CN106749291A - A kind of method that alkali ionic liquid catalysis prepares pyrans simultaneously [2,3 c] pyrazole derivatives - Google Patents
A kind of method that alkali ionic liquid catalysis prepares pyrans simultaneously [2,3 c] pyrazole derivatives Download PDFInfo
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- CN106749291A CN106749291A CN201611046412.4A CN201611046412A CN106749291A CN 106749291 A CN106749291 A CN 106749291A CN 201611046412 A CN201611046412 A CN 201611046412A CN 106749291 A CN106749291 A CN 106749291A
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- ionic liquid
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- pyrazole derivatives
- pyrans simultaneously
- aromatic aldehyde
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- 150000003217 pyrazoles Chemical class 0.000 title claims abstract description 62
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 57
- 239000003513 alkali Substances 0.000 title claims abstract description 39
- 150000004880 oxines Chemical class 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 claims abstract description 32
- GKKZMYDNDDMXSE-UHFFFAOYSA-N Ethyl 3-oxo-3-phenylpropanoate Chemical compound CCOC(=O)CC(=O)C1=CC=CC=C1 GKKZMYDNDDMXSE-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000967 suction filtration Methods 0.000 claims abstract description 17
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000003934 aromatic aldehydes Chemical class 0.000 claims abstract description 14
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 17
- 239000000706 filtrate Substances 0.000 claims description 15
- 238000001556 precipitation Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 14
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 11
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 claims description 9
- 229940067157 phenylhydrazine Drugs 0.000 claims description 9
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 7
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 claims description 6
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 6
- CMWKITSNTDAEDT-UHFFFAOYSA-N 2-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC=C1C=O CMWKITSNTDAEDT-UHFFFAOYSA-N 0.000 claims description 4
- SUISZCALMBHJQX-UHFFFAOYSA-N 3-bromobenzaldehyde Chemical compound BrC1=CC=CC(C=O)=C1 SUISZCALMBHJQX-UHFFFAOYSA-N 0.000 claims description 4
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 claims description 4
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 claims description 3
- ZETIVVHRRQLWFW-UHFFFAOYSA-N 3-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC(C=O)=C1 ZETIVVHRRQLWFW-UHFFFAOYSA-N 0.000 claims description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims 2
- 150000001299 aldehydes Chemical class 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000010992 reflux Methods 0.000 abstract description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 26
- ZENKESXKWBIZCV-UHFFFAOYSA-N 2,2,4,4-tetrafluoro-1,3-benzodioxin-6-amine Chemical group O1C(F)(F)OC(F)(F)C2=CC(N)=CC=C21 ZENKESXKWBIZCV-UHFFFAOYSA-N 0.000 description 22
- 239000002994 raw material Substances 0.000 description 17
- 206010011703 Cyanosis Diseases 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 13
- 238000004587 chromatography analysis Methods 0.000 description 13
- 238000001514 detection method Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 239000003643 water by type Substances 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- -1 nitrogen-containing heterocycle compound Chemical class 0.000 description 5
- 150000004031 phenylhydrazines Chemical class 0.000 description 5
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 4
- 150000003935 benzaldehydes Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UJHSIDUUJPTLDY-UHFFFAOYSA-N (2-nitrophenyl)-phenylmethanone Chemical compound [O-][N+](=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 UJHSIDUUJPTLDY-UHFFFAOYSA-N 0.000 description 2
- ZYMCBJWUWHHVRX-UHFFFAOYSA-N (4-nitrophenyl)-phenylmethanone Chemical class C1=CC([N+](=O)[O-])=CC=C1C(=O)C1=CC=CC=C1 ZYMCBJWUWHHVRX-UHFFFAOYSA-N 0.000 description 2
- BXOAIZOIDUQOFA-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;hydroxide Chemical compound [OH-].CCCC[N+]=1C=CN(C)C=1 BXOAIZOIDUQOFA-UHFFFAOYSA-M 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical group C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 125000006275 3-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C([H])C(*)=C1[H] 0.000 description 2
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical class BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 241000894007 species Species 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- SQPFPKSOPRMSDP-UHFFFAOYSA-N C(CCC)N1CN(C=C1)C.O Chemical class C(CCC)N1CN(C=C1)C.O SQPFPKSOPRMSDP-UHFFFAOYSA-N 0.000 description 1
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 description 1
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical class CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 241000565675 Oncomelania Species 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 101150113535 chek1 gene Proteins 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002532 enzyme inhibitor Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- KQWWVLVLVYYYDT-UHFFFAOYSA-N ethyl 3-oxohexanoate Chemical compound CCCC(=O)CC(=O)OCC KQWWVLVLVYYYDT-UHFFFAOYSA-N 0.000 description 1
- SYFFHRPDTQNMQB-UHFFFAOYSA-N ethyl 3-oxopropanoate Chemical compound CCOC(=O)CC=O SYFFHRPDTQNMQB-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/04—Ortho-condensed systems
- C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
- C07D491/052—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being six-membered
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of method that alkali ionic liquid catalysis prepares pyrans simultaneously [2,3 c] pyrazole derivatives, belongs to technical field of organic synthesis.The mol ratio of aromatic aldehyde, ethyl acetoacetate or ethyl benzoylacetate, malononitrile and hydrazine is 1 in preparation reaction：1：1~1.2：1, the mole of alkaline ionic liquid catalyst is the 4~6% of aromatic aldehyde used, the volume of the ethanol water of reaction dissolvent 90% in terms of milliliter be by mM in terms of 3~5 times of aromatic aldehyde mole, reflux time is 12~40min, reaction is cooled to room temperature after terminating, suction filtration, pyrans simultaneously [2,3 c] pyrazole derivatives are obtained after filter residue vacuum drying.The present invention is compared with the preparation method that other ionic liquids make catalyst, with catalyst preparation low cost, can be recycled often, be readily biodegradable, purification of products process is simple, whole preparation process economical and efficient and the features such as be easy to industrialization to mass produce.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of alkali ionic liquid catalysis prepare pyrans simultaneously [2,
3-c] pyrazole derivatives method.
Background technology
Pyrans simultaneously [2,3-c] pyrazole derivatives be nitrogen-containing heterocycle compound an important component, be also constitute day
The important feature unit of right product, with important bioactivity and pharmacological activity, such as has antibacterial, desinsection, anticancer, anti-inflammatory
Effect.Additionally, such compound also has kills oncomelania activity, it is also potential human body Chk1 enzyme inhibitors.This kind of compound is passed
The preparation method of system is, by the use of organic bases such as piperidines, triethylamine, N-methylmorpholines as catalyst, to flow back to come in organic solvent
It is prepared.But the shortcomings of there is reaction time long, low yield, environmental pollution, catalyst and can not recycle in this method.This
Outward, the reaction is also promoted using technologies such as microwave, ultrasound, grindings.But these methods are still suffered from, and the reaction time is long, it is special to need
The shortcomings of equipment, complex operation.As people are to the pay attention to day by day of environment, a kind of pyrans simultaneously [2,3-c] pyrazole derivatives are developed
Efficient, green preparation method turn into many organic synthesis worker questions of common concern.
Functionalized ion liquid, bronsted alkali ionic liquid particularly more stable to water and air, due to it
With species it is many, active site density is high, uniform intensity distribution, active sites are not easily runed off the features such as and be applied to pyrans simultaneously [2,
3-c] pyrazole derivatives preparation reaction in.Such as Guo Hong clouds etc. are in alkali ionic liquid hydroxide 1- butyl -3- methylimidazoles
Under [Bmim] OH catalytic action, being prepared for one by aromatic aldehyde, malononitrile, ethyl benzoylacetate and hydrazine or phenylhydrazine " one kettle way " is
Row Isosorbide-5-Nitrae-dihydropyran simultaneously [2,3-c] pyrazole derivatives.The method have that reaction condition is gentle, the reaction time is short, yield is high and
Environmentally friendly the features such as, (alkali ionic liquid catalysis " one kettle way " synthesized Isosorbide-5-Nitrae-dihydropyran simultaneously [2,3-c] pyrazoles [J], has
Chemical machine, 2012,32：127~132).But because the catalysis activity of [Bmim] OH is relatively low, cause usage amount larger, in addition, by
Can not participate in recycling in reaction dissolvent ethanol so that the whole process economy for preparing pyrans simultaneously [2,3-c] pyrazole derivatives
Benefit is relatively low.In order to overcome disadvantages mentioned above, Luo Jun etc. to make catalyst with triethylamine functional polyethylene glycol gemini ionic liquid,
Four component one pot reactions in water phase with aromatic aldehyde, malononitrile, ethyl acetoacetate, hydrazine hydrate or phenylhydrazine as raw material, prepare
16 kinds of pyrans containing different substituents simultaneously [2,3-c] pyrazole derivatives, the mole dosage of wherein catalyst is only former reaction
Expect the 5mol% of aromatic aldehyde consumption.The method has catalyst amount few, simple to operate, (triethylamine the advantages of product is easily separated
Functional polyethylene glycol gemini ionic liquid catalyzes and synthesizes pyrans simultaneously [2,3-c] pyrazoles [J], organic chemistry, 2013,33：2016
~2021).
It is above-mentioned to make catalyst in alkali ionic liquid, prepare pyrans simultaneously under the reaction condition of ethanol as solvent or water as solvent
Because the structural matrix of catalyst is difficult to biodegradable imidazole ring during [2,3-c] pyrazole derivatives, price is prepared
Higher, this is disagreed with the policy of green chemical industry.Meanwhile, the purification process of product is more complicated, it is necessary to using washing, weight
The modes such as crystallization, whole operation process is more complicated.Further, since the catalyst containing glyoxaline structure and product pyrans simultaneously [2,
3-c] pyrazole derivatives intersolubility it is larger, cause the loss amount of catalyst larger, catalytic efficiency change less in the case of,
It is relatively low that catalyst can be recycled number of times, ionic-liquid catalyst prepare it is expensive in the case of, be unfavorable in industrialization
By large-scale use in production.
The content of the invention
The alkali ionic liquid containing glyoxaline structure is utilized to be catalyzed preparation in the prior art it is an object of the invention to overcome
Pyrans simultaneously catalyst present in [2,3-c] pyrazole derivatives process easily biological-degradable, preparation cost be not high, recycle in flow
Vector is larger, it is less that number of times can be recycled and purification of products process complicated, the low shortcoming of reaction raw materials utilization rate, and provides
It is a kind of that catalyst is made with alkali ionic liquid biodegradable, that recycling number of times is more, it is solvent bar with ethanol water
The method that catalysis prepares pyrans simultaneously [2,3-c] pyrazole derivatives under part.
The structural formula of alkaline ionic liquid catalyst used in the present invention is：
The method that a kind of alkali ionic liquid catalysis provided by the present invention prepares pyrans simultaneously [2,3-c] pyrazole derivatives,
Its chemical equation is：
Wherein：
Aromatic aldehyde (I), ethyl acetoacetate or ethyl benzoylacetate (II), malononitrile (III) and hydrazine in above-mentioned reaction
(IV) mol ratio is 1：1：1~1.2：1, the mole of alkaline ionic liquid catalyst is the 4~6% of aromatic aldehyde used, with
The volume of the ethanol water of reaction dissolvent 90% of milliliter meter be by mM in terms of 3~5 times of aromatic aldehyde mole, reaction
Pressure is an atmospheric pressure, and reflux time is 12~40min.Reaction is cooled to room temperature after terminating, and pulverizes the solid of precipitation,
Stand, suction filtration, pyrans simultaneously [2,3-c] pyrazole derivatives (V) are obtained after filter residue vacuum drying.The alkali ion liquid contained in filtrate
Body and the complete raw material of a small amount of unreacted, can reuse without treatment.
Aromatic aldehyde used by the present invention is benzaldehyde, 4-chloro-benzaldehyde, p-tolyl aldehyde, paranitrobenzaldehyde, to bromine
Appointing in benzaldehyde, parahydroxyben-zaldehyde, P-methoxybenzal-dehyde, 3-bromobenzaldehyde, m-nitrobenzaldehyde, o-nitrobenzaldehyde
It is a kind of.
Hydrazine used by the present invention is any one in hydrazine hydrate and phenylhydrazine.
The preparation method of alkaline ionic liquid catalyst used in the present invention, is shown in pertinent literature (Biodiesel
production by transesterification catalyzed by an efficient choline ionic
Liquid catalyst, Applied Energy, 108 (2013), 333-339).
The present invention compared with the preparation method that other alkali ionic liquids make catalyst, with advantages below：
1st, catalyst loss amount in recycling is less, number of times can be recycled more；
2nd, the catalysis activity of catalyst is stronger, and usage amount is less, and the species of catalytic reaction thing is more；
3rd, the preparation cost of catalyst is than relatively low, preparation process is simple；
4th, reaction raw materials utilization rate is high, and loss of product amount is few；
5th, purification of products process is simple, energy-saving and emission-reduction；
6th, whole course of reaction green economy, is easy to industrialization to mass produce.
Specific embodiment
Substantive features of the invention and remarkable result can be emerged from from following embodiments, but they are not to this
Invention is imposed any restrictions, and those skilled in the art's content of the invention makes some nonessential modifications and adaptations,
Belong to protection scope of the present invention.Below by specific embodiment, the present invention is further illustrated, wherein in embodiment
The test of product is characterized and uses German Bruker companies, the NMR of model AVANCE-II 500MHz；
The fusing point of product is determined using capillary tube method.
Embodiment 1
By 1mmol benzaldehydes, 1mmol ethyl benzoylacetates, 1.2mmol malononitrile, the hydrazine hydrates of 1mmol 80% and
0.05mmol alkali ionic liquids be added to fill the ethanol waters of 3ml 90% (volume ratio) with stirrer and condenser pipe
25ml single port bottles in.Lower back flow reaction 28min is stirred vigorously, TLC (thin plate chromatography) detections, raw material point disappears, and is cooled to room
Temperature, pulverizes the solid of precipitation, stands, and suction filtration obtains 6- amino -3,4- diphenyl -5- cyano group-Isosorbide-5-Nitraes-after filter residue is vacuum dried
Dihydropyran simultaneously [2,3-c] pyrazoles, yield is 84%.Be directly added into filtrate benzaldehyde, ethyl benzoylacetate, malononitrile and
80% hydrazine hydrate is reused.
6- amino -3,4- diphenyl -5- cyano group-Isosorbide-5-Nitrae-dihydropyran simultaneously [2,3-c] pyrazoles：M.p.262~264 DEG C；1H
NMR (500MHz, DMSO-d6)：δ=4.96 (s, 1H), 6.89 (s, 2H), 7.08~7.42 (m, 10H), 12.86 (s, 1H)
Embodiment 2
By 1mmol 4-chloro-benzaldehydes, 1mmol ethyl benzoylacetates, 1.0mmol malononitrile, the hydrazine hydrates of 1mmol 80%
Be added to 0.04mmol alkali ionic liquids fill the ethanol waters of 5ml 90% (volume ratio) with stirrer and condensation
In the 25ml single port bottles of pipe.Lower back flow reaction 12min is stirred vigorously, TLC (thin plate chromatography) detections, raw material point disappears, is cooled to
Room temperature, pulverizes the solid of precipitation, stand, suction filtration, obtained after filter residue is vacuum dried 6- amino -4- (4- chlorphenyls) -3- phenyl -
5- cyano group-Isosorbide-5-Nitrae-dihydropyran simultaneously [2,3-c] pyrazoles, yield is 90%.4-chloro-benzaldehyde, benzoyl second are directly added into filtrate
Acetoacetic ester, malononitrile and 80% hydrazine hydrate are reused.
6- amino -4- (4- chlorphenyls) -3- phenyl -5- cyano group-Isosorbide-5-Nitrae-dihydropyran simultaneously [2,3-c] pyrazoles：M.p.241~
244℃；1H NMR (500MHz, DMSO-d6)：δ=4.99 (s, 1H), 6.97 (s, 2H), 7.10~7.44 (m, 9H), 12.91
(s, 1H)
Embodiment 3
1mmol p-tolyl aldehydes, 1mmol ethyl benzoylacetates, 1.2mmol malononitrile, 1mmol 80% are hydrated
Hydrazine and 0.06mmol alkali ionic liquids be added to fill the ethanol waters of 4ml 90% (volume ratio) with stirrer and cold
In the 25ml single port bottles of solidifying pipe.Lower back flow reaction 26min is stirred vigorously, TLC (thin plate chromatography) detections, raw material point disappears, cooling
To room temperature, the solid of precipitation is pulverized, stood, suction filtration obtains 6- amino -4- (4- aminomethyl phenyls) -3- after filter residue is vacuum dried
Phenyl -5- cyano group-Isosorbide-5-Nitrae-dihydropyran simultaneously [2,3-c] pyrazoles, yield is 87%.Be directly added into filtrate p-tolyl aldehyde,
Ethyl benzoylacetate, malononitrile and 80% hydrazine hydrate are reused.
6- amino -4- (4- aminomethyl phenyls) -3- phenyl -5- cyano group-Isosorbide-5-Nitrae-dihydropyran simultaneously [2,3-c] pyrazoles：m.p.244
~246 DEG C；1H NMR (500MHz, DMSO-d6)：δ=2.18 (s, 3H), 4.91 (s, 1H), 6.87 (s, 2H), 6.95~7.43
(m, 9H), 12.92 (s, 1H)
Embodiment 4
1mmol paranitrobenzaldehydes, 1mmol ethyl benzoylacetates, 1.1mmol malononitrile, 1mmol 80% are hydrated
Hydrazine and 0.05mmol alkali ionic liquids be added to fill the ethanol waters of 5ml 90% (volume ratio) with stirrer and cold
In the 25ml single port bottles of solidifying pipe.Lower back flow reaction 23min is stirred vigorously, TLC (thin plate chromatography) detections, raw material point disappears, cooling
To room temperature, the solid of precipitation is pulverized, stood, suction filtration obtains 6- amino -4- (4- nitrobenzophenones) -3- after filter residue is vacuum dried
Phenyl -5- cyano group-Isosorbide-5-Nitrae-dihydropyran simultaneously [2,3-c] pyrazoles, yield is 89%.Be directly added into filtrate paranitrobenzaldehyde,
Ethyl benzoylacetate, malononitrile and 80% hydrazine hydrate are reused.
6- amino -4- (4- nitrobenzophenones) -3- phenyl -5- cyano group-Isosorbide-5-Nitrae-dihydropyran simultaneously [2,3-c] pyrazoles：m.p.248
~250 DEG C；1H NMR (500MHz, DMSO-d6)：δ=5.25 (s, 1H), 7.09 (s, 2H), 7.29~7.34 (m, 3H), 7.37
~7.40 (d, J=10.0Hz, 2H), 7.42~7.45 (t, J=6.8Hz, 2H), 8.06~8.09 (d, J=10.0Hz, 2H),
12.98 (s, 1H)
Embodiment 5
By 1mmol 3-bromobenzaldehydes, 1mmol ethyl benzoylacetates, 1.0mmol malononitrile, the hydrazine hydrates of 1mmol 80%
Be added to 0.05mmol alkali ionic liquids fill the ethanol waters of 4ml 90% (volume ratio) with stirrer and condensation
In the 25ml single port bottles of pipe.Lower back flow reaction 16min is stirred vigorously, TLC (thin plate chromatography) detections, raw material point disappears, is cooled to
Room temperature, pulverizes the solid of precipitation, stand, suction filtration, obtained after filter residue is vacuum dried 6- amino -4- (3- bromophenyls) -3- phenyl -
5- cyano group-Isosorbide-5-Nitrae-dihydropyran simultaneously [2,3-c] pyrazoles, yield is 87%.3-bromobenzaldehyde, benzoyl second are directly added into filtrate
Acetoacetic ester, malononitrile and 80% hydrazine hydrate are reused.
6- amino -4- (3- bromophenyls) -3- phenyl -5- cyano group-Isosorbide-5-Nitrae-dihydropyran simultaneously [2,3-c] pyrazoles：M.p.249~
251℃；1H NMR (500MHz, DMSO-d6)：δ=5.06 (s, 1H), 7.02 (s, 2H), 7.08~7.44 (m, 9H), 12.91
(s, 1H)
Embodiment 6
By 1mmol benzaldehydes, 1mmol ethyl benzoylacetates, 1.2mmol malononitrile, 1mmol phenylhydrazines and 0.06mmol alkali
Property ionic liquid is added to the 25ml single port with stirrer and condenser pipe for filling the ethanol waters of 3ml 90% (volume ratio)
In bottle.Lower back flow reaction 34min is stirred vigorously, TLC (thin plate chromatography) detections, raw material point disappears, and is cooled to room temperature, pulverizes precipitation
Solid, stand, suction filtration obtains 6- amino -1,3,4- triphenyl -5- cyano group-Isosorbide-5-Nitrae-dihydropyran after filter residue is vacuum dried
And [2,3-c] pyrazoles, yield is 83%.Benzaldehyde, ethyl benzoylacetate, malononitrile and phenylhydrazine are directly added into filtrate to be carried out
Reuse.
6- amino -1,3,4- triphenyl -5- cyano group-Isosorbide-5-Nitrae-dihydropyran simultaneously [2,3-c] pyrazoles：M.p.190~192 DEG C；1H NMR (500MHz, DMSO-d6)：δ=5.07 (s, 1H), 7.12~7.93 (m, 17H)
Embodiment 7
By 1mmol parahydroxyben-zaldehydes, 1mmol ethyl benzoylacetates, 1.2mmol malononitrile, 1mmol phenylhydrazines and
0.06mmol alkali ionic liquids be added to fill the ethanol waters of 5ml 90% (volume ratio) with stirrer and condenser pipe
25ml single port bottles in.Lower back flow reaction 31min is stirred vigorously, TLC (thin plate chromatography) detections, raw material point disappears, and is cooled to room
Temperature, pulverizes the solid of precipitation, stands, and suction filtration obtains 6- amino -1,3- diphenyl-(4- hydroxy benzenes after filter residue is vacuum dried
Base) -5- cyano group-Isosorbide-5-Nitrae-dihydropyran simultaneously [2,3-c] pyrazoles, yield is 82%.Parahydroxyben-zaldehyde, benzene are directly added into filtrate
Formyl acetic acid ethyl ester, malononitrile and phenylhydrazine are reused.
6- amino -1,3- diphenyl-(4- hydroxy phenyls) -5- cyano group-Isosorbide-5-Nitrae-dihydropyran simultaneously [2,3-c] pyrazoles：
M.p.235~237 DEG C；1H NMR (500MHz, DMSO-d6)：δ=4.94 (s, 1H), 6.57~7.91 (m, 16H), 9.22 (s,
1H)
Embodiment 8
By 1mmol P-methoxybenzal-dehyde, 1mmol ethyl benzoylacetates, 1.2mmol malononitrile, 1mmol phenylhydrazines and
0.06mmol alkali ionic liquids be added to fill the ethanol waters of 4ml 90% (volume ratio) with stirrer and condenser pipe
25ml single port bottles in.Lower back flow reaction 38min is stirred vigorously, TLC (thin plate chromatography) detections, raw material point disappears, and is cooled to room
Temperature, pulverizes the solid of precipitation, stands, and suction filtration obtains 6- amino -1,3- diphenyl-(4- methoxybenzenes after filter residue is vacuum dried
Base) -5- cyano group-Isosorbide-5-Nitrae-dihydropyran simultaneously [2,3-c] pyrazoles, yield is 79%.Be directly added into filtrate P-methoxybenzal-dehyde,
Ethyl benzoylacetate, malononitrile and phenylhydrazine are reused.
6- amino -1,3- diphenyl-(4- methoxyphenyls) -5- cyano group-Isosorbide-5-Nitrae-dihydropyran simultaneously [2,3-c] pyrazoles：
M.p.225~227 DEG C；1H NMR (500MHz, DMSO-d6)：δ=3.62 (s, 3H), 5.04 (s, 1H), 6.77~7.93 (m,
16H)
Embodiment 9
By 1mmol benzaldehydes, 1mmol ethyl acetoacetates, 1mmol malononitrile, the hydrazine hydrates of 1mmol 80% and
0.05mmol alkali ionic liquids be added to fill the ethanol waters of 3ml 90% (volume ratio) with stirrer and condenser pipe
25ml single port bottles in.Lower back flow reaction 18min is stirred vigorously, TLC (thin plate chromatography) detections, raw material point disappears, and is cooled to room
Temperature, pulverizes the solid of precipitation, stand, suction filtration, obtained after filter residue is vacuum dried 3- methyl -6- amino-5-cyano -4- phenyl -
Isosorbide-5-Nitrae-dihydropyran simultaneously [2,3-c] pyrazoles, yield is 89%.Benzaldehyde, ethyl acetoacetate, malononitrile are directly added into filtrate
Reused with 80% hydrazine hydrate.
3- methyl -6- amino-5-cyanos -4- phenyl-Isosorbide-5-Nitrae-dihydropyran simultaneously [2,3-c] pyrazoles：M.p.242~244 DEG C
；1H NMR (500MHz, DMSO-d6)：δ=1.85 (s, 3H), 4.64 (s, 1H), 6.76 (s, 2H), 7.14 (d, J=7.0Hz,
2H), 7.35 (t, J=7.0Hz, 1H), 7.42 (t, J=7.0Hz, 2H), 12.06 (s, 1H)
Embodiment 10
By 1mmol p-bromobenzaldehydes, 1mmol ethyl acetoacetates, 1mmol malononitrile, the hydrazine hydrates of 1mmol 80% and
0.04mmol alkali ionic liquids be added to fill the ethanol waters of 4ml 90% (volume ratio) with stirrer and condenser pipe
25ml single port bottles in.Lower back flow reaction 14min is stirred vigorously, TLC (thin plate chromatography) detections, raw material point disappears, and is cooled to room
Temperature, pulverizes the solid of precipitation, stands, and suction filtration obtains 3- methyl -6- amino-5-cyanos -4- (4- bromines after filter residue is vacuum dried
Phenyl)-Isosorbide-5-Nitrae-dihydropyran simultaneously [2,3-c] pyrazoles, yield is 91%.P-bromobenzaldehyde, acetoacetate are directly added into filtrate
Ethyl ester, malononitrile and 80% hydrazine hydrate are reused.
3- methyl -6- amino-5-cyanos -4- (4- bromophenyls)-Isosorbide-5-Nitrae-dihydropyran simultaneously [2,3-c] pyrazoles：M.p.213~
215℃；1H NMR (500MHz, DMSO-d6)：δ=1.82 (s, 3H), 4.65 (s, 1H), 6.83 (s, 2H), 7.13 (d, J=
8.2Hz, 2H), 7.51 (t, J=8.2Hz, 2H), 12.12 (s, 1H)
Embodiment 11
By 1mmol o-nitrobenzaldehydes, 1mmol ethyl acetoacetates, 1.2mmol malononitrile, the hydrazine hydrates of 1mmol 80%
Be added to 0.05mmol alkali ionic liquids fill the ethanol waters of 5ml 90% (volume ratio) with stirrer and condensation
In the 25ml single port bottles of pipe.Lower back flow reaction 22min is stirred vigorously, TLC (thin plate chromatography) detections, raw material point disappears, is cooled to
Room temperature, pulverizes the solid of precipitation, stands, and suction filtration obtains 3- methyl -6- amino-5-cyano -4- (2- after filter residue is vacuum dried
Nitrobenzophenone)-Isosorbide-5-Nitrae-dihydropyran simultaneously [2,3-c] pyrazoles, yield is 88%.O-nitrobenzaldehyde, second are directly added into filtrate
Ethyl acetoacetic acid ethyl ester, malononitrile and 80% hydrazine hydrate are reused.
3- methyl -6- amino-5-cyanos -4- (2- nitrobenzophenones)-Isosorbide-5-Nitrae-dihydropyran simultaneously [2,3-c] pyrazoles：m.p.220
~222 DEG C；1H NMR (500MHz, DMSO-d6)：δ=1.84 (s, 3H), 4.95 (s, 1H), 6.91 (s, 2H), 7.22 (s, 1H),
7.41~7.46 (m, 2H), 7.77 (s, 1H), 12.13 (s, 1H)
Embodiment 12
By 1mmol benzaldehydes, 1mmol ethyl acetoacetates, 1.2mmol malononitrile, 1mmol phenylhydrazines and 0.05mmol alkalescence
Ionic liquid is added to the 25ml single port bottles with stirrer and condenser pipe for filling the ethanol waters of 3ml 90% (volume ratio)
In.Lower back flow reaction 25min is stirred vigorously, TLC (thin plate chromatography) detections, raw material point disappears, and is cooled to room temperature, pulverizes precipitation
Solid, stands, and suction filtration obtains 3- methyl -6- amino-5-cyanos-Isosorbide-5-Nitrae-diphenyl-Isosorbide-5-Nitrae-dihydro pyrrole after filter residue is vacuum dried
Mutter simultaneously [2,3-c] pyrazoles, yield is 86%.Benzaldehyde, ethyl acetoacetate, malononitrile and phenylhydrazine are directly added into filtrate to be carried out
Reuse.
3- methyl -6- amino-5-cyanos-Isosorbide-5-Nitrae-diphenyl-Isosorbide-5-Nitrae-dihydropyran simultaneously [2,3-c] pyrazoles：M.p.171~
173℃；1H NMR (500MHz, DMSO-d6)：δ=1.93 (s, 3H), 4.62 (s, 1H), 4.79 (s, 2H), 7.12~7.29 (m,
10H)
Embodiment 13
By 1mmol 4-chloro-benzaldehydes, 1mmol ethyl acetoacetates, 1mmol malononitrile, 1mmol phenylhydrazines and 0.05mmol alkali
Property ionic liquid is added to the 25ml single port with stirrer and condenser pipe for filling the ethanol waters of 5ml 90% (volume ratio)
In bottle.Lower back flow reaction 19min is stirred vigorously, TLC (thin plate chromatography) detections, raw material point disappears, and is cooled to room temperature, pulverizes precipitation
Solid, stand, suction filtration obtains 3- methyl -6- amino-5-cyanos -4- (4- chlorphenyls) -1- benzene after filter residue is vacuum dried
Base-Isosorbide-5-Nitrae-dihydropyran simultaneously [2,3-c] pyrazoles, yield is 91%.4-chloro-benzaldehyde, acetoacetate second are directly added into filtrate
Ester, malononitrile and phenylhydrazine are reused.
3- methyl -6- amino-5-cyanos -4- (4- chlorphenyls) -1- phenyl-Isosorbide-5-Nitrae-dihydropyran simultaneously [2,3-c] pyrazoles：
M.p.174~176 DEG C；1H NMR (500MHz, DMSO-d6)：δ=1.87 (s, 3H), 4.71 (s, 1H), 6.32 (s, 2H), 7.24
~7.35 (m, 3H), 7.41 (d, J=7.6Hz, 2H), 7.46~7.50 (m, 2H), 7.73 (d, J=7.6Hz, 2H)
Embodiment 14
With embodiment 2 as probe reaction, make the active replica test of catalysts alkali ionic liquid, ionic liquid
Reuse 8 times, product 6- amino -4- (4- chlorphenyls) -3- phenyl -5- cyano group-Isosorbide-5-Nitrae-dihydropyran simultaneously [2,3-c] pyrazoles
Yield change is shown in Table 1.
The alkali ionic liquid of table 1 is preparing 6- amino -4- (4- chlorphenyls) -3- phenyl -5- cyano group-Isosorbide-5-Nitrae-dihydropyran simultaneously
Active replica test result in [2,3-c] pyrazoles
| Alkaline ionic liquid catalyst access times | Yield (%) |
| 1 | 90 |
| 2 | 88 |
| 3 | 88 |
| 4 | 90 |
| 5 | 89 |
| 6 | 89 |
| 7 | 87 |
| 8 | 87 |
| 9 | 85 |
Embodiment 15
With embodiment 7 as probe reaction, make the active replica test of catalysts alkali ionic liquid, ionic liquid
Reuse 8 times, product 6- amino -1,3- diphenyl-(4- hydroxy phenyls) -5- cyano group-Isosorbide-5-Nitrae-dihydropyran simultaneously [2,3-c] pyrrole
The yield change of azoles is shown in Table 2.
The alkali ionic liquid of table 2 is preparing 6- amino -1,3- diphenyl-(4- hydroxy phenyls) -5- cyano group-Isosorbide-5-Nitrae-dihydro pyrroles
The active replica test result muttered in simultaneously [2,3-c] pyrazoles
Embodiment 16
With embodiment 10 as probe reaction, make the active replica test of catalysts alkali ionic liquid, ionic liquid
Body is reused 8 times, product 3- methyl -6- amino-5-cyanos -4- (4- bromophenyls)-Isosorbide-5-Nitrae-dihydropyran simultaneously [2,3-c] pyrazoles
Yield change be shown in Table 3.
The alkali ionic liquid of table 3 is preparing 3- methyl -6- amino-5-cyanos -4- (4- bromophenyls)-Isosorbide-5-Nitrae-dihydropyran simultaneously
Active replica test result in [2,3-c] pyrazoles
| Alkaline ionic liquid catalyst access times | Yield (%) |
| 1 | 91 |
| 2 | 91 |
| 3 | 91 |
| 4 | 89 |
| 5 | 89 |
| 6 | 90 |
| 7 | 86 |
| 8 | 87 |
| 9 | 86 |
Embodiment 17
With embodiment 13 as probe reaction, make the active replica test of catalysts alkali ionic liquid, ionic liquid
Body reuse 8 times, product 3- methyl -6- amino-5-cyanos -4- (4- chlorphenyls) -1- phenyl-Isosorbide-5-Nitrae-dihydropyran simultaneously [2,
3-c] pyrazoles yield change be shown in Table 4.
The alkali ionic liquid of table 4 is preparing 3- methyl -6- amino-5-cyanos -4- (4- chlorphenyls) -1- phenyl-Isosorbide-5-Nitrae-two
Hydrogen pyrans active replica test result simultaneously in [2,3-c] pyrazoles
| Alkaline ionic liquid catalyst access times | Yield (%) |
| 1 | 91 |
| 2 | 89 |
| 3 | 89 |
| 4 | 90 |
| 5 | 91 |
| 6 | 88 |
| 7 | 87 |
| 8 | 87 |
| 9 | 85 |
Be can be seen that by table 1,2,3 and 4：Catalyst alkali ionic liquid is recycling catalysis preparation 6- amino -4- (4-
Chlorphenyl) -3- phenyl -5- cyano group-Isosorbide-5-Nitrae-dihydropyran simultaneously [2,3-c] pyrazoles, 6- amino -1,3- diphenyl-(4- hydroxy benzenes
Base) -5- cyano group-Isosorbide-5-Nitrae-dihydropyran simultaneously [2,3-c] pyrazoles, 3- methyl -6- amino-5-cyanos -4- (4- bromophenyls)-Isosorbide-5-Nitrae-two
Simultaneously [2,3-c] pyrazoles and 3- methyl -6- amino-5-cyanos -4- (4- chlorphenyls) -1- phenyl-Isosorbide-5-Nitrae-dihydropyran be simultaneously for hydrogen pyrans
Yield is in a slight decrease during [2,3-c] pyrazoles, but it is smaller to reduce amplitude.It could therefore be concluded that going out the catalyst alkali
Property ionic liquid prepares pyrans and can simultaneously be recycled during [2,3-c] pyrazole derivatives in catalysis, its catalysis activity
It is not obviously lowered.
Claims (4)
1. a kind of method that alkali ionic liquid catalysis prepares pyrans simultaneously [2,3-c] pyrazole derivatives, it is characterised in that the system
The mol ratio of aromatic aldehyde, ethyl acetoacetate or ethyl benzoylacetate, malononitrile and hydrazine is 1 in standby reaction：1：1~1.2：1,
The mole of alkaline ionic liquid catalyst is the 4~6% of aromatic aldehyde used, and the ethanol of reaction dissolvent 90% in terms of milliliter is water-soluble
The volume of liquid be by mM in terms of 3~5 times of aromatic aldehyde mole, reaction pressure is an atmospheric pressure, during back flow reaction
Between be 12~40min, reaction terminate after be cooled to room temperature, pulverize the solid of precipitation, stand, suction filtration, filter residue vacuum drying after
To pyrans simultaneously [2,3-c] pyrazole derivatives；
The structural formula of the alkaline ionic liquid catalyst is：
2. the method that a kind of alkali ionic liquid catalysis as claimed in claim 1 prepares pyrans simultaneously [2,3-c] pyrazole derivatives,
Characterized in that, described aromatic aldehyde be benzaldehyde, 4-chloro-benzaldehyde, p-tolyl aldehyde, paranitrobenzaldehyde, to bromobenzene first
Any in aldehyde, parahydroxyben-zaldehyde, P-methoxybenzal-dehyde, 3-bromobenzaldehyde, m-nitrobenzaldehyde, o-nitrobenzaldehyde
Kind.
3. the method that a kind of alkali ionic liquid catalysis as claimed in claim 1 prepares pyrans simultaneously [2,3-c] pyrazole derivatives,
Characterized in that, the hydrazine is hydrazine hydrate or phenylhydrazine.
4. the method that a kind of alkali ionic liquid catalysis as claimed in claim 1 prepares pyrans simultaneously [2,3-c] pyrazole derivatives,
Characterized in that, the filtrate after suction filtration can be reused at least 8 times without any treatment.
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| CN105801595A (en) * | 2016-05-17 | 2016-07-27 | 安徽工业大学 | Method for catalytically preparing 4,5-dihydropyran[c]chromene derivative |
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| CN105801595A (en) * | 2016-05-17 | 2016-07-27 | 安徽工业大学 | Method for catalytically preparing 4,5-dihydropyran[c]chromene derivative |
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| Title |
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| 李晓君等: "碱性离子液体催化"一锅法"合成1,4-二氢吡喃并[2,3-c]吡唑", 《有机化学》 * |
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