CN106513045A - (R)-1(2-(naphthyl) ethyl) thiourea unilateral modified Fe-Anderson type heteropolyacid catalyst, preparing method and application of (R)-1(2-(naphthyl) ethyl) thiourea unilateral modified Fe-Anderson type heteropolyacid catalyst - Google Patents
(R)-1(2-(naphthyl) ethyl) thiourea unilateral modified Fe-Anderson type heteropolyacid catalyst, preparing method and application of (R)-1(2-(naphthyl) ethyl) thiourea unilateral modified Fe-Anderson type heteropolyacid catalyst Download PDFInfo
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Abstract
The invention discloses an (R)-1(2-(naphthyl) ethyl) thiourea unilateral modified Fe-Anderson type heteropolyacid catalyst, a preparing method and application of the (R)-1(2-(naphthyl) ethyl) thiourea unilateral modified Fe-Anderson type heteropolyacid catalyst. The method comprises the steps that firstly, ammonium molybdate and ferric sulfate are subjected to the reaction to generate Fe-Anderson type heteropolyacid; then the Fe-Anderson type heteropolyacid is subjected to the reaction under a backflow condition, and amidogen unilateral modified Fe-Anderson type polyoxometallate is obtained; (R)-1-(2-(naphthyl) ethyl) isothiocyanate is synthesized; and finally, the polyoxometallate is utilized for being subjected to the reaction with the (R)-1-(2-(naphthyl) ethyl) isothiocyanate, and a target product is obtained. The preparing reaction conditions are moderate, environment-friendliness is achieved, the catalyst is used for the oxidation coupling reaction of arylmethyl amine compounds, and the catalyst is environment-friendly, efficient and easy to recycle.
Description
Technical field
The present invention relates to catalysis technical field, especially asymmetric selective catalysis field, specifically one kind (R) -1-
The Fe-Anderson type heteropolyacid catalysts of the unilateral modification of (2- (naphthyl) ethyl) thiourea, preparation method and applications.
Background technology
Polyacid is the inorganic cluster compound formed by some early transition metal elements and oxygen atom.Its classes of compounds is various,
Complex structure is various, and it has nano level molecular dimension, possesses colourful light, magnetic, electric and peculiar catalysis and medicine
Thing activity etc..And carry out organic decoration to polyacid and extensive and deep grinding can have been obtained in the last few years with its property of Effective Regulation
Study carefully.
To the sixties in last century, the research of polyacid also rests on laboratory stage, the determination of polyacid basic structure mostly
Theoretical research fails to find application in real life and its development is more slow with relevant rudimentary.1972, Japan realized
Catalyzed by Silicotungstic Acid propylene hydration reaction prepares the industrial mass production of isopropanol and succeeds, and with phosphomolybdic acid is again later
Catalyst isobutene hydration reaction generates the tert-butyl alcohol, gives birth to by the reaction of catalyst tetrahydrofuran ring opening polymerization of phosphotungstic acid
Into polybutadiene alcohol ether, with phosphomolybdic acid as catalyst methylacrolein gas phase oxidation synthesizing methyl acrylic acid etc., this
Show that polyacid compound can be used for commercial production as new catalyst, be that the development of Chemistry of Polyacids is filled with new vitality.
Polyacid has many advantages, such as that as catalyst such as activity is high, and selectivity is good, and corrosiveness is little, and reaction condition is gentle etc..Grind from this
Research of the person of studying carefully to heteropoly acid in catalytic field generates great interest, has many document reports heteropoly acid in organic reaction
The achievement in research of middle catalytic performance.Organometallic group or organic group is introduced in polyacid, realizes organic ligand to polyacid cluster
The replacement of middle peripheral oxygen atom, extends the structure of polyacid, and this polyacid is organic with the polyacid that organic compound covalently connects derivative
Thing, the not only advantage comprising organic moiety easy-regulating structure and electronic property, also comprising inorganic polyacid cluster high stability, good
, while two parts can be brought to combine the cooperative effect for producing, there is new property in the characteristics such as electron acceptability.And the polyacid has
Machine derivant can be further reacted as building unit, more complicated more high-dimensional with excellent come composite structure by rear modification
The novel organic-inorganic hybrid material of good characteristic.So by the modification and expansion to polyacid structure, the surface to polyacid is realized
Property is adjusted and improves, and gained novel organic-inorganic hybrid body is had in the fields such as material, catalysis and pharmaceutical chemistry
Bigger using value.So far substantial amounts of polyacid organic metal or organic derivative have been synthesized, and it is organic that polyacid has been developed
This new Chemistry of Polyacids field of derivatives chemical.However, the new material combined with polyacid by existing chiral organic micromolecule,
Catalytic mechanism can't further be probed into, it is impossible to explain the synergism of chiral organic micromolecule and polyacid, and poor repeatability, be produced
Rate is not high, is not easy to reclaim.
The content of the invention
For above-mentioned technical problem of the prior art, the invention provides one kind (R) -1- (2- (naphthyl) ethyl) thiourea
The Fe-Anderson type heteropolyacid catalysts of unilateral modification, preparation method and applications.The preparation method yield of the present invention is high,
Can carry out in the aqueous solution of acid medium, catalyst can be used for the autoxidation coupling reaction of aromatic aminomethane class compound, solve
Existing chiral organic micromolecule catalyst activity is relatively low, consumption is high and is not easily recycled and the technical problem such as utilizes.
Mentality of designing of the present invention from organic micromolecule catalyst, innovatively proposes using concerted catalysis strategy,
Using the chiral organic micromolecule with potential catalysis activity as precursor, by methods such as organic decorations, dexterously make organic
Small molecule is combined with the vacant polyanionic of peracidity, is constructed the thinking of chiral polyacid material, and is being realized the same of this thinking
When, the polyacid of organic decoration not only remains the original structure of polyacid, and has expanded the research field of polyacid so as to urging
There is in terms of change, medicine and functional material potential using value.To expect to realize high catalysis activity and high enantioselectivity
While catalysis, the problems such as expensive catalyst can also being solved and recycled and reused.
The present invention provides the Fe-Anderson type heteropoly acids of the unilateral modification of one kind (R) -1- (2- (naphthyl) ethyl) thiourea and urges
The preparation method of agent, comprises the following steps that：
1) by ammonium molybdate, the reaction under conditions of pH value is for 2～4 generates Fe-Anderson type heteropoly acid parents with iron sulfate
(NH4)3(H2O)6[FeMo6O18(OH)6]·25H2O；
2) Fe-Anderson types heteropoly acid parent (NH4)3(H2O)6[FeMo6O18(OH)6]·25H2O and trihydroxy methyl ammonia
After methylmethane back flow reaction, then the Fe-Anderson types for obtaining the unilateral modification of amino with tetrabutyl ammonium bromide TBAB room temperature reaction
Polyoxometallate；
3) (R) -1- (2- (naphthyl) ethyl) isothiocyanate with (R)-(+) -1- (2- naphthyls) ethamine as Material synthesis；
4) by step 2) the Fe-Anderson types polyoxometallate of the unilateral modification of the amino that obtains and step 3) obtain
(R) reaction of -1- (2- (naphthyl) ethyl) isothiocyanate obtains the Fe- of the unilateral modification of (R) -1- (2- (naphthyl) ethyl) thiourea
Anderson type heteropolyacid catalysts.
In the present invention, step 1) in, the mol ratio of iron sulfate and ammonium molybdate is 1:1～1:2, reaction temperature be 80 DEG C～
100 DEG C, the response time is 30min～1h.
In the present invention, step 1) in, with hydrochloric acid or other acid for adjusting pH.
In the present invention, step 2) in, heteropoly acid parent (NH4)3(H2O)6[FeMo6O18(OH)6]·25H2O and trihydroxy methyl
The mol ratio of aminomethane is 1:2～1:5；Polyacid parent (NH4)3(H2O)6[FeMo6O18(OH)6]·25H2O and tetrabutyl bromine
The mol ratio for changing ammonium TBAB is 1:3～1:5.
In the present invention, step 4) in, the Fe-Anderson types polyoxometallate and (R) -1- (2- of the unilateral modification of amino
(naphthyl) ethyl) isothiocyanate mol ratio be 1:3～1:5；Reaction temperature is 45～55 DEG C, and the response time is 2～3 days,
Aprotic polar solvent is adopted for solvent.
The present invention also provides the unilateral modification of (R) -1- (2- (naphthyl) ethyl) thiourea that a kind of above-mentioned preparation method is obtained
Fe-Anderson type heteropolyacid catalysts.
The Fe-Anderson types that the present invention also provides a kind of unilateral modification of above-mentioned (R) -1- (2- (naphthyl) ethyl) thiourea are miscellaneous
Many acid catalysts generate the application in imines in the autoxidation coupling reaction of aromatic aminomethane class compound.Autoxidation coupling reaction
When, with aromatic aminomethane class compound as raw material, under oxygen effect, the temperature, the condition with acetonitrile as solvent at 60 DEG C～100 DEG C
Under, the Fe-Anderson types heteropolyacid catalyst reaction of the unilateral modification of (R) -1- (2- (naphthyl) ethyl) thiourea is added, Asia is obtained
Amine.
In the present invention, (R) throwing of -1- (2- (naphthyl) ethyl) thiourea modified Fe-Anderson type heteropolyacid catalysts
0.5mol%～5mol% of the dosage for aromatic aminomethane class compound.
In the present invention, after autoxidation coupling reaction terminates, organic solvent (ether, ethanol, methanol is added in phase system
Deng) after, polyacid is separated out, and is filtered, vacuum drying, the autoxidation that the polyacid of recovery is used further to aromatic aminomethane class compound is coupled anti-
Should.
Compared to the prior art, the beneficial effects of the present invention is：The present invention is with high symmetric heteropoly acid parent
It is unilateral to introduce organic molecule so that inorganic heteropoly acid parent becomes an entirety with the organic moiety of modification, so as to produce association
Same-action obtains some novel properties and improves activity of catalyst etc..The catalyst has that reaction condition is gentle, environment
The advantages of friendly, efficient, high corresponding selection and recoverable, and centered on common base metal Fe, with more pushing away
The value for extensively utilizing, is applicable to industrialized production.
Description of the drawings
Fig. 1 is the synthetic route chart of the present invention.
Fig. 2 is parent (NH4)3(H2O)6[FeMo6O18(OH)6]·25H2The infrared spectrum of O.
Fig. 3 is the nuclear magnetic spectrogram of (R) -1- (2- (naphthyl) ethyl) isothiocyanate.
Fig. 4 is the infrared spectrum of unilateral amido modified Fe-Anderson type polyoxometallates.
Fig. 5 is the nuclear-magnetism spectrum of the thiourea modified Fe-Anderson type heteropolyacid catalysts of (R) -1- (2- (naphthyl) ethyl)
Figure.
Specific embodiment
Below using embodiment describing embodiments of the present invention in detail, whereby to the present invention how application technology means
To solve technical problem, and reach technique effect realize that process can fully understand and implement according to this.
The synthetic route of the present invention is as shown in Figure 1.
Embodiment 1
Fe-Anderson type heteropoly acid parent (NH4)3(H2O)6[FeMo6O18(OH)6]·25H2The preparation of O
Take 15.9g (12.9mmol) ammonium molybdate to be added in 250ml deionized waters, be sufficiently stirred for obtaining transparency liquid, afterwards
The PH of system is transferred to 2～3 by Deca acid.Boiling is heated to, 3.2g (9.3mmol) iron sulfate solid is slowly added to, is stirred 1h, have
A small amount of solid is produced, and stops stirring, while hot sucking filtration, obtains brown liquid, is placed at room temperature, is stood 48h, recrystallization one
It is secondary, obtain white solid (NH4)3(H2O)6[FeMo6O18(OH)6]·25H2O, yield are 80.3%.
Parent (NH4)3(H2O)6[FeMo6O18(OH)6]·25H2The infrared spectrum of O is as shown in Figure 2.
Embodiment 2
(R) preparation of -1- (2- (naphthyl) ethyl) isothiocyanate
(R)-(+) -1- (2- naphthyls) ethamine (0.8562g, 5mmol) is added in dry reaction vessel, uses 20mL second
Alcohol dissolves, and is subsequently respectively added slowly to plus CS2(0.1142g, 15mmol) and triethylamine (0.506mg, 5mmol), stirs in room temperature
Mix after reacting 1h, subsequently the addition Bis(tert-butoxycarbonyl)oxide (Boc under the conditions of 0 DEG C2O) (1.091mg, 5mmol) and 4- diformazan ammonia
Yl pyridines (DMAP) (18mg, 0.15mmol), after reaction 2h is stirred at room temperature (there is gas to produce in the process of stirring, it should be noted that
Deflate and reduce pressure), 0.8448g (R) -1- (2- (naphthyl) ethyl) isothiocyanate can be obtained.Yield is 79.6%.
(R) the nuclear magnetic spectrogram data of -1- (2- (naphthyl) ethyl) isothiocyanate are as shown in Figure 3.
1H NMR(501MHz,CDCl3) δ 7.94 7.77 (m, 4H), 7.50 (ddd, J=10.0,7.1,1.8Hz, 3H),
5.12 (d, J=6.8Hz, 1H), 1.79 (d, J=6.8Hz, 3H).
Embodiment 3
The preparation of unilateral amido modified Fe-Anderson type polyoxometallates
Take 1.5g (1mmol) parent (NH4)3(H2O)6[FeMo6O18(OH)6]·25H2O is dissolved with 10ml deionized waters,
After stirring obtains pale yellow solution, 0.2g (1.9mmol) trishydroxymethylaminomethane is slowly added to, afterwards above-mentioned reactant liquor is added
Enter water heating kettle, be heated to 140 DEG C in water heating kettle, after reaction carries out 24h, by 0.9g (3.0mmol) TBAB under the conditions of 85 DEG C
In adding reaction system, a large amount of slightly yellow precipitations i.e. crude product is instantly available, sucking filtration obtains light yellow liquid, and placement is tied
Crystalline substance, i.e. Fe-Anderson types polyacid [TBA]3{[NH2C(CH2O)3]FeMo6O18(OH)3}。
The infrared spectrum of unilateral amido modified Fe-Anderson type polyoxometallates is as shown in Figure 4.
Embodiment 4
(R) preparation of -1- (2- (naphthyl) ethyl) thiourea modified Fe-Anderson type heteropolyacid catalysts
By organic one side amido modified [TBA]3{[NH2C(CH2O)3]FeMo6O18(OH)35.1g (0.3mmol) is with 5mL
After DMF is dissolved under the conditions of 50 DEG C, (R) -1- (2- (naphthyl) ethyl) isothiocyanate 0.2g (1.4mmol) is added, maintain 50
Under DEG C stirring condition, 48h is reacted, pale yellow crystals in ether atmosphere, are obtained, that is, obtain (R) -1- (2- (naphthyl) ethyl) thiourea
The Fe-Anderson type heteropolyacid catalysts of modification.
(R) the nuclear magnetic spectrogram data of -1- (2- (naphthyl) ethyl) thiourea modified Fe-Anderson type heteropolyacid catalysts
As shown in Figure 5.
1H NMR (501MHz, DMSO) δ 7.90 (s, 2H), 7.22 (d, J=52.0Hz, 5H), 2.99 (d, J=
136.8Hz, 23H), 1.52 (s, 24H), 1.23 (d, J=43.5Hz, 24H), 0.89 (s, 36H).
Application Example
(R) -1- (2- (naphthyl) ethyl) the thiourea modified many acid catalysiss aromatic aminomethane class compounds of Fe-Anderson types from
Body oxidative coupling reaction
The Fe- in clean reaction tube adding 0.086g (0.05mmol) (R) -1- (2- (naphthyl) ethyl) thiourea modified
The many acid catalysts of Anderson types and 0.53g (5mmol) aromatic aminomethane class compound, add 6ml acetonitriles as solvent, finally exist
Add an oxygen ball on reaction tube, react 24h, take 4ml ethanol and add reaction system, centrifugation to make catalyst sedimentation, add 2ml
Ethanol separating catalyst, filtration again, obtains catalyst, is vacuum dried.Jing after extraction, column chromatography for separation obtains Asia to reaction system
Amines, obtain product 0.90g, and yield is 91%.In order to investigate the universality of reaction substrate, we have expanded a series of
Substrate, the product and yield of catalysis the results are shown in Table 1.
It is coupled with the autoxidation of benzylamine and does template reaction, is reclaimed the catalyst for obtaining and be directly used in next reaction (benzyl
The autoxidation coupling reaction of amine).What catalyst recycling was resulting the results are shown in Table 2.
The autoxidation coupling reaction experimental result of many acid catalysiss aromatic aminomethane class compounds of table 1Fe-Anderson types
The experimental result that 2 catalyst of table is recycled
All above-mentioned this intellectual properties of primarily enforcement, setting limit this new product of enforcement of other forms
And/or new method.Those skilled in the art will be using this important information, and the above modification, to realize similar execution feelings
Condition.But, all modifications or transformation belong to the right of reservation based on new product of the present invention.
The above, is only presently preferred embodiments of the present invention, is not the restriction for making other forms to the present invention, is appointed
What those skilled in the art possibly also with the disclosure above technology contents changed or be modified as equivalent variations etc.
Effect embodiment.But it is every without departing from technical solution of the present invention content, according to the technical spirit of the present invention to above example institute
Any simple modification, equivalent variations and the remodeling made, still falls within the protection domain of technical solution of the present invention.
Claims (9)
1. the preparation side of the Fe-Anderson type heteropolyacid catalysts of the unilateral modification of one kind (R) -1- (2- (naphthyl) ethyl) thiourea
Method, it is characterised in that comprise the following steps that：
1) by ammonium molybdate, the reaction under conditions of pH value is for 2～4 generates Fe-Anderson type heteropoly acid parents with iron sulfate
(NH4)3(H2O)6[FeMo6O18(OH)6]·25H2O；
2) Fe-Anderson types heteropoly acid parent (NH4)3(H2O)6[FeMo6O18(OH)6]·25H2O and trihydroxy methyl amino first
It is after alkane back flow reaction then how golden with the Fe-Anderson types that tetrabutyl ammonium bromide TBAB room temperature reaction obtains the unilateral modification of amino
Category oxygen hydrochlorate；
3) (R) -1- (2- (naphthyl) ethyl) isothiocyanate with (R)-(+) -1- (2- naphthyls) ethamine as Material synthesis；
4) by step 2) the Fe-Anderson types polyoxometallate of the unilateral modification of the amino that obtains and step 3) obtain (R)-
The reaction of 1- (2- (naphthyl) ethyl) isothiocyanate obtains the Fe- of the unilateral modification of (R) -1- (2- (naphthyl) ethyl) thiourea
Anderson type heteropolyacid catalysts.
2. preparation method as claimed in claim 1, it is characterised in that：Step 1) in, the mol ratio of iron sulfate and ammonium molybdate is
1:1～1:2, reaction temperature is 80 DEG C～100 DEG C, and the response time is 30min～1h.
3. preparation method as claimed in claim 1, it is characterised in that：Step 1) in, use acid for adjusting pH.
4. preparation method as claimed in claim 1, it is characterised in that step 2) in, Fe-Anderson type heteropoly acid parents
(NH4)3(H2O)6[FeMo6O18(OH)6]·25H2O is 1 with the mol ratio of trishydroxymethylaminomethane:2～1:5；Fe-
Anderson type heteropoly acid parent (NH4)3(H2O)6[FeMo6O18(OH)6]·25H2The mol ratio of O and TBAB is 1:3～1:5.
5. preparation method as claimed in claim 1, it is characterised in that step 4) in, the Fe-Anderson of the unilateral modification of amino
The mol ratio of type polyoxometallate and (R) -1- (2- (naphthyl) ethyl) isothiocyanate is 1:3～1:5；Reaction temperature is
45-55 DEG C, the response time is 2～3 days, adopts aprotic polar solvent for solvent.
6. repair (R) -1- (2- (naphthyl) ethyl) the thiourea one side that a kind of preparation method as described in one of claim 1-5 is obtained
The Fe-Anderson type heteropolyacid catalysts of decorations.
7. a kind of Fe-Anderson types of the unilateral modification of (R) -1- (2- (naphthyl) ethyl) thiourea as claimed in claim 6 are miscellaneous
Many acid catalysts generate the application in imines in aromatic aminomethane class compound autoxidation coupling reaction.
8. it is as claimed in claim 7 to apply, it is characterised in that during autoxidation coupling reaction, with aromatic aminomethane class compound to be
Raw material, oxygen effect under, the temperature at 60 DEG C～100 DEG C, with acetonitrile as solvent under conditions of, add (R) -1- (2- (naphthalenes
Base) ethyl) the unilateral Fe-Anderson types heteropolyacid catalyst reaction modified of thiourea, obtain imines.
9. it is as claimed in claim 8 to apply, it is characterised in that (R) Fe- of the unilateral modification of -1- (2- (naphthyl) ethyl) thiourea
0.5mol%～5mol% of the dosage of Anderson type heteropolyacid catalysts for aromatic aminomethane class compound.
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| CN110483246A (en) * | 2018-05-15 | 2019-11-22 | 中国石油天然气股份有限公司 | A kind of β-Anderson type heteropolymolybdate organic derivative of unilateral modification |
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