CN106938976B - A method of imine compound is prepared by catalytic material oxidation of alkohol and amine - Google Patents
A method of imine compound is prepared by catalytic material oxidation of alkohol and amine Download PDFInfo
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- CN106938976B CN106938976B CN201710230999.2A CN201710230999A CN106938976B CN 106938976 B CN106938976 B CN 106938976B CN 201710230999 A CN201710230999 A CN 201710230999A CN 106938976 B CN106938976 B CN 106938976B
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- 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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- C07—ORGANIC CHEMISTRY
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- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
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Abstract
The invention discloses a kind of methods for preparing imine compound as catalytic material oxidation using alkohol and amine, the method are as follows: using alcohol compound and aminated compounds as reaction substrate, molar ratio 100:100 ~ 160 of the alcohol compound and aminated compounds；Using 9- azabicyclo [3.3.1] nonane-N- oxygen radical as catalyst, using potassium hydroxide as auxiliary agent, the molar ratio of the aminated compounds and 9- azabicyclo [3.3.1] nonane-N- oxygen radical, potassium hydroxide is 100:1 ~ 6:10 ~ 50；Using air as oxidant, in organic solvent, the quality dosage of the organic solvent is 2.5 ~ 5 times of reaction substrate aminated compounds to reaction substrate；Under normal pressure, it is reacted under conditions of 70 ~ 110 DEG C of temperature, the reaction time is 2 ~ 12h, post-treated after reaction to obtain the imine compound；Operation of the present invention handy and safe is that oxidant reduces Environmental costs using clean oxygen, avoids transition metal contamination problem without using transition-metal catalyst.
Description
Technical field
The invention belongs to compound synthesis fields, more particularly to a kind of aoxidized using alkohol and amine as catalytic material to prepare imines
The method of compound.
Background technique
Imine compound that is to say schiff base compounds, be synthesis have drug and bioactive compound and
The intermediate of fine chemicals.C=N key in imine compound molecule be also widely used for such as reduction, addition, cyclisation with
And a variety of organic transformation reactions such as aziridine.The classical synthetic method of imine compound be by aminated compounds and
Aldehyde, ketone compounds are condensed to yield, and dehydrated reagent or lewis acid catalyst is needed to exist in many cases.
In recent years, the synthetic method for developing new imine compound has attracted the attention of a large number of researchers.Various
In the new synthetic method of the imine compound of various kinds, due to raw material be easy to get and molecular oxygen or air as terminal oxidant this
Two advantages, three kinds of methods are especially noticeable below.(1) cross-coupling of alkohol and amine；(2) coupling certainly of primary amine；(3) secondary amine
Oxidative dehydrogenation.Wherein, by the advantages of cross-coupling reaction synthesizing imine class compound of alkohol and amine be byproduct of reaction only
It is water, and selects different substrates that can synthesize all kinds of imine compounds symmetrically or non-symmetrically.In this kind of reaction, big portion
Pd, Au, Mn, Ce, Cu, Fe class transition-metal catalyst will be added by dividing, and thus easily cause transition metal contamination.There is researcher
Promote the reaction with KOH, but KOH needs stoichiometry to use, and the reaction time it is long (Green Chemistry 2012,14, 2384).Also have using NaOH as the catalyst reaction, but reaction time length, the yield of product imine are relatively low, and react
It can only carry out under solvent-free conditions, so that reaction substrate range is restricted (European Journal of
Organic Chemistry 2012,4457).
Summary of the invention
To solve the above-mentioned problems, the present invention provides one kind and prepares imine compound by catalytic material oxidation of alkohol and amine
Method, whole preparation process without transition metal participate in, achieve the purpose that environmental protection.
It adopts the following technical scheme that thus
A method of imine compound is prepared by catalytic material oxidation of alkohol and amine, it is characterised in that the method
Are as follows: using alcohol compound and aminated compounds as reaction substrate, the alcohol compound and aminated compounds feed intake mole
Than 100:100 ~ 160；Using 9- azabicyclo [3.3.1] nonane-N- oxygen radical as catalyst, using potassium hydroxide as auxiliary agent, institute
The molar ratio of the aminated compounds stated and 9- azabicyclo [3.3.1] nonane-N- oxygen radical, potassium hydroxide be 100:1 ~
6:10 ~ 50；Using air as oxidant, in organic solvent, the quality dosage of the organic solvent is reaction substrate to reaction substrate
2.5 ~ 5 times of aminated compounds；Under normal pressure, it is reacted under conditions of 70 ~ 110 DEG C of temperature, the reaction time is 2 ~ 12h, instead
It is post-treated after answering to obtain the imine compound；
The structure of the substrate alcohol compound is as shown in the formula (II), the structure such as formula of the substrate aminated compounds
(III) shown in, obtained product structure is as shown in the formula (I)；
In formula (I) or formula (II), R1For phenyl, substituted phenyl, heteroaryl perfume base, substituted heteroaryl perfume base, naphthalene or take
The naphthalene in generation；The heteroaryl perfume base can be ring and include the heteroatomic aromatic radical such as N, O, S；The substituted phenyl takes
The heteroaryl perfume base and substituted naphthalene in generation refer to that the hydrogen on phenyl ring, miscellaneous aromatic rings and naphthalene nucleus is substituted by one or more substituents,
The substituent group is each independently selected from one of following: halogen, the alkyl of C1 ~ C4, the alkoxy of C1-C4, methyl mercapto and trifluoro
Methyl；
In formula (I) or formula (III), R2For phenyl, substituted phenyl, naphthalene, substituted naphthalene or alkyl；The substitution
Phenyl and substituted naphthalene refer to that the hydrogen on phenyl ring and naphthalene nucleus is substituted by one or more substituents, the substituent group is respectively
It is independently selected from one of following: halogen, the alkyl of C1 ~ C4, the alkoxy of C1-C4, methyl mercapto and trifluoromethyl.
Further, in formula (I) or formula (II), preferably R1It is taken for phenyl, halogenophenyl, alkyl-substituted phenyl, alkoxy
For phenyl, methyl mercapto substituted-phenyl or thienyl；In formula (I) or formula (III), preferably R2Replace for phenyl, halogenophenyl, alkyl
Phenyl, alkoxy substituted phenyl, naphthalene or C3-C8 alkyl.
Further, the organic solvent is toluene, Mixed XYLENE, chlorobenzene or dioxane.
Further, the mass ratio of the material of the reaction substrate aminated compounds and reaction substrate alcohol compound is 100:
100~130。
Further, the aminated compounds and 9- azabicyclo [3.3.1] nonane-N- oxygen radical, potassium hydroxide
Molar ratio be 100:2 ~ 4:25 ~ 35.
Further, the reaction temperature is 80 ~ 100 DEG C.
Further, the reaction time is 4 ~ 8h.
Further, the method for the post-processing are as follows: after reaction, evaporating solvent under reduced pressure, then column chromatography for separation is carried out,
Using petroleum ether/triethylamine volume ratio 100:1 mixed liquor as eluant, eluent, the eluent containing target compound is collected, solvent is evaporated off
Up to product imine class compound.
The present invention specifically recommends the catalysis oxidation synthetic method of the imine compound to follow the steps below:
In organic solvent, aminated compounds, alcohol compound, 9- azabicyclo [3.3.1] nonane-N- oxygen radical (9- is added
Azabicyclo [3.3.1] nonane-N-oxy, ABNO) and KOH, under the conditions of atmospheric oxygen, react 4 at 80 ~ 100 DEG C ~
8h obtains imine compound；The organic solvent is toluene, Mixed XYLENE, chlorobenzene or dioxane；The reaction substrate
The mass ratio of the material of aminated compounds and reaction substrate alcohol compound is 100:100 ~ 130；The reaction substrate amine chemical combination
The mass ratio of the material of object and ABNO, KOH are 100:2 ~ 4:25 ~ 35.
After above-mentioned fully reacting, it can purify to obtain imine compound using conventional column separation.
Operation of the present invention handy and safe, its advantages essentially consist in:
A it is oxidant that clean oxygen, which) is employed herein, greatly reduces Environmental costs.
B it) avoids in the present invention using transition-metal catalyst, so as to avoid transition metal contamination problem.
Specific embodiment
Below by specific embodiment, the invention will be further described, but protection scope of the present invention is not limited to
This.
The structural formula of imine compound obtained by following embodiments is respectively as shown in formula (1) ~ (26):
Embodiment 1:NThe preparation of benzyl alkene aniline (formula 1)
In the tube sealing of 35mL, ABNO, 0.3mmol of the aniline of 1mmol, the benzylalcohol of 1.2mmol, 0.03mmol is added
The toluene of KOH and 0.5mL after the closed bottleneck of rubber stopper, is inserted into oxygen ball, reaction flask is put with replacement of oxygen inner air tube
Enter to be heated to 80 DEG C in advance in the oil bath pan to heat up, reacts 4h.Then column chromatography for separation is carried out, directly with ethyl acetate/tri- second
The mixed liquor of amine volume ratio 100:1 is eluant, eluent, collects the eluent containing target compound, solvent is evaporated off up to productNBenzyl alkene
Aniline, separation yield 90%.
Embodiment 2:NThe preparation of benzyl alkene aniline (formula 1)
Reaction step is with embodiment 1, except that toluene is changed to Mixed XYLENE,NThe separation yield of benzyl alkene aniline is
85%。
Embodiment 3:NThe preparation of benzyl alkene aniline (formula 1)
Reaction step is with embodiment 1, except that toluene is changed to chlorobenzene,NThe separation yield of benzyl alkene aniline is 84%.
Embodiment 4:NThe preparation of benzyl alkene aniline (formula 1)
Reaction step is with embodiment 1, except that toluene is changed to dioxane, reacts 6h,NThe separation of benzyl alkene aniline
Yield is 70%.
Embodiment 5:NThe preparation of benzyl alkene aniline (formula 1)
Reaction step is with embodiment 1, except that temperature is changed to 70 DEG C, reacts 8h,NThe separation yield of benzyl alkene aniline
It is 72%.
Embodiment 6:NThe preparation of benzyl alkene aniline (formula 1)
Reaction step is with embodiment 1, except that temperature is changed to 100 DEG C,NThe separation yield of benzyl alkene aniline is 88%.
Embodiment 7:NThe preparation of benzyl alkene aniline (formula 1)
Reaction step is with embodiment 1, except that temperature is changed to 110 DEG C,NThe separation yield of benzyl alkene aniline is 87%.
Embodiment 8:NThe preparation of benzyl alkene aniline (formula 1)
Reaction step is with embodiment 1, except that benzylalcohol dosage is changed to 1mmol,NThe separation yield of benzyl alkene aniline is
84%。
Embodiment 9:NThe preparation of benzyl alkene aniline (formula 1)
Reaction step is with embodiment 1, except that benzylalcohol dosage is changed to 1.6mmol,NThe separation yield of benzyl alkene aniline
It is 91%.
Embodiment 10:NThe preparation of benzyl alkene aniline (formula 1)
Reaction step is with embodiment 1, except that benzylalcohol dosage is changed to 1.3mmol,NThe separation yield of benzyl alkene aniline
It is 90%.
Embodiment 11:NThe preparation of benzyl alkene aniline (formula 1)
Reaction step is with embodiment 1, except that ABNO dosage is changed to 0.06mmol, reacts 2h,NBenzyl alkene aniline
Separation yield is 88%.
Embodiment 12:NThe preparation of benzyl alkene aniline (formula 1)
Reaction step is with embodiment 1, except that ABNO dosage is changed to 0.01mmol, KOH dosage is changed to 0.5mmol,NThe separation yield of benzyl alkene aniline is 71%.
Embodiment 13:NThe preparation of benzyl alkene aniline (formula 1)
Reaction step is with embodiment 1, except that ABNO dosage is changed to 0.04mmol, KOH dosage is changed to 0.1mmol,NThe separation yield of benzyl alkene aniline is 74%.
Embodiment 14:NThe preparation of benzyl alkene aniline (formula 1)
Reaction step is with embodiment 1, except that ABNO dosage is changed to 0.02mmol, KOH dosage is changed to 0.35mmol,NThe separation yield of benzyl alkene aniline is 85%.
Embodiment 15:NThe preparation of benzyl alkene aniline (formula 1)
Reaction step is with embodiment 1, except that KOH dosage is changed to 0.25mmol,NThe separation yield of benzyl alkene aniline
It is 86%.
Embodiment 16:NThe preparation of benzyl alkene -2-aminotoluene (formula 2)
In the tube sealing of 35mL, be added the 2-aminotoluene of 1mmol, the benzylalcohol of 1.2mmol, 0.03mmol ABNO,
The toluene of the KOH and 0.5mL of 0.3mmol after the closed bottleneck of rubber stopper, are inserted into oxygen ball with replacement of oxygen inner air tube, will
Reaction flask, which is put into the oil bath pan to heat up in advance, is heated to 80 DEG C, reacts 12h.Then column chromatography for separation is carried out, directly with acetic acid
Ethyl ester/triethylamine volume ratio 100:1 mixed liquor is eluant, eluent, collects the eluent containing target compound, solvent is evaporated off to obtain the final product
ProductNBenzyl alkene -2-aminotoluene, separation yield 85%.
Embodiment 17:NThe preparation of benzyl alkene -3- methylaniline (formula 3)
In the tube sealing of 35mL, be added the 3- methylaniline of 1mmol, the benzylalcohol of 1.2mmol, 0.03mmol ABNO,
The toluene of the KOH and 0.5mL of 0.3mmol after the closed bottleneck of rubber stopper, are inserted into oxygen ball with replacement of oxygen inner air tube, will
Reaction flask, which is put into the oil bath pan to heat up in advance, is heated to 80 DEG C, reacts 8h.Then column chromatography for separation is carried out, directly with acetic acid second
Ester/triethylamine volume ratio 100:1 mixed liquor is eluant, eluent, collects the eluent containing target compound, and solvent is evaporated off up to producing
ObjectNBenzyl alkene -3- methylaniline, separation yield 90%.
Embodiment 18:NThe preparation of benzyl alkene -4- methylaniline (formula 4)
In the tube sealing of 35mL, be added the 4- methylaniline of 1mmol, the benzylalcohol of 1.2mmol, 0.03mmol ABNO,
The toluene of the KOH and 0.5mL of 0.3mmol after the closed bottleneck of rubber stopper, are inserted into oxygen ball with replacement of oxygen inner air tube, will
Reaction flask, which is put into the oil bath pan to heat up in advance, is heated to 80 DEG C, reacts 8h.Then column chromatography for separation is carried out, directly with acetic acid second
Ester/triethylamine volume ratio 100:1 mixed liquor is eluant, eluent, collects the eluent containing target compound, and solvent is evaporated off up to producing
ObjectNBenzyl alkene -4- methylaniline, separation yield 95%.
Embodiment 19:NThe preparation of benzyl alkene -4- aminoanisole (formula 5)
In the tube sealing of 35mL, be added the 4- aminoanisole of 1mmol, the benzylalcohol of 1.2mmol, 0.03mmol ABNO,
The toluene of the KOH and 0.5mL of 0.3mmol after the closed bottleneck of rubber stopper, are inserted into oxygen ball with replacement of oxygen inner air tube, will
Reaction flask, which is put into the oil bath pan to heat up in advance, is heated to 80 DEG C, reacts 8h.Then column chromatography for separation is carried out, directly with acetic acid second
Ester/triethylamine volume ratio 100:1 mixed liquor is eluant, eluent, collects the eluent containing target compound, and solvent is evaporated off up to producing
ObjectNBenzyl alkene -4- aminoanisole, separation yield 92%.
Embodiment 20:NThe preparation of benzyl alkene -4- bromaniline (formula 6)
In the tube sealing of 35mL, be added the 4- bromaniline of 1mmol, the benzylalcohol of 1.2mmol, 0.03mmol ABNO,
The toluene of the KOH and 0.5mL of 0.3mmol after the closed bottleneck of rubber stopper, are inserted into oxygen ball with replacement of oxygen inner air tube, will
Reaction flask, which is put into the oil bath pan to heat up in advance, is heated to 80 DEG C, reacts 6h.Then column chromatography for separation is carried out, directly with acetic acid second
Ester/triethylamine volume ratio 100:1 mixed liquor is eluant, eluent, collects the eluent containing target compound, and solvent is evaporated off up to producing
ObjectNBenzyl alkene -4- bromaniline, separation yield 93%.
Embodiment 21:NThe preparation of benzyl alkene -4- chloroaniline (formula 7)
In the tube sealing of 35mL, be added the 4- chloroaniline of 1mmol, the benzylalcohol of 1.2mmol, 0.03mmol ABNO,
The toluene of the KOH and 0.5mL of 0.3mmol after the closed bottleneck of rubber stopper, are inserted into oxygen ball with replacement of oxygen inner air tube, will
Reaction flask, which is put into the oil bath pan to heat up in advance, is heated to 80 DEG C, reacts 8h.Then column chromatography for separation is carried out, directly with acetic acid second
Ester/triethylamine volume ratio 100:1 mixed liquor is eluant, eluent, collects the eluent containing target compound, and solvent is evaporated off up to producing
ObjectNBenzyl alkene -4- chloroaniline, separation yield 91%.
Embodiment 22:NThe preparation of benzyl alkene -4- fluoroaniline (formula 8)
In the tube sealing of 35mL, be added the 4- fluoroaniline of 1mmol, the benzylalcohol of 1.2mmol, 0.03mmol ABNO,
The toluene of the KOH and 0.5mL of 0.3mmol after the closed bottleneck of rubber stopper, are inserted into oxygen ball with replacement of oxygen inner air tube, will
Reaction flask, which is put into the oil bath pan to heat up in advance, is heated to 80 DEG C, reacts 8h.Then column chromatography for separation is carried out, directly with acetic acid second
Ester/triethylamine volume ratio 100:1 mixed liquor is eluant, eluent, collects the eluent containing target compound, and solvent is evaporated off up to producing
ObjectNBenzyl alkene -4- fluoroaniline, separation yield 89%.
Embodiment 23:NThe preparation of (4- benzyl chloride alkene) aniline (formula 9)
In the tube sealing of 35mL, be added the aniline of 1mmol, the 4- chlorobenzyl alcohol of 1.2mmol, 0.03mmol ABNO,
The toluene of the KOH and 0.5mL of 0.3mmol after the closed bottleneck of rubber stopper, are inserted into oxygen ball with replacement of oxygen inner air tube, will
Reaction flask, which is put into the oil bath pan to heat up in advance, is heated to 80 DEG C, reacts 6h.Then column chromatography for separation is carried out, directly with acetic acid second
Ester/triethylamine volume ratio 100:1 mixed liquor is eluant, eluent, collects the eluent containing target compound, and solvent is evaporated off up to producing
ObjectN(4- benzyl chloride alkene) aniline, separation yield 95%.
Embodiment 24:NThe preparation of (4- methyl benzyl alkene) aniline (formula 10)
In the tube sealing of 35mL, be added the aniline of 1mmol, the 4- xylyl alcohol of 1.2mmol, 0.03mmol ABNO,
The toluene of the KOH and 0.5mL of 0.3mmol after the closed bottleneck of rubber stopper, are inserted into oxygen ball with replacement of oxygen inner air tube, will
Reaction flask, which is put into the oil bath pan to heat up in advance, is heated to 80 DEG C, reacts 6h.Then column chromatography for separation is carried out, directly with acetic acid second
Ester/triethylamine volume ratio 100:1 mixed liquor is eluant, eluent, collects the eluent containing target compound, and solvent is evaporated off up to producing
ObjectN(4- methyl benzyl alkene) aniline, separation yield 94%.
Embodiment 25:NThe preparation of (4- methoxybenzyl alkene) aniline (formula 11)
In the tube sealing of 35mL, be added the aniline of 1mmol, the 4- methoxyl group benzylalcohol of 1.2mmol, 0.03mmol ABNO,
The toluene of the KOH and 0.5mL of 0.3mmol after the closed bottleneck of rubber stopper, are inserted into oxygen ball with replacement of oxygen inner air tube, will
Reaction flask, which is put into the oil bath pan to heat up in advance, is heated to 80 DEG C, reacts 8h.Then column chromatography for separation is carried out, directly with acetic acid second
Ester/triethylamine volume ratio 100:1 mixed liquor is eluant, eluent, collects the eluent containing target compound, and solvent is evaporated off up to producing
ObjectN(4- methoxybenzyl alkene) aniline, separation yield 92%.
Embodiment 26:NThe preparation of (4- methyl mercapto benzyl alkene) aniline (formula 12)
In the tube sealing of 35mL, be added the aniline of 1mmol, the 4- methyl mercapto benzylalcohol of 1.2mmol, 0.03mmol ABNO,
The toluene of the KOH and 0.5mL of 0.3mmol after the closed bottleneck of rubber stopper, are inserted into oxygen ball with replacement of oxygen inner air tube, will
Reaction flask, which is put into the oil bath pan to heat up in advance, is heated to 80 DEG C, reacts 5h.Then column chromatography for separation is carried out, directly with acetic acid second
Ester/triethylamine volume ratio 100:1 mixed liquor is eluant, eluent, collects the eluent containing target compound, and solvent is evaporated off up to producing
ObjectN(4- methyl mercapto benzyl alkene) aniline, separation yield 94%.
Embodiment 27:NThe preparation of (4- methoxybenzyl alkene) -4- aminoanisole (formula 13)
In the tube sealing of 35mL, the 4- aminoanisole of 1mmol, 4- methoxyl group benzylalcohol, the 0.03mmol of 1.2mmol is added
ABNO, 0.3mmol KOH and 0.5mL toluene, with replacement of oxygen inner air tube, after the closed bottleneck of rubber stopper, be inserted into oxygen
Reaction flask is put into the oil bath pan to heat up in advance and is heated to 80 DEG C by balloon, reacts 6h.Then column chromatography for separation is directly carried out,
Using ethyl acetate/triethylamine volume ratio 100:1 mixed liquor as eluant, eluent, the eluent containing target compound is collected, is evaporated off molten
Agent is up to productN(4- methoxybenzyl alkene) -4- aminoanisole, separation yield 92%.
Embodiment 28:NThe preparation of (4- benzyl chloride alkene) -4- chloroaniline (formula 14)
In the tube sealing of 35mL, be added the 4- chloroaniline of 1mmol, the 4- chlorobenzyl alcohol of 1.2mmol, 0.03mmol ABNO,
The toluene of the KOH and 0.5mL of 0.3mmol after the closed bottleneck of rubber stopper, are inserted into oxygen ball with replacement of oxygen inner air tube, will
Reaction flask, which is put into the oil bath pan to heat up in advance, is heated to 80 DEG C, reacts 6h.Then column chromatography for separation is carried out, directly with acetic acid second
Ester/triethylamine volume ratio 100:1 mixed liquor is eluant, eluent, collects the eluent containing target compound, and solvent is evaporated off up to producing
ObjectN(4- benzyl chloride alkene) -4- chloroaniline, separation yield 95%.
Embodiment 29:NThe preparation of (4- methyl benzyl alkene) -4- methylaniline (formula 15)
In the tube sealing of 35mL, the 4- methylaniline of 1mmol, the 4- xylyl alcohol of 1.2mmol, 0.03mmol is added
The toluene of the KOH and 0.5mL of ABNO, 0.3mmol after the closed bottleneck of rubber stopper, are inserted into oxygen with replacement of oxygen inner air tube
Reaction flask is put into the oil bath pan to heat up in advance and is heated to 80 DEG C by ball, reacts 6h.Then column chromatography for separation is directly carried out, with
Ethyl acetate/triethylamine volume ratio 100:1 mixed liquor is eluant, eluent, collects the eluent containing target compound, solvent is evaporated off
Up to productN(4- methyl benzyl alkene) -4- methylaniline, separation yield 94%.
Embodiment 30:NThe preparation of (4- methoxybenzyl alkene) -4- chloroaniline (formula 16)
In the tube sealing of 35mL, the 4- chloroaniline of 1mmol, the 4- methoxyl group benzylalcohol of 1.2mmol, 0.03mmol is added
The toluene of the KOH and 0.5mL of ABNO, 0.3mmol after the closed bottleneck of rubber stopper, are inserted into oxygen with replacement of oxygen inner air tube
Reaction flask is put into the oil bath pan to heat up in advance and is heated to 80 DEG C by ball, reacts 12h.Then column chromatography for separation is directly carried out, with
Ethyl acetate/triethylamine volume ratio 100:1 mixed liquor is eluant, eluent, collects the eluent containing target compound, solvent is evaporated off
Up to productN(4- methoxybenzyl alkene) -4- chloroaniline, separation yield 80%.
Embodiment 31:NThe preparation of (4- methyl benzyl alkene) -4- aminoanisole (formula 17)
In the tube sealing of 35mL, the 4- aminoanisole of 1mmol, the 4- xylyl alcohol of 1.2mmol, 0.03mmol is added
The toluene of the KOH and 0.5mL of ABNO, 0.3mmol after the closed bottleneck of rubber stopper, are inserted into oxygen with replacement of oxygen inner air tube
Reaction flask is put into the oil bath pan to heat up in advance and is heated to 80 DEG C by ball, reacts 6h.Then column chromatography for separation is directly carried out, with
Ethyl acetate/triethylamine volume ratio 100:1 mixed liquor is eluant, eluent, collects the eluent containing target compound, solvent is evaporated off
Up to productN(4- methyl benzyl alkene) -4- aminoanisole, separation yield 90%.
Embodiment 32:NThe preparation of (4- benzyl chloride alkene) -4- methylaniline (formula 18)
In the tube sealing of 35mL, the 4- methylaniline of 1mmol, the 4- chlorobenzyl alcohol of 1.2mmol, 0.03mmol is added
The toluene of the KOH and 0.5mL of ABNO, 0.3mmol after the closed bottleneck of rubber stopper, are inserted into oxygen with replacement of oxygen inner air tube
Reaction flask is put into the oil bath pan to heat up in advance and is heated to 80 DEG C by ball, reacts 4h.Then column chromatography for separation is directly carried out, with
Ethyl acetate/triethylamine volume ratio 100:1 mixed liquor is eluant, eluent, collects the eluent containing target compound, solvent is evaporated off
Up to productN(4- benzyl chloride alkene) -4- methylaniline, separation yield 96%.
Embodiment 33:NThe preparation of benzyl alkene naphthalene -2- amine (formula 19)
In the tube sealing of 35mL, ABNO, 0.3mmol of the 2- naphthylamines of 1mmol, the benzylalcohol of 1.2mmol, 0.03mmol is added
KOH and 0.5mL toluene, with replacement of oxygen inner air tube, after the closed bottleneck of rubber stopper, be inserted into oxygen ball, by reaction flask
It is put into the oil bath pan to heat up in advance and is heated to 80 DEG C, react 8h.Then column chromatography for separation is carried out, directly with ethyl acetate/tri-
The mixed liquor of ethamine volume ratio 100:1 is eluant, eluent, collects the eluent containing target compound, solvent is evaporated off up to productNBenzyl
Alkene naphthalene -2- amine, separation yield 90%.
Embodiment 34:NThe preparation of (4- methoxybenzyl alkene) naphthalene -2- amine (formula 20)
In the tube sealing of 35mL, the 2- naphthylamines of 1mmol, the 4- methoxyl group benzylalcohol of 1.2mmol, 0.03mmol is added
The toluene of the KOH and 0.5mL of ABNO, 0.3mmol after the closed bottleneck of rubber stopper, are inserted into oxygen with replacement of oxygen inner air tube
Reaction flask is put into the oil bath pan to heat up in advance and is heated to 80 DEG C by ball, reacts 8h.Then column chromatography for separation is directly carried out, with
Ethyl acetate/triethylamine volume ratio 100:1 mixed liquor is eluant, eluent, collects the eluent containing target compound, solvent is evaporated off
Up to productN(4- methoxybenzyl alkene) naphthalene -2- amine, separation yield 88%.
Embodiment 35:NThe preparation of (- 2 methylene of thiophene) aniline (formula 21)
In the tube sealing of 35mL, be added the aniline of 1mmol, the thiophene -2- base methanol of 1.2mmol, 0.03mmol ABNO,
The toluene of the KOH and 0.5mL of 0.3mmol after the closed bottleneck of rubber stopper, are inserted into oxygen ball with replacement of oxygen inner air tube, will
Reaction flask, which is put into the oil bath pan to heat up in advance, is heated to 80 DEG C, reacts 6h.Then column chromatography for separation is carried out, directly with acetic acid second
Ester/triethylamine volume ratio 100:1 mixed liquor is eluant, eluent, collects the eluent containing target compound, and solvent is evaporated off up to producing
ObjectN(- 2 methylene of thiophene) aniline, separation yield 91%.
Embodiment 36:NThe preparation of (- 2 methylene of thiophene) -4- aminoanisole (formula 22)
In the tube sealing of 35mL, be added the 4- aminoanisole of 1mmol, the thiophene -2- base methanol of 1.2mmol,
The toluene of the KOH and 0.5mL of ABNO, 0.3mmol of 0.03mmol, with replacement of oxygen inner air tube, with the closed bottleneck of rubber stopper
Afterwards, it is inserted into oxygen ball, reaction flask is put into the oil bath pan to heat up in advance and is heated to 80 DEG C, reacts 5h.Then column is directly carried out
Chromatography collects the elution containing target compound using ethyl acetate/triethylamine volume ratio 100:1 mixed liquor as eluant, eluent
Solvent is evaporated off up to product in liquidN(- 2 methylene of thiophene) -4- aminoanisole, separation yield 90%.
Embodiment 37:NThe preparation of benzyl alkene butyl- 1- amine (formula 23)
In the tube sealing of 35mL, ABNO, 0.3mmol of the n-butylamine of 1mmol, the benzylalcohol of 1.2mmol, 0.03mmol is added
KOH and 0.5mL toluene, with replacement of oxygen inner air tube, after the closed bottleneck of rubber stopper, be inserted into oxygen ball, by reaction flask
It is put into the oil bath pan to heat up in advance and is heated to 80 DEG C, react 4h.Then column chromatography for separation is carried out, directly with ethyl acetate/tri-
The mixed liquor of ethamine volume ratio 100:1 is eluant, eluent, collects the eluent containing target compound, solvent is evaporated off up to productNBenzyl
Alkene butyl- 1- amine, separation yield 90%.
Embodiment 38:NThe preparation of (4- methoxybenzyl alkene) butyl- 1- amine (formula 24)
In the tube sealing of 35mL, the n-butylamine of 1mmol, the 4- methoxyl group benzylalcohol of 1.2mmol, 0.03mmol is added
The toluene of the KOH and 0.5mL of ABNO, 0.3mmol after the closed bottleneck of rubber stopper, are inserted into oxygen with replacement of oxygen inner air tube
Reaction flask is put into the oil bath pan to heat up in advance and is heated to 80 DEG C by ball, reacts 4h.Then column chromatography for separation is directly carried out, with
Ethyl acetate/triethylamine volume ratio 100:1 mixed liquor is eluant, eluent, collects the eluent containing target compound, solvent is evaporated off
Up to productN(4- methoxybenzyl alkene) butyl- 1- amine, separation yield 91%.
Embodiment 39:NThe preparation of (4- benzyl chloride alkene) butyl- 1- amine (formula 25)
In the tube sealing of 35mL, be added the n-butylamine of 1mmol, the 4- chlorobenzyl alcohol of 1.2mmol, 0.03mmol ABNO,
The toluene of the KOH and 0.5mL of 0.3mmol after the closed bottleneck of rubber stopper, are inserted into oxygen ball with replacement of oxygen inner air tube, will
Reaction flask, which is put into the oil bath pan to heat up in advance, is heated to 80 DEG C, reacts 4h.Then column chromatography for separation is carried out, directly with acetic acid second
Ester/triethylamine volume ratio 100:1 mixed liquor is eluant, eluent, collects the eluent containing target compound, and solvent is evaporated off up to producing
ObjectN(4- benzyl chloride alkene) butyl- 1- amine, separation yield 90%.
Embodiment 40:NThe preparation of benzyl alkene cyclohexylamine (formula 26)
In the tube sealing of 35mL, ABNO, 0.3mmol of the cyclohexylamine of 1mmol, the benzylalcohol of 1.2mmol, 0.03mmol is added
KOH and 0.5mL toluene, with replacement of oxygen inner air tube, after the closed bottleneck of rubber stopper, be inserted into oxygen ball, by reaction flask
It is put into the oil bath pan to heat up in advance and is heated to 80 DEG C, react 4h.Then column chromatography for separation is carried out, directly with ethyl acetate/tri-
The mixed liquor of ethamine volume ratio 100:1 is eluant, eluent, collects the eluent containing target compound, solvent is evaporated off up to productNBenzyl
Alkene cyclohexylamine, separation yield 90%.
Claims (7)
1. a kind of method for preparing imine compound as catalytic material oxidation using alkohol and amine, it is characterised in that the method
Are as follows: using alcohol compound and aminated compounds as reaction substrate, the reaction substrate aminated compounds and reaction substrate alcohols
The mass ratio of the material for closing object is 100:100~130；Using 9- azabicyclo [3.3.1] nonane-N- oxygen radical as catalyst, with
Potassium hydroxide is auxiliary agent, the aminated compounds and 9- azabicyclo [3.3.1] nonane-N- oxygen radical, potassium hydroxide
Molar ratio is 100:1~6:10~50；Using air as oxidant, reaction substrate in organic solvent, the organic solvent
Quality dosage be 2.5~5 times of reaction substrate aminated compounds；Under normal pressure, it carries out under conditions of 70~110 DEG C of temperature anti-
It answers, the reaction time is 2~12h, post-treated after reaction to obtain the imine compound；
Shown in the structure such as formula (II) of the substrate alcohol compound, structure such as formula (III) institute of the substrate aminated compounds
Show, shown in obtained product structure such as formula (I)；
In formula (I) or formula (II), R1For phenyl, substituted phenyl, naphthalene, substituted naphthalene or thienyl；The substituted benzene
Base, substituted naphthalene refer to that phenyl ring, the hydrogen on naphthalene nucleus are substituted by one or more substituents, and the substituent group respectively independently selects
From one of following: halogen, the alkyl of C1~C4, the alkoxy of C1-C4, methyl mercapto and trifluoromethyl；
In formula (I) or formula (III), R2For the alkyl of phenyl, substituted phenyl, naphthalene, substituted naphthalene or C3-C8；Described takes
The phenyl in generation and substituted naphthalene refer to that the hydrogen on phenyl ring and naphthalene nucleus is substituted by one or more substituents, and the substituent group is each
It is one of following from being independently selected from: halogen, the alkyl of C1~C4, the alkoxy of C1-C4, methyl mercapto and trifluoromethyl.
2. a kind of method that imine compound is prepared as catalytic material oxidation using alkohol and amine described in accordance with the claim 1,
It is characterized in that: in formula (I) or formula (II), R1For phenyl, halogenophenyl, the alkyl-substituted phenyl of C1-C4, C1-C4 alkoxy
Substituted-phenyl, methyl mercapto substituted-phenyl or thienyl；In formula (I) or formula (III), R2For phenyl, halogenophenyl, C1-C4 alkane
Base substituted-phenyl, the alkoxy substituted phenyl of C1-C4, naphthalene or C3-C8 alkyl.
3. a kind of method that imine compound is prepared as catalytic material oxidation using alkohol and amine described in accordance with the claim 1,
Be characterized in that: the organic solvent is toluene, Mixed XYLENE, chlorobenzene or dioxane.
4. a kind of method that imine compound is prepared as catalytic material oxidation using alkohol and amine described in accordance with the claim 1,
Be characterized in that: the aminated compounds rubs with 9- azabicyclo [3.3.1] nonane-N- oxygen radical, feeding intake for potassium hydroxide
You are than being 100:2~4:25~35.
5. a kind of method that imine compound is prepared as catalytic material oxidation using alkohol and amine described in accordance with the claim 1,
Be characterized in that: the reaction temperature is 80~100 DEG C.
6. a kind of method that imine compound is prepared as catalytic material oxidation using alkohol and amine described in accordance with the claim 1,
Be characterized in that: the reaction time is 4~8h.
7. a kind of method that imine compound is prepared as catalytic material oxidation using alkohol and amine described in accordance with the claim 1,
It is characterized in that: the method for the post-processing are as follows: after reaction, evaporating solvent under reduced pressure, then column chromatography for separation is carried out, with petroleum
Ether/triethylamine volume ratio 100:1 mixed liquor is eluant, eluent, collects the eluent containing target compound, and solvent is evaporated off up to producing
Object imine compound.
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| CN109232308B (en) * | 2018-09-26 | 2022-11-29 | 河南师范大学 | Method for preparing imine by catalyzing amine and alcohol cross coupling by using copper catalyst |
| CN109734623A (en) * | 2019-01-11 | 2019-05-10 | 南阳师范学院 | A kind of preparation method of group with imine moiety |
| EP3696249A1 (en) | 2019-02-14 | 2020-08-19 | Konica Minolta, Inc. | Photoresponsive low-molecular weight material, adhesive, toner, and image forming method |
| CN115521225B (en) * | 2022-09-28 | 2024-01-26 | 中国科学院兰州化学物理研究所 | Method for preparing imine by cross-coupling of amine and alcohol by using composition of modified red mud and manganese oxide |
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| Title |
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| KOH-mediated transition metal-free synthesis of imines from alcohols and amines;Jian Xu et al.;《Green Chemistry》;20120620(第14期);2384-2387 * |
| NaOH-Catalyzed Imine Synthesis: Aerobic Oxidative Coupling of Alcohols and Amines;Ramachandra Reddy Donthiri et al.;《Eur. J. Org. Chem.》;20121231;4457-4460 * |
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