioned steps are obtained are dissolved in 350g methanol, are added at 5 DEG C
After 0.1mol potassium borohydrides, 30min being stirred at this temperature, being then warmed to room temperature, reacted 5 hours at room temperature, adding water is carried out
Reaction is quenched, then first saturated common salt is washed to neutrality, then with anhydrous sodium sulfate drying, it is concentrated in vacuo to obtain N- normal-butyls-orange blossom
Aldehyde amines crude compound, gained crude product carry out purification with silica gel column chromatography, with n-hexane-ethyl acetate=1：10 (v/v) are washed
It is de-, corresponding purification N- normal-butyls-neral aminated compoundss are obtained, yield is 96.1%, purity 98.8%.
Embodiment 5
Catalyst in embodiment 4 is separated into taking-up after the completion of reaction, after drying process according to embodiment 4 reaction condition
Carry out 5 reuses.N- normal-butyls-orange blossom aldimine when reusing for wherein the 1st time, yield is 96.3%, purity
98.5%；N- normal-butyls-neral aminated compoundss, yield is 96.0%, purity 98.4%；N- positive fourths when the 5th is reused
Base-orange blossom aldimine, yield is 94.7%, purity 98.0%；N- normal-butyls-neral aminated compoundss, yield is 95.1%, pure
Degree 98.0%.
Comparative example 1
The neral of 15.2g is added in 250ml flasks, and adds 100ml thiacyclohexanes, stirred, then at 10 DEG C to
1.3g catalyst boron trifluoride diethyl etherate is wherein added, and 7.3g n-butylamines are added drop-wise in reactant liquor, reacting 2h while stirring will
It is separated by filtration after reaction and obtains catalyst and reactant liquor, by reactant liquor saturated common salt water washing three times, and collects organic faciess, have
Machine mutually uses anhydrous sodium sulfate drying, concentrating under reduced pressure to remove solvent thiacyclohexane and obtain crude product, and gained crude product silica gel column chromatography carries out pure
Change, first silicagel column is neutralized with n-butylamine, then with n-hexane-ethyl acetate=2：10 (v/v) eluting, obtains corresponding pure
Change N- normal-butyls-orange blossom aldimine, yield is 76.3%, purity 91.2%.
Whole N- normal-butyls-orange blossom aldimines that above-mentioned steps are obtained are dissolved in 350g methanol, are added at 5 DEG C
After 0.1mol potassium borohydrides, 30min being stirred at this temperature, being then warmed to room temperature, reacted 5 hours at room temperature, adding water is carried out
Reaction is quenched, then first saturated common salt is washed to neutrality, then with anhydrous sodium sulfate drying, it is concentrated in vacuo to obtain N- normal-butyls-orange blossom
Aldehyde amines crude compound, gained crude product carry out purification with silica gel column chromatography, with n-hexane-ethyl acetate=1：10 (v/v) are washed
It is de-, corresponding purification N- normal-butyls-neral aminated compoundss are obtained, yield is 83.7%, purity 94.5%.
Comparative example 2
The neral of 15.2g is added in 250ml flasks, and adds 100ml thiacyclohexanes, stirred, then at 10 DEG C to
1.3g catalyst boron trifluoride diethyl etherate is wherein added, and 7.3g n-butylamines are added drop-wise in reactant liquor, reacting 6h while stirring will
It is separated by filtration after reaction and obtains catalyst and reactant liquor, by reactant liquor saturated common salt water washing three times, and collects organic faciess, have
Machine mutually uses anhydrous sodium sulfate drying, concentrating under reduced pressure to remove solvent thiacyclohexane and obtain crude product, and gained crude product silica gel column chromatography carries out pure
Change, first silicagel column is neutralized with n-butylamine, then with n-hexane-ethyl acetate=2：10 (v/v) eluting, obtains corresponding pure
Change N- normal-butyls-orange blossom aldimine, yield is 96.3%, purity 94.2%.
Whole N- normal-butyls-orange blossom aldimines that above-mentioned steps are obtained are dissolved in 350g methanol, are added at 5 DEG C
After 0.1mol potassium borohydrides, 30min being stirred at this temperature, being then warmed to room temperature, reacted 5 hours at room temperature, adding water is carried out
Reaction is quenched, then first saturated common salt is washed to neutrality, then with anhydrous sodium sulfate drying, it is concentrated in vacuo to obtain N- normal-butyls-orange blossom
Aldehyde amines crude compound, gained crude product carry out purification with silica gel column chromatography, with n-hexane-ethyl acetate=1：10 (v/v) are washed
It is de-, corresponding purification N- normal-butyls-neral aminated compoundss are obtained, yield is 94.6%, purity 93.1%.
Embodiment described above only expresses embodiments of the present invention, and its description is more concrete and detailed, but can not
Therefore the restriction to the scope of the claims of the present invention is interpreted as, as long as the skill obtained in the form of equivalent or equivalent transformation
Art scheme, all should fall within the scope and spirit of the invention.
Claims (8)
1. a kind of method for preparing neral aminated compoundss, comprises the steps：（1）Neral is dissolved in into solvent, in 5-15
Catalyst and amine are added under conditions of DEG C, reaction 1-3h is carried out in the presence of catalyst, reaction is filtered to remove catalysis after terminating
Agent, obtains N- replacement-neral imine compounds；（2）By step（1）N- replacement-neral the imine compounds for obtaining
Being dissolved in alcohol, reducing agent being added at 0-10 DEG C, in the presence of reducing agent, room temperature reaction 2-5 hours obtain N- replacements-orange blossom
Aldehyde amines compound；Catalyst wherein used by step (1) is in terms of parts by weight including following components：A) 30～80 parts of load
Body, at least one of the carrier in the intrinsic microporous polymer of PIM-1, PIM-2, PIM-6 in PIMs；Be loaded in b thereon) 20
～70 parts are selected from SO4 2-、Cl-、S2O8 2-In at least one solid super-strong acid.
2. the method for preparing neral aminated compoundss according to claim 1, it is characterised in that：Catalyst amount be with
Quality is calculated as the 5%～10% of neral.
3. the method for preparing neral aminated compoundss according to claim 1, it is characterised in that：Solvent is dichloromethane
One or two in alkane, thiacyclohexane.
4. the method for preparing neral aminated compoundss according to claim 1, it is characterised in that：Amine is n-butylamine, benzyl
One kind in amine, cyclohexylamine, 1-Aminooctane, aniline, preferred n-butylamine or aniline.
5. the method for preparing neral aminated compoundss according to claim 4, it is characterised in that：Neral is rubbed with amine
You are than being 1:1-1.5.
6. the method for preparing neral aminated compoundss according to claim 1, it is characterised in that：Alcohol is methanol, ethanol
In one or two, 20-30 times for N- replacement-orange blossom imine compound weight of the consumption of alcohol.
7. the method for preparing neral aminated compoundss according to claim 1, it is characterised in that：Catalyst is selected from
SO4 2-/PIM-1、SO4 2-/PIM-2、SO4 2-/PIM-6、Cl-/PIM-1、Cl-/PIM-2、Cl-/PIM-6、S2O8 2-/PIM-1、
S2O8 2-/PIM-2、S2O8 2-At least one in/PIM-6.
8. the method for preparing neral aminated compoundss according to claim 1, it is characterised in that：Catalyst is separated dry
Dry Posterior circle is utilized.
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| CN201610977194.XA CN106565501A (en) | 2016-11-08 | 2016-11-08 | Method for preparing neral amine compound |
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| CN201610977194.XA CN106565501A (en) | 2016-11-08 | 2016-11-08 | Method for preparing neral amine compound |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1386735A (en) * | 2001-05-23 | 2002-12-25 | 中国科学院化学研究所 | Process for condensating salicyladehyde with arylamine |
| CN104387278A (en) * | 2014-08-29 | 2015-03-04 | 中国林业科学研究院亚热带林业研究所 | N-substituted-citral amine compound, synthesis method and application thereof |
-
2016
- 2016-11-08 CN CN201610977194.XA patent/CN106565501A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1386735A (en) * | 2001-05-23 | 2002-12-25 | 中国科学院化学研究所 | Process for condensating salicyladehyde with arylamine |
| CN104387278A (en) * | 2014-08-29 | 2015-03-04 | 中国林业科学研究院亚热带林业研究所 | N-substituted-citral amine compound, synthesis method and application thereof |
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Application publication date: 20170419 |