CN106748802A - A kind of method for preparing fluorine-containing secondary amine - Google Patents

A kind of method for preparing fluorine-containing secondary amine Download PDF

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Publication number
CN106748802A
CN106748802A CN201611220037.0A CN201611220037A CN106748802A CN 106748802 A CN106748802 A CN 106748802A CN 201611220037 A CN201611220037 A CN 201611220037A CN 106748802 A CN106748802 A CN 106748802A
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fluorine
amine
reaction
fluorinated alohol
catalyst
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CN106748802B (en
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蔡春
陈淑杰
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Nanjing University of Science and Technology
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Nanjing University of Science and Technology
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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
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
    • C07C209/18—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
    • C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • 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
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a kind of synthetic method of fluorine secondary-amine compound.With pentamethylcyclopentadiene iridium chloride dimer as metallic catalyst, fluorinated alohol is originated for fluoroalkyl, and alkali prepares fluorine secondary amine through the following steps as co-catalyst：In organic solvent, in the presence of transition metal iridium catalyst and alkali, primary amine reacts with fluorinated alohol, and fluorine-containing secondary-amine compound is obtained.The method that the present invention is provided overcomes in the prior art, and fluorine-containing alkylating reagent toxicity is big, unstable, need to prepare in advance, and operation is complicated, the defect such as complex steps, and can obtain considerable yield.The fluorinated alohol of use is readily available and stable chemical nature, toxicity are low.The method course of reaction is simple, and with Atom economy and step economy very high, energy-conserving and environment-protective are simple to operate.Using [Cp*IrCl2]2As catalyst, part need not be added in course of reaction, system is easily realized.

Description

A kind of method for preparing fluorine-containing secondary amine
Technical field
The invention belongs to organic synthesis field, and in particular to a kind of method for preparing fluorine-containing secondary amine.
Background technology
Secondary amine is a kind of very important construction unit, is widely present in medicine, agricultural chemicals and natural products molecule.Primary amine Alkylation be prepare secondary amine it is a kind of basis but important means.Since mid-twentieth century, fluorochemical is each Importance in individual field is increasingly highlighted, especially in life science.According to statistics, approved more than 20% The agricultural chemicals of the commercialization of medicine and 30-40% is fluorine-containing.If it is contemplated that introduced in primary amine containing fluoroalkyl chain, prepared Fluorine-containing secondary amine be possible to can have some special pharmaceutical activity.Therefore not only possesses reason for research prepared by fluorine-containing secondary amine It is also of far-reaching significance in practical application by upper meaning.
The preparation method of current fluorine-containing secondary amine is mainly as follows：1) the fluorine-containing alkane of halo or the plan fluorine-containing alkane of halo are used as alkane Base reagent：Primary amine fluorine-containing secondary amine corresponding with the reaction generation of fluorine-containing alkylating reagent is (such as formula a).The shortcoming of the method is fluorine-containing The toxicity of halogenated alkane is higher, and the Atom economy of reaction is also poor, and the spent acid of generation needs stoichiometric alkali as tiing up acid Agent.Additionally, much fluorine-containing alkylating reagents are not commercially available, it is necessary to prepare in advance.2) fluorine-containing fatty aldehyde is used as alkylation Reagent：First there is condensation reaction in fluorine-containing fatty aldehyde, obtain fluorine-containing imine product, then obtain fluorine-containing secondary amine (such as through reduction with primary amine Formula b).The defect of the reaction is that reaction needs two steps, and step economy is poor, and fluorine-containing fatty aldehyde is mostly unstable, with waving Hair property, and be not mostly commercially available.3) halogen exchange prepares fluorine-containing secondary amine：Primary amine prepares halo acyl with halo anhydride reaction Amine, fluoro acid amides is obtained through halogen exchange, and fluorine-containing secondary amine most is obtained (such as formula c) through reduction afterwards.Such reaction shortcoming is mainly step Rapid cumbersome, efficiency comparison is low.
Transfer hydrogenation amino-alkylation is a kind of relatively new reaction type, and its specific reaction mechanism is：In transition gold In the presence of category, there is dehydrogenation generation aldehyde and generate reducing metal hydride simultaneously in alcohol, then in generated in-situ aldehyde and system Primary amine occur condensation reaction, formed imine intermediate, the metal hydride reduction that last imine intermediate is formed by the first step, Obtain final alkylate.
Alcohol is stable in properties with abundance compared to aldehyde or halides as alkylating reagent, good economy performance etc. Advantage.Using alcohol as alkylating reagent, also become in recent years in research of the transition metal-catalyzed lower realization to the alkylation of primary amine The study hotspot for coming.However, current research is mostly focused on the substrates such as alkylol, aryl alcohol, amino alcohol, for grinding for fluorine alcohol Study carefully then much less.
The content of the invention
It is an object of the present invention to provide under one kind is transition metal-catalyzed, fluorinated alohol synthesizes fluorine-containing secondary as fluoroalkyl source The method of aminated compounds.
In order to solve the above-mentioned technical problem technical scheme is provided as follows：
A kind of method for preparing fluorine-containing secondary amine, comprises the following steps：
By in the transition metal iridium catalyst of catalytic amount, alkali mixing addition organic solution, under nitrogen protection, sequentially add Formulas I primary amine compound, Formula II fluorination alcohol compound, 90-100 DEG C of heating, stirring reaction 24h, after reaction terminates, revolving is removed Solvent, column chromatography is gone to obtain fluorine-containing secondary-amine compound formula III after purification.
Specific reaction equation is as follows：
Substituent R in Formulas I, Formula II, Rf is each independent, and R is selected from aryl, C3~C10Alkyl, C3~C10Alkoxy, It is CH that Rf is selected from end2F、CHF2Or CF3Containing fluoroalkyl chain.
The present invention compared with prior art, with remarkable advantage：
(1) instant invention overcomes in the prior art, fluorine-containing alkylating reagent toxicity is big, unstable, need to prepare in advance, instead The defects such as complex operation, complex steps are answered, and considerable yield can be obtained.
(2) fluoroalkylation reagent is fluorinated alohol in the method that the present invention is provided, and such reagent has been realized commercialization, easily obtained Obtain and stable chemical nature, toxicity are low.Meanwhile, the step of the method one can just complete reaction, with Atom economy very high and Step economy, energy-conserving and environment-protective are simple to operate.Realize the direct fluoroalkylation of primary amine compound and prepare fluorine-containing secondary amine class chemical combination Thing.
(3) [the Cp*IrCl of commodity in use2]2As catalyst, part need not be added in course of reaction, system is held Easily realize.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to described reality Apply among a scope.
Embodiment 1
Under nitrogen protection, toward sequentially adding [Cp*IrCl in pressure pipe2]20.006mmol, aniline 0.3mmol, fluoroethanol 0.33mmol, sodium acid carbonate 0.006mmol and toluene 0.5mL, are heated to 100 DEG C and react 24h.After reaction terminates, room is down to Temperature, adds a small amount of water, 15mL ethyl acetate to extract three times, merges organic phase, then saturated common salt water washing, and anhydrous magnesium sulfate is done It is dry, remove solvent under reduced pressure, it is 76% that column chromatography for separation obtains secondary amine yield
Embodiment 2
Under nitrogen protection, toward sequentially adding [Cp*IrCl in pressure pipe2]20.006mmol, aniline 0.3mmol, fluoroethanol 0.33mmol, triethylamine 0.03mmol and toluene 0.5mL, are heated to 100 DEG C and react 24h.After reaction terminates, room temperature is down to, Add a small amount of water, 15mL ethyl acetate to extract three times, merge organic phase, then saturated common salt water washing, anhydrous magnesium sulfate is dried, Remove solvent under reduced pressure, it is 75% that column chromatography for separation obtains secondary amine yield.
Embodiment 3
Under nitrogen protection, toward sequentially adding [Cp*IrCl in pressure pipe2]20.006mmol, aniline 0.3mmol, fluoroethanol 0.33mmol, sodium acid carbonate 0.006mmol and dioxane 0.5mL, are heated to 100 DEG C and react 24h.After reaction terminates, drop To room temperature, add a small amount of water, 15mL ethyl acetate to extract three times, merge organic phase, then saturated common salt water washing, anhydrous slufuric acid Magnesium is dried, and removes solvent under reduced pressure, and it is 75% that column chromatography for separation obtains secondary amine yield.
Embodiment 4
Under nitrogen protection, toward sequentially adding [Cp*IrCl in pressure pipe2]20.006mmol, aniline 0.3mmol, fluoroethanol 0.33mmol, sodium acid carbonate 0.006mmol and tert-pentyl alcohol 0.5mL, are heated to 100 DEG C and react 24h.After reaction terminates, it is down to Room temperature, adds a small amount of water, 15mL ethyl acetate to extract three times, merges organic phase, then saturated common salt water washing, anhydrous magnesium sulfate Dry, remove solvent under reduced pressure, it is 79% that column chromatography for separation obtains secondary amine yield.
Embodiment 5
Under nitrogen protection, toward sequentially adding [Cp*IrCl in pressure pipe2]20.006mmol, n-amylamine 0.3mmol, fluorine second Alcohol 0.33mmol, sodium acid carbonate 0.006mmol and tert-pentyl alcohol 0.5mL, are heated to 100 DEG C and react 24h.After reaction terminates, drop To room temperature, add a small amount of water, 15mL ethyl acetate to extract three times, merge organic phase, then saturated common salt water washing, anhydrous slufuric acid Magnesium is dried, and removes solvent under reduced pressure, and it is 70% that column chromatography for separation obtains secondary amine yield.
Embodiment 6
Under nitrogen protection, toward sequentially adding [Cp*IrCl in pressure pipe2]20.006mmol, 2- phenoxyethylamine 0.3mmol, fluoroethanol 0.33mmol, sodium acid carbonate 0.006mmol and tert-pentyl alcohol 0.5mL, are heated to 100 DEG C and react 24h.Instead After should terminating, room temperature is down to, adds a small amount of water, 15mL ethyl acetate to extract three times, merge organic phase, then saturated common salt washing Wash, anhydrous magnesium sulfate is dried, remove solvent under reduced pressure, it is 81% that column chromatography for separation obtains secondary amine yield.
Embodiment 7
Under nitrogen protection, toward sequentially adding [Cp*IrCl in pressure pipe2]20.006mmol, aniline 0.3mmol, 3,3,3- Three fluoro- 1- propyl alcohol 0.33mmol, sodium acid carbonate 0.006mmol and tert-pentyl alcohol 0.5mL, are heated to 100 DEG C and react 24h.Reaction After end, room temperature is down to, adds a small amount of water, 15mL ethyl acetate to extract three times, merge organic phase, then saturated common salt washing Wash, anhydrous magnesium sulfate is dried, remove solvent under reduced pressure, it is 75% that column chromatography for separation obtains secondary amine yield.
Embodiment 8
Under nitrogen protection, toward sequentially adding [Cp*IrCl in pressure pipe2]20.006mmol, aniline 0.3mmol, 3,3,3- Three fluoro- n-butyl alcohol 0.33mmol, sodium acid carbonate 0.006mmol and tert-pentyl alcohol 0.5mL, are heated to 100 DEG C and react 24h.Reaction After end, room temperature is down to, adds a small amount of water, 15mL ethyl acetate to extract three times, merge organic phase, then saturated common salt washing Wash, anhydrous magnesium sulfate is dried, remove solvent under reduced pressure, it is 83% that column chromatography for separation obtains secondary amine yield.
Embodiment 9
Under nitrogen protection, toward sequentially adding [Cp*IrCl in pressure pipe2]20.006mmol, aniline 0.3mmol, 3,3- bis- Fluoro- 1- propyl alcohol 0.45mmol, sodium acid carbonate 0.006mmol and tert-pentyl alcohol 0.5mL, are heated to 100 DEG C and react 24h.Reaction knot Shu Hou, is down to room temperature, adds a small amount of water, 15mL ethyl acetate to extract three times, merges organic phase, then saturated common salt water washing, Anhydrous magnesium sulfate is dried, and removes solvent under reduced pressure, and it is 45% that column chromatography for separation obtains secondary amine yield.
Embodiment 10
Under nitrogen protection, toward sequentially adding [Cp*IrCl in pressure pipe2]20.006mmol, aniline 0.3mmol, 3,3- bis- Fluoro- 1- propyl alcohol 0.33mmol, sodium acid carbonate 0.006mmol and tert-pentyl alcohol 0.5mL, are heated to 90 DEG C and react 24h.Reaction terminates Afterwards, room temperature is down to, adds a small amount of water, 15mL ethyl acetate to extract three times, merge organic phase, then saturated common salt water washing, nothing Water magnesium sulfate is dried, and removes solvent under reduced pressure, and it is 85% that column chromatography for separation obtains secondary amine yield.

Claims (7)

1. a kind of method for preparing fluorine-containing secondary amine, it is characterised in that comprise the following steps：
The transition metal iridium catalyst of catalytic amount, alkali are mixed and add organic solution, under nitrogen protection, sequentially add primary amine I, Fluorinated alohol II, is heated to 90-100 DEG C of stirring reaction 24h, and after reaction terminates, revolving removes solvent, and column chromatography is contained after purification Fluorine secondary-amine compound III；
Specific reaction equation is as follows：
Substituent R in Formulas I, Formula II, Rf is each independent, and R is selected from aryl, C3~C10Alkyl, C3~C10Alkoxy, Rf choosing It is CH from end2F、CHF2Or CF3Containing fluoroalkyl chain.
2. method according to claim 1, it is characterised in that：Described alkali is sodium acid carbonate or triethylamine.
3. method according to claim 1, it is characterised in that：Described transition metal iridium catalyst is [Cp*IrCl2]2。
4. method according to claim 1, it is characterised in that：Described primary amine is aromatic amine or fatty amine.
5. method according to claim 1, it is characterised in that：Described fluorinated alohol is single fluorine alcohol, difluoro alcohol or Trifluridol.
6. method according to claim 1, it is characterised in that：It is toluene, dioxane or uncle that described organic solvent is Amylalcohol.
7. method according to claim 1, it is characterised in that：Described primary amine is 1 with the mol ratio of fluorinated alohol:1.1 to 1:1.5。
CN201611220037.0A 2016-12-26 2016-12-26 A method of preparing fluorine-containing secondary amine Expired - Fee Related CN106748802B (en)

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CN109206319A (en) * 2018-10-15 2019-01-15 四川大学 A kind of synthetic method of tertiary amine
CN109422654A (en) * 2017-08-21 2019-03-05 南京理工大学 The method of synthetic fatty amine methylated compounds

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CN109422654A (en) * 2017-08-21 2019-03-05 南京理工大学 The method of synthetic fatty amine methylated compounds
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CN109206319A (en) * 2018-10-15 2019-01-15 四川大学 A kind of synthetic method of tertiary amine

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