CN107469858A - A kind of immobilized chiral diamine of pentaerythrite derives thiourea catalyst and preparation method and application - Google Patents
A kind of immobilized chiral diamine of pentaerythrite derives thiourea catalyst and preparation method and application Download PDFInfo
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- C07C335/04—Derivatives of thiourea
- C07C335/16—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C335/20—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups
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Abstract
The invention discloses a kind of immobilized chiral diamine of pentaerythrite to derive thiourea catalyst and its preparation method and application.Its structure such as formula（I）It is shown.The preparation method that a kind of immobilized chiral diamine of pentaerythrite derives thiourea catalyst comprises the following steps：a.（S,S）‑NBoc cyclohexanediamine is in acetonitrile and K2CO3In the presence of elder generation and CH3I react at room temperature, then with Br (CH2)nBr reacts, and intermediate is made（1）；B. intermediate（1）With F3CCO2H reactions prepare intermediate（2）；C. intermediate（2）With 3,5 2（Trifluoromethyl）Isothiocyanates reacts at room temperature, and intermediate is made（3）；D. intermediate（3）Reacted with pentaerythrite in the presence of alkali and phase transfer catalyst, the immobilized chiral diamine of pentaerythrite is made and derives thiourea catalyst formula（I).The immobilized chiral diamine of the pentaerythrite, which derives thiourea catalyst, to be applied in asymmetric Michael addition reaction.It is isolated and purified simply, can iterative cycles utilization. tu1
Description
Technical field
The present invention relates to catalysis organic synthesis field, specifically, is related to the immobilized chiral diamine of pentaerythrite and derives sulphur
Urea catalyst and preparation method and application.
Background technology
Michael addition reactions are that α, the conjugate addition of β unsaturated carbonyl class compounds are formed newly using nucleopilic reagent
One of the important method of carbon-carbon bond, in the reaction that asymmetric C-C keys are formed, serve important function.In recent years, with setting about
The appearance of property catalyst, asymmetric Michael addition reaction have obtained fast development.Research shows, sulphur derived from chiral diamine
Urea catalyst can be very good to be catalyzed asymmetric Michael addition reaction.It can be with substrate by electric body moleculeα,β- unsaturated
The carbonyl or nitro of compound form dihydrogen bond, improve the electrophilic performance by electric body.Thiourea catalyst knot derived from chiral diamine
Tertiary amine moieties in structure, have the function that organic base, and the active hydrogen that can capture Michael addition reactions substrate power supply body is formed
Enol-type structure, the enol-type structure under stereochemical structure and the hydrogen bond control of catalyst, can only from specific direction and substrate by
The unsaturated double-bond reaction of electric body, Michael addition compound products are obtained with good enantioselectivity.But derived from chiral diamine
Thiourea catalyst is expensive, is not easy to separate with product, recovery trouble, therefore, on the premise of its catalytic activity is ensured, by it
It is immobilized on suitable carrier, being the effective way that solves catalyst recovery and recycle.
The present invention is carrier with pentaerythrite, and thiourea catalyst derived from chiral diamines carries out immobilized, it is intended to simplicity
Method solve the problems, such as the recovery of such catalyst.
The content of the invention
It is an object of the invention to provide the immobilized chiral diamine of pentaerythrite to derive thiourea catalyst and preparation method thereof
With application.
The immobilized chiral diamine of pentaerythrite provided by the invention derives thiourea catalyst, structure such as formula（I shown in)：
In formula, n is 3-6 integer.
The present invention also provides the preparation method that the immobilized chiral diamine of the pentaerythrite derives thiourea catalyst, the side
Method comprises the following steps：
a.（S,S）-N- Boc- cyclohexanediamine is in acetonitrile and K2CO3In the presence of elder generation and CH3I react at room temperature, then with Br (CH2)nBr is anti-
Should, intermediate is made（1）；
B. intermediate（1）With F3CCO2H reactions prepare intermediate（2）；
C. intermediate（2）With 3,5- bis-（Trifluoromethyl）Isothiocyanates reacts at room temperature, and intermediate is made（3）；
D. intermediate（3）Reacted with pentaerythrite in the presence of alkali and phase transfer catalyst, the immobilized chirality of pentaerythrite is made
Diamines derives thiourea catalyst formula（I).Its synthetic route is as follows：
In formula, n is 3-6 integer.
In the immobilized chiral diamine of above-mentioned pentaerythrite derives the preparation method of thiourea catalyst, in described step d
Alkali be CsOH, KOH, NaOH；Phase transfer catalyst is n-Bu4NI, n-Bu4NBr, PEG2000；Solvent is DMF, DMSO,
One or more in NMP.
Present invention also offers the immobilized chiral diamine of the pentaerythrite to derive thiourea catalyst in asymmetric Michael
Applied in addition reaction.
, will in above-mentioned application（E)-β- Nitrostyrene is dissolved in toluene with diethyl malonate, in described season
The immobilized chiral diamine of penta tetrol derives under thiourea catalyst effect, reacts at room temperature 48h, filtering, filter cake toluene, dichloromethane
Washing, vacuum drying, reclaim catalyst and recycle.Filtrate decompression is evaporated, and column chromatography purifying, is obtained corresponding Michael and is added
Into product.
In above-mentioned application, using THF as solvent, by 4 hydroxy coumarin and 4- phenyl-α, β- unsaturated butanone is described
The immobilized chiral diamine of pentaerythrite derive under thiourea catalyst effect, react at room temperature 120h, be concentrated under reduced pressure into original volume
1/3rd, a certain amount of ether is added dropwise, separates out catalyst, filtering, filter cake is washed with ether, dichloromethane, is dried in vacuo, and is returned
Receive catalyst and recycle.Filtrate decompression is evaporated, and column chromatography purifying, is obtained（S）- neodicoumarin.
It is described in above-mentioned application（E）-β- Nitrostyrene has following structure：
In formula, R each stands alone as phenyl, substituted-phenyl, naphthyl, substituted naphthyl, aromatic heterocyclic.
The beneficial effects are mainly as follows：The immobilized chiral diamine of the pentaerythrite that is related to derives thiourea catalyst
Synthetic route is simple, high income, can be catalyzed the asymmetric Michael addition reaction of a variety of substrates.Catalyst easily divides with product
From recycling 5 times, catalytic activity is constant.
Embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This：
Embodiment 1
Intermediate（1）Preparation：
In 25mL flasks, 7mLCH is added3CN, 214mg (1mmol)（S,S）-N- Boc- cyclohexanediamine, 331mg
(2.4mmol)K2CO3With 156mg (1.1mmol) CH3I, react at room temperature 36h, then add 238mg (1.1mmol) Isosorbide-5-Nitrae-
Dibromobutane, room temperature continue to react 48h, filtered, and concentration, column chromatography purifying, intermediate are made（1）, yield 93%.
Embodiment 2
Intermediate（2）Preparation：
By 363mg (1mmol) intermediate（1）It is added to the CH of 171mg (1.5mmol) trifluoroacetic acid2Cl2（4mL）Mix molten
In liquid, 1h is stirred at room temperature, adds 30uL Et3N, 0.5h is stirred, evaporated under reduced pressure, column chromatography purifying, obtains intermediate（2）, yield
95%。
Embodiment 3
Intermediate（3）Preparation：
By 263mg（1mmol）Intermediate（2）It is dissolved in 5mLCH2Cl2In, add 165mg (1.2mmol) K2CO3, it is stirred at room temperature,
325mg (1.2mmol) 3,5- bis- is added dropwise（Trifluoromethyl）The CH of isothiocyanates2Cl2（3mL）Solution, react at room temperature 8h, mistake
Filter, concentration, column chromatography purifying（VCH2Cl2：VCH3OH=20:1）, obtain intermediate（3）, yield 98%.IR (CHCl3): 1723cm-1。
Embodiment 4
Catalyst（Formulas I, n=4）Preparation：
By 2.35g (4.4mmol) intermediate（3）It is dissolved in 8mLDMF, adds 136mg (1mmol) pentaerythrite, 660mg
(4.4mmol) CsOH and a small amount of n-Bu4NI, 12h is reacted at room temperature, add 15mLCH2Cl2, use H2O（15mLx5）Washing, do
It is dry, 1/3rd of original volume is concentrated into, ether is added dropwise, separates out precipitation, filtering, successively with ether, CH2Cl2Washing, vacuum are done
It is dry, catalyst is made（Formulas I, n=4）.Yield 81%, [α]D 23 = -50.2˚ (c 0.65, CH2Cl2)。
Embodiment 5
Catalyst（Formulas I, n=6）Preparation：
238mg (1.1mmol) Isosorbide-5-Nitrae-dibromobutane is replaced with 268mg (1.1mmol) 1,6- dibromo-hexanes, other operations are the same as real
A 1-4 is applied, catalyst is made（Formulas I, n=6）.Yield 79%, [α]D 23 = -51.0˚ (c 0.85, CH2Cl2)。
Embodiment 6
Catalyst（Formulas I, n=5）Preparation：
With 253mg (1.1mmol) 1, pentamethylene bromide replaces 238mg (1.1mmol) Isosorbide-5-Nitrae-dibromobutane, and other operations are the same as real
A 1-4 is applied, catalyst is made（Formulas I, n=5）.Yield 81%, [α]D 23 = -49.7˚ (c 0.90, CH2Cl2)。
Embodiment 7
（S）The preparation of -2- [1- phenyl -2- nitro-ethyls] diethyl malonate：
By 149mg (1mmol)（E）-β- nitrostyrolene and 320mg (2mmol) diethyl malonate are added to 5mL toluene
In, add 0.01mmol catalyst（Formulas I, n=4）, 48h, filtering are reacted at room temperature, filter cake is washed 3 times with toluene, is dried, and is returned
Receive catalyst, catalyst recovery yield 97%.Filtrate concentrates, column chromatography purifying（VN-hexane：VEthyl acetate=8:2）, obtained Michael adds
Into product（S）- 2- [1- phenyl -2- nitro-ethyls] diethyl malonate, yield 89%, ee:92%, mp:41-42℃.
Embodiment 8
（S）-2-[1-（4- bromophenyls）- 2- nitro-ethyls] diethyl malonate preparation：
With 228mg (1mmol)（E）-β- nitro-replaces 149mg (1mmol) to bromstyrol（E）-β- nitrostyrolene, use
0.01mmol catalyst（Formulas I, n=6）For catalyst, Michael addition compound products are made with embodiment 7 in other operations（S）-
2-[1-（4- bromophenyls）- 2- nitro-ethyls] diethyl malonate, yield 92%, ee:90%, mp:58-60℃.
Embodiment 9
（S）- 3- (α -2- acetonyl benzyls）- 4 hydroxy coumarin（Neodicoumarin）Preparation：
By 162mg (1mmol) 4 hydroxy coumarin, 160mg (1.1mmol) 4- phenyl-α, β-unsaturated butanone and
The immobilized chiral diamine of 0.02mmol pentaerythrites derives thiourea catalyst（Formulas I, n=5) add in 7mLTHF, room temperature reaction
120h, 1/3rd of original volume is concentrated under reduced pressure into, ether is added dropwise, separate out catalyst, filtering, filter cake ether, dichloromethane
Washing, vacuum drying, reclaim catalyst, catalyst recovery yield 96%.Filtrate decompression is evaporated, and column chromatography purifying, is obtained（S）- Hua Fa
Order.Yield 90%, ee:83%, IR（Nujol mull）：2924,2854,1721,1669, 1632,1516,1412,760 cm-1。
Embodiment 10
Catalyst recycling performance study：
It is catalyzed and is prepared with catalyst (Formulas I, n=4)（S）Exemplified by -2- [1- phenyl -2- nitro-ethyls] diethyl malonate, operation
It is identical with the method for embodiment 7, after catalyst recovery, circulate for the asymmetric Michael addition reaction, the results are shown in Table 1.Knot
Fruit shows that catalyst recycling 5 times, activity does not subtract.
Claims (6)
1. a kind of immobilized chiral diamine of pentaerythrite derives thiourea catalyst, it is characterised in that its structure such as formula（I）It is shown：
tu1
In formula, n is 3-6 integer.
2. a kind of immobilized chiral diamine of pentaerythrite according to claim 1 derives the preparation method of thiourea catalyst,
It is characterized in that comprise the following steps：
a.（S,S）-N- Boc- cyclohexanediamine is in acetonitrile and K2CO3In the presence of, elder generation and CH3I react at room temperature, then with Br (CH2)nBr is anti-
Should, intermediate is made（1）；
B. intermediate（1）With F3CCO2H reactions prepare intermediate（2）；
C. intermediate（2）With 3,5- bis-（Trifluoromethyl）Isothiocyanates reacts at room temperature, and intermediate is made（3）；
D. intermediate（3）Reacted with pentaerythrite in the presence of alkali and phase transfer catalyst, the immobilized chirality of pentaerythrite is made
Diamines derives thiourea catalyst formula（I), its synthetic route is as follows：
tu2
In formula, n is 3-6 integer.
3. preparation method according to claim 2, it is characterised in that the alkali in described step d is CsOH, KOH,
NaOH；Phase transfer catalyst is n-Bu4NI, n-Bu4NBr, PEG2000；Solvent is DMF, the one or more in DMSO, NMP.
4. the immobilized chiral diamine of pentaerythrite according to claim 1 derives thiourea catalyst, can be in asymmetry
Applied in Michael addition reactions.
5. application according to claim 4, it is characterised in that comprise the following steps：
Will（E）-β- Nitrostyrene is dissolved in toluene with diethyl malonate, in the chirality two that described pentaerythrite is immobilized
Amine derives under thiourea catalyst effect, reacts at room temperature 48h, filtering, and filter cake is washed with toluene, dichloromethane, is dried in vacuo, recovery
Catalyst is simultaneously recycled, and filtrate decompression is evaporated, and column chromatography purifying, obtains corresponding Michael addition compound products, using THF as solvent,
4 hydroxy coumarin and 4- phenyl-α, β-unsaturated butanone are derived into thiocarbamide in described pentaerythrite immobilized chiral diamine to urge
Under agent effect, 120h is reacted at room temperature, is concentrated under reduced pressure into 1/3rd of original volume, a certain amount of ether is added dropwise, separate out catalysis
Agent, filtering, filter cake are washed with ether, dichloromethane, are dried in vacuo, and are reclaimed catalyst and are recycled, filtrate decompression is evaporated, post
Chromatographic purifying, obtain（S）- neodicoumarin.
6. application according to claim 5, it is characterised in that described（E)-β- Nitrostyrene has following knot
Structure：
tu3
In formula, R each stands alone as phenyl, substituted-phenyl, naphthyl, substituted naphthyl, aromatic heterocyclic.
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| CN109046449A (en) * | 2018-09-28 | 2018-12-21 | 石家庄学院 | A kind of tertiary amine-Thiourea bifunctional chiral catalyst and the preparation method and application thereof |
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| CN109046449A (en) * | 2018-09-28 | 2018-12-21 | 石家庄学院 | A kind of tertiary amine-Thiourea bifunctional chiral catalyst and the preparation method and application thereof |
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