CN106631718B - A kind of synthetic method of asymmetric conjugation diine - Google Patents
A kind of synthetic method of asymmetric conjugation diine Download PDFInfo
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- CN106631718B CN106631718B CN201611137371.XA CN201611137371A CN106631718B CN 106631718 B CN106631718 B CN 106631718B CN 201611137371 A CN201611137371 A CN 201611137371A CN 106631718 B CN106631718 B CN 106631718B
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- 230000021615 conjugation Effects 0.000 title claims abstract description 45
- 238000010189 synthetic method Methods 0.000 title claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 238000000605 extraction Methods 0.000 claims abstract description 14
- 238000010992 reflux Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 14
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims abstract description 7
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000007445 Chromatographic isolation Methods 0.000 claims abstract description 6
- 238000011097 chromatography purification Methods 0.000 claims abstract description 6
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 46
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 43
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 38
- 239000000047 product Substances 0.000 claims description 32
- 239000003208 petroleum Substances 0.000 claims description 31
- 229960004643 cupric oxide Drugs 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 20
- 229910052786 argon Inorganic materials 0.000 claims description 19
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000005751 Copper oxide Substances 0.000 claims description 17
- 229910000431 copper oxide Inorganic materials 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 12
- 238000004440 column chromatography Methods 0.000 claims description 10
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 10
- 241000251511 Holothuroidea Species 0.000 claims description 9
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 9
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 7
- 125000001246 bromo group Chemical group Br* 0.000 claims description 5
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims 2
- 238000003810 ethyl acetate extraction Methods 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 39
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 23
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- 238000005481 NMR spectroscopy Methods 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 150000002170 ethers Chemical class 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 8
- -1 alkenyl phosphine Chemical compound 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 5
- 239000001273 butane Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000006880 cross-coupling reaction Methods 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000007818 Grignard reagent Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 0 CC(*)(C#CNI)O Chemical compound CC(*)(C#CNI)O 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical class C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 206010001497 Agitation Diseases 0.000 description 1
- 235000008658 Artemisia capillaris Nutrition 0.000 description 1
- 241000092668 Artemisia capillaris Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- QDJZBFLFHUMZBE-UHFFFAOYSA-N acetylene;bromobenzene Chemical group C#C.BrC1=CC=CC=C1 QDJZBFLFHUMZBE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000004303 annulenes Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000036436 anti-hiv Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940126678 chinese medicines Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 208000006278 hypochromic anemia Diseases 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The present invention provides a kind of synthetic methods of asymmetric conjugation diine, include the following steps：A, after mixing catalyst with Phen and highly basic, cis- alkene bromine, end-group alkyne and solvent are added in argon atmosphere, reaction 20 is stirred at reflux under conditions of 140 150 DEG C for 24 hours；B, product obtains asymmetric conjugation diine by column chromatographic isolation and purification after extraction, drying, concentration.Compared with prior art, synthetic method of the present invention is at low cost, and raw material is easy to get, and operation is more convenient, and efficient, use scope is wide, is suitble to a variety of substrate reactions, and catalyst being capable of recycling.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of synthetic method of asymmetric conjugation diine.
Background technology
Conjugation diyne is the important source material and intermediate of organic synthesis field, and starting material can be used as big for synthesizing
Annulene, conjugation alkynes oligomer etc..Meanwhile or a variety of natural products and the skeleton structure with bioactive compound.Contain
There are some compounds of 1,3- diine structures to be determined high efficiency anti-tumor, antibacterial, anti-inflammatory and HIV-resistant activity.Such as：From
19 carbon diacetylenic acids of traditional Chinese medicine ingredient 19- (2- furyls) -5,7- separated in Artemisia capillaris etc..
The method for the asymmetric conjugation diine of synthesis reported in document is mainly the following：
(1) 2000 year E.Negishi seminar synthesizes asymmetric 1,3- conjugation two using Pd catalysed cross coupling selectivities
Alkynes.
Although the experimental method yield is higher, but needs a point three steps ability synthesis of conjugate diine, reaction is more complex.
(2) 2008 years Lei seminars report the synthesis of the asymmetric conjugation diine of palladium chtalyst.The reaction is with bromobenzene
Acetylene and end-group alkyne are substrate, Pd (dba)2For catalyst, a kind of alkenyl phosphine is ligand, and triethylamine is organic weak base, and is added
CuI makees co-catalyst.
The applicability of the reaction substrate is wider, has good selectivity, yield higher.But the method has used noble metal to urge
Agent and Phosphine ligands, synthesis cost are high.
(3) 2009 years, Lei seminars were on the working foundation of early period, by the way that NiCl is added2·2H2O makees catalyst and adds
Enter CuI and make co-catalyst, is equipped with TMEDA complexings, enabling obtain the cross-coupling products of higher yields.
Bimetallic catalyst is not used only in the experimental method, and TMEDA ligand complex is added, and reaction needs one kind
Alkynes is excessive.
(4) 2012 years Ranu synthesize asymmetrical diine using the complex-catalyzed cis- bromostyrenes of Cu-HAP.Herein
In reaction, trans-styryl bromide generally yields trans- eneyne product, and cis- styrene bromide is produced by elimination reaction
The cross-coupling of raw alkynes and another alkynes, generates two acetylene compounds of conjugation.
The experimental method utilizes the copper complex of specific structure, the synthesis of this complex more complex.
(5) 2013 years Xie Meihua seminars reported for work nickel catalysis alkyl Grignard reagent and alkynyl sulfone cross-coupling it is anti-
Asymmetric 1,3 diines should be synthesized.In the synthesis, Isosorbide-5-Nitrae-diaryl 1,3- diines can obtain moderate to good yield, and right
It is relatively low (30-54%) in alkyl-substituted 1,3- diines yield.
The alkyl Grignard reagent that the experimental method uses is not unstable, easy to operate.
(6) 2014 years Ranu seminars, without ligand catalyst, pass through Cs using bimetallicp-CspCoupling synthesis is asymmetric
1,3- diines.
The experimental method substrate wide adaptability, but used bimetallic catalyst.
In conclusion the method for prior art synthesis of conjugate diine is although more, but these methods some need by compared with
For complicated synthesis step；The reactant of some is unstable, and operation has certain difficulty；Some reaction time are long, and
Reaction yield is relatively low；Some easily cause environmental pollution using organic phosphine drug.More importantly this kind of reaction mostly uses palladium, nickel
Equal noble metals or bimetallic are catalyst, and reaction cost is not costly and recyclable, is not suitable for industrial production.
Therefore it provides a kind of novel method for synthesizing of asymmetric conjugation diine is necessary.
Invention content
The purpose of the present invention is to provide a kind of synthetic methods of asymmetric conjugation diine, make protection gas using argon gas, receive
The cis- alkene bromine of rice copper oxide catalyzation and end-group alkyne directly react the asymmetric conjugation diine of preparation, and synthetic method is at low cost, and raw material is easy
, operation is more convenient, and efficient, use scope is wide, is suitble to a variety of substrate reactions, and catalyst being capable of recycling.
A kind of synthetic method of asymmetric conjugation diine provided by the invention, includes the following steps：
A, after catalyst being mixed with Phen and highly basic, be added in argon atmosphere cis- alkene bromine, end-group alkyne with it is molten
Agent is stirred at reflux reaction 20-24h under conditions of 140-150 DEG C；
B, product obtains asymmetric conjugation diine by column chromatographic isolation and purification after extraction, drying, concentration.
Cis- alkene bromine in step A, end-group alkyne, catalyst, highly basic, Phen molar ratio be 1：1.2-1.5：0.05-
0.1：2-2.5：0.15-0.2.
The cis- alkene bromine and the amount ratio of solvent are：1：2-4mmol/mL.
Further, relative to the cis- alkene bromine of 1mmol, the dosage 1.2-1.5mmol of the end-group alkyne, institute in step A
The dosage for stating catalyst is 0.05-0.1mmol, and the dosage of the highly basic is 2-2.5mmol, and the dosage of the Phen is
The dosage of 0.15-0.2mmol, the organic solvent are 2-4mL.
Cis- alkene bromine structural formula described in step A is：
Wherein R1Selected from 4-H, 4-CH3、4-OCH3、3-OCH3、2-OCH3、4-Cl、3-Cl、2-Cl
Or 4-CF3In any one.
The structural formula of end-group alkyne described in step A is：
Wherein R2Selected from 4-H, 4-CH3、4-OCH3、3-OCH3、2-OCH3、4-Cl、3-Cl、2-
Cl、4-Br、4-F、4-C(CH3)3In any one.
Catalyst described in step A is fusiformis nano cupric oxide, copper oxide nano particle, flake nano copper oxide, sea cucumber
Any one of shape nano cupric oxide or flower-like nanometer copper oxide can be recycled and be recycled, wherein sea cucumber shape nano-catalytic
Agent catalytic effect is especially pronounced.
The specific preparation method of various catalyst is as follows in step A：
It takes the distilled water of 40mL to be added in 100mL beakers, weighs the Cu (CH of 0.3194g3COO)2·H2O solids are placed in
In beaker, made it dissolve in the case of 30 DEG C of magnetic agitations, then be slowly dropped into the NH of 1M3·H2O solution adjusts pH value, will burn
Cup preservative film package is put in baking oven, is reacted under the conditions of 65 DEG C and is cooled to room temperature for 24 hours, then uses distilled water and anhydrous respectively
Ethyl alcohol respectively twice of cleaning, separation centrifuge, and vacuum drying 5h can be prepared by the nano cupric oxide of different-shape under the conditions of 60 DEG C.This is anti-
Middle pH is answered to obtain fusiformis nano cupric oxide for 7；PH be 8 sea cucumber shape nano cupric oxide pH be 8.5 flake nano copper oxide；PH is
9.5 obtain flower-like nanometer copper oxide.
The preparation method of copper oxide nano particle described in step A：Take the Cu (CH of 0.4525g3COO)2It is anhydrous to be dissolved in 50mL
In ethyl alcohol, waits for that its dissolving is placed in the polytetrafluoroethylene (PTFE) autoclave of capacity 60mL and react 20h under the conditions of 150 DEG C, be cooled to
Room temperature, then 2 times and washes of absolute alcohol 3 times, separation centrifugation are dried in vacuo to obtain black under room temperature wash with distilled water respectively
Powder, i.e. copper oxide nano particle.
Highly basic described in step A is any one in sodium hydroxide, potassium hydroxide, sodium tert-butoxide or cesium carbonate.
Solvent described in step A is diethylene glycol dimethyl ether DGDE, n,N-Dimethylformamide DMF or dimethyl sulfoxide (DMSO)
Any one in DMSO.
Step B is specially：Products therefrom petroleum ether, ethyl acetate are extracted, anhydrous sodium sulfate drying is concentrated under reduced pressure,
Crude product is obtained, using pure petroleum ether as solvent, 1,3- of asymmetry is obtained by column chromatography for separation and is conjugated diine.
The structural formula of the asymmetric conjugation diine isWherein R1It is selected from
4-H、4-CH3、4-OCH3、3-OCH3、2-OCH3, 4-Cl, 3-Cl, 2-Cl or 4-CF3In any one, R2Selected from 4-H, 4-
CH3、4-OCH3、3-OCH3、2-OCH3、4-Cl、3-Cl、2-Cl、4-Br、4-F、4-C(CH3)3In any one.
Preferably, the synthetic method of the asymmetric conjugation diine, includes the following steps：
A, after 0.05mmol sea cucumber shapes nano cupric oxide, 0.15mmol Phens and 2mmol sodium hydroxides being mixed,
The cis- alkene bromines of 1mmol, 1.2mmol end-group alkynes and 3mL DGDE are added in argon atmosphere to be stirred at reflux under conditions of 145 DEG C instead
It should for 24 hours；
B, product obtains asymmetric conjugation diine by petroleum ether column chromatographic isolation and purification after extraction, drying, concentration.
Compared with prior art, the present invention uses nanometer copper oxide catalyst, simple easily system, performance to stablize, catalytic effect
Well and it can recycle；Raw material is reacted with cis- bromo alkene and end-group alkyne, and reaction condition is mild, need not use gold
Belong to Grignard Reagent, also without using noble metal or bimetallic catalyst；This reaction system is of low cost, is simple and efficient, environment friend
It is good, 1,3 diines of asymmetric conjugation of high yield can be synthesized, industrial production is conducive to.
Description of the drawings
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 1；
Fig. 2 is the carbon-13 nmr spectra figure of embodiment 1；
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 2；
Fig. 4 is the carbon-13 nmr spectra figure of embodiment 2；
Fig. 5 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 3；
Fig. 6 is the carbon-13 nmr spectra figure of embodiment 3；
Fig. 7 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 4；
Fig. 8 is the carbon-13 nmr spectra figure of embodiment 4；
Fig. 9 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 5；
Figure 10 is the carbon-13 nmr spectra figure of embodiment 5；
Figure 11 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 6；
Figure 12 is the carbon-13 nmr spectra figure of embodiment 6；
Figure 13 is the hydrogen nuclear magnetic resonance spectrogram of embodiment 7；
Figure 14 is the carbon-13 nmr spectra figure of embodiment 7；
Figure 15 is the reaction equation of the present invention.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, it is not limited to these embodiments.In embodiment, the alkynes of different substituents,
Phen, sodium hydroxide, potassium hydroxide, sodium tert-butoxide, cesium carbonate, DGDE, DMF, DMSO have for Chinese medicines group chemical reagent
Limit Products.
Embodiment 1
A kind of synthetic method of asymmetric conjugation diine, includes the following steps：
A, the fusiformis nano cupric oxide of 0.05mmol, 0.15mmol Phens are weighed respectively, and 2mmol sodium hydroxides are put into
In the reaction tube of clean dried, reaction tube is placed in anhydrous and oxygen-free system, vacuumize and is passed through argon gas cycle three times, in argon
Cis--the 1- of 1mmol (2- bromo vinyls) -4- tert-butyl benzenes, 1.2mmol 1- acetenyl -4- methoxies are sequentially added under gas shielded
Base benzene and 3mL diethylene glycol dimethyl ethers are stirred at reflux 20 hours under the conditions of 140 DEG C；
B, stop reaction postcooling to room temperature, with petroleum ether extraction 3 times, each 10mL petroleum ethers, and by gained organic phase
It is dried with anhydrous magnesium sulfate, after concentration, solvent column chromatography for separation is made with petroleum ether and purifies to obtain white solid i.e. 1- tertiary butyls -4-
[4- (4- methoxyphenyls) butane -1,3- diynyl] benzene, yield 80%, fusing point are 88-90 DEG C.
Product structure formula：
The hydrogen nuclear magnetic resonance modal data of product：
1H NMR(300MHz,CDCl3):δ 7.48-7.45 (m, 4H), 7.35 (d, J=8.2Hz, 2H), 6.86 (d, J=
8.6Hz,2H),3.82(s,3H),1.34(s,9H)；
The carbon-13 nmr spectra data of product：
13C NMR(75MHz,CDCl3):δ160.3,152.5,134.1,132.2,125.5,118.9,114.1,113.8,
81.4,79.1,73.5,72.9,55.4,34.9,31.1。
Embodiment 2
A kind of synthetic method of asymmetric conjugation diine, includes the following steps：
A, the sea cucumber shape nano cupric oxide of 0.05mmol, 0.15mmol Phens are weighed respectively, and 2mmol potassium hydroxide is put
In the reaction tube for entering clean dried, reaction tube is placed in anhydrous and oxygen-free system, vacuumize and is passed through argon gas cycle three times,
Cis--the 1- of 1mmol (2- bromo vinyls) -4- methylbenzenes are sequentially added under argon gas protection, 1.2mmol 1- acetenyls -4- is fluorine-based
Benzene and 3mL n,N-Dimethylformamide are stirred at reflux 20 hours under the conditions of 140 DEG C.
B, stop reaction postcooling to room temperature, with petroleum ether extraction 3 times, each 10mL petroleum ethers, and by gained organic phase
It is dried, is concentrated with anhydrous magnesium sulfate.Make solvent column chromatography for separation with petroleum ether and purifies to obtain the fluoro- 4- of white solid i.e. 1- [4- (4-
Aminomethyl phenyl) butane -1,3- diynyl] benzene, yield 85%, fusing point is 148-150 DEG C.
Product structure formula：
The hydrogen nuclear magnetic resonance modal data of product：
1H NMR δ 7.53-7.49 (m, 2H), 7.42 (d, J=7.2Hz, 2H), 7.14 (d, J=6.3Hz, 2H), 7.06-
7.00(m,2H),2.36(s,3H)；
The carbon-13 nmr spectra data of product：
13C NMR(CDCl3,75MHz):δ 163.0 (d, J=240.9Hz), 139.6 (d, J=15.3Hz), 134.5,
132.4,129.3,118.7 (d, J=19.1Hz), 115.9 (d, J=21.8Hz), 81.9,80.4,73.8,73.5,21.7.
Embodiment 3
A kind of synthetic method of asymmetric conjugation diine, includes the following steps：
A, the flake nano copper oxide of 0.1mmol is weighed respectively, and 0.3mmol Phens, 4mmol sodium hydroxides are put into clean
Only in dry reaction tube, reaction tube is placed in anhydrous and oxygen-free system, vacuumize and is passed through argon gas cycle three times, in argon gas
Cis--the 1- of 2mmol (2- bromo vinyls) benzene, the fluorine-based benzene of 2.4mmol 1- acetenyls -4- and 4mL diethyls are sequentially added under protection
Glycol dimethyl ether is stirred at reflux 20 hours under the conditions of 140 DEG C；
B, stop reaction postcooling to room temperature, with petroleum ether extraction 3 times, each 10mL petroleum ethers, and by gained organic phase
It is dried, is concentrated with anhydrous magnesium sulfate.Making the i.e. white solid i.e. 1- of solvent column chromatography for separation purification with petroleum ether, [(4- is fluorine-based by 4-
Phenyl) butane -1,3- diynyl] benzene, yield 61%, fusing point is 121-123 DEG C.
Product structure formula：
The hydrogen nuclear magnetic resonance modal data of product：
1H NMR(CDCl3,300MHz):δ 7.53 (d, J=5.3Hz, 4H), 7.36 (s, 3H), 7.04 (t, J=8.4Hz,
2H)；
The carbon-13 nmr spectra data of product：
13C NMR(CDCl3,75MHz):δ 163.0 (d, J=250.5Hz), 134.5 (d, J=8.3Hz), 132.5,
129.2,128.4,121.6,117.9 (d, J=3.0Hz), 115.8 (d, J=22.5Hz), 81.5,80.4,73.7,73.7.
Embodiment 4
A kind of synthetic method of asymmetric conjugation diine, includes the following steps：
A, the flower-like nanometer copper oxide of 0.5mmol, 1.5mmol Phens are weighed respectively, and 20mmol sodium hydroxides are put into
In the reaction tube of clean dried, reaction tube is placed in anhydrous and oxygen-free system, vacuumize and is passed through argon gas cycle three times.In argon
Cis--the 1- of 10mmol (2- bromo vinyls) -4- methoxybenzenes, 12mmol phenylacetylenes and 20mL diethyls are sequentially added under gas shielded
Glycol dimethyl ether is stirred at reflux 20 hours under the conditions of 150 DEG C.
B, stop reaction postcooling to room temperature, with petroleum ether extraction 3 times, each 40mL petroleum ethers, and by gained organic phase
It is dried, is concentrated with anhydrous magnesium sulfate.Make solvent column chromatography for separation with petroleum ether and purifies to obtain white solid i.e. 1- [4- (4- methoxies
Base phenyl) butane -1,3- diynyl] benzene, yield 61%, fusing point is 93-94 DEG C.
Product structure formula:
The hydrogen nuclear magnetic resonance modal data of product：
1H NMR(CDCl3,300MHz):δ 7.46-7.53 (m, 4H), 7.35 (s, 3H), 6.86 (d, J=8.2Hz, 2H),
3.83(s,3H)；
The carbon-13 nmr spectra data of product：
13C NMR(CDCl3,75MHz):δ=160.3,134.0,132.3,129.0,128.4,121.9,114.1,
113.6,81.8,81.0,74.2,72.7,55.2.
Embodiment 5
A kind of synthetic method of asymmetric conjugation diine, includes the following steps：
A, the sea cucumber shape nano cupric oxide of 0.5mmol, 1.5mmol Phens are weighed respectively, and 20mmol sodium hydroxides are put
In the reaction tube for entering clean dried, reaction tube is placed in anhydrous and oxygen-free system, vacuumize and is passed through argon gas cycle three times,
Cis--the 1- of 10mmol (2- bromo vinyls) -4- methylbenzenes are sequentially added under argon gas protection, 12mmol 1- acetenyls -4- is fluorine-based
Benzene and 20mL dimethyl sulfoxide (DMSO)s are stirred at reflux 20 hours under the conditions of 140 DEG C；
B, stop reaction postcooling to room temperature, with petroleum ether extraction 3 times, each 10mL petroleum ethers, and by gained organic phase
It is dried, is concentrated with anhydrous magnesium sulfate.Make solvent column chromatography for separation with petroleum ether and purifies to obtain the fluoro- 4- of white solid i.e. 1- [4- (4-
Aminomethyl phenyl) butane -1,3- diynyl] benzene, yield 78%, fusing point is 148-150 DEG C.
Product structure formula：
The hydrogen nuclear magnetic resonance modal data of product：
1H NMR δ 7.53-7.49 (m, 2H), 7.42 (d, J=7.2Hz, 2H), 7.14 (d, J=6.3Hz, 2H), 7.06-
7.00(m,2H),2.36(s,3H)；
The carbon-13 nmr spectra data of product：
13C NMR(CDCl3,75MHz):δ 163.0 (d, J=240.9Hz), 139.6 (d, J=15.3Hz), 134.5,
132.4,129.3,118.7 (d, J=19.1Hz), 115.9 (d, J=21.8Hz), 81.9,80.4,73.8,73.5,21.7.
Embodiment 6
A kind of synthetic method of asymmetric conjugation diine, includes the following steps：
A, the fusiformis nano cupric oxide of 0.025mmol, 0.075mmol Phens are weighed respectively, and 1mmol sodium tert-butoxides are put
In the reaction tube for entering clean dried, reaction tube is placed in anhydrous and oxygen-free system, vacuumize and is passed through argon gas cycle three times,
Cis--the 1- of 0.5mmol (2- bromo vinyls) -4- chloro benzene, -4 first of 0.6mmol 1- acetenyls are sequentially added under argon gas protection
Oxygroup benzene and 2mL diethylene glycol dimethyl ethers are stirred at reflux 24 hours under the conditions of 140 DEG C.
B, stop reaction postcooling to room temperature, with petroleum ether extraction 3 times, each 10mL petroleum ethers, and by gained organic phase
It is dried, is concentrated with anhydrous magnesium sulfate.With petroleum ether make solvent column chromatography for separation purify faint yellow solid i.e.
1- chloro- 4-[4- (4- methoxyphenyls) butane-1,3- diynyl] benzene, yield 80%, fusing point are 160-162 DEG C.
Product structure formula：
The hydrogen nuclear magnetic resonance modal data of product：
1H NMR(300MHz,CDCl3):δ 7.49-7.43 (m, 4H), 7.30 (d, J=9.0Hz, 2H), 6.87 (d, J=
9.0Hz,2H),3.83(s,3H).
The hydrogen nuclear magnetic resonance modal data of product：
13C NMR(75MHz,CDCl3):δ160.1,135.1,134.2,133.6,128.8,120.5,114.2,113.5,
82.4,79.8,75.2,72.5,55.4.
Embodiment 7
A kind of synthetic method of asymmetric conjugation diine, includes the following steps：
A, the copper oxide nano particle of 0.1mmol, 0.15mmol Phens are weighed respectively, and 2mmol cesium carbonates are put into clean
Only in dry reaction tube, reaction tube is placed in anhydrous and oxygen-free system, vacuumize and is passed through argon gas cycle three times, in argon gas
- 4 chloro benzene of the cis- -1- of 1mmol (2- bromo vinyls), 1.2mmol phenylacetylenes and 3mL diethylene glycols two are sequentially added under protection
Methyl ether is stirred at reflux 20 hours under the conditions of 150 DEG C；
B, stop reaction postcooling to room temperature, with petroleum ether extraction 3 times, each 10mL petroleum ethers, and by gained organic phase
It is dried, is concentrated with anhydrous magnesium sulfate.Make solvent column chromatography for separation with petroleum ether and purifies to obtain white solid i.e. 1- [4- (4- chloros
Phenyl) butane -1,3- diynyl] benzene, yield 80%, fusing point is 151-152 DEG C.
Product structure formula：
The hydrogen nuclear magnetic resonance modal data of product：
1H NMR(300MHz,CDCl3):δ7.54-7.30(m,9H).
The carbon-13 nmr spectra data of product：
13C NMR(75MHz,CDCl3):δ135.4,133.7,132.5,128.9,128.5,121.6,120.3,82.1,
80.3,74.9,73.6.
Embodiment 8
A kind of synthetic method of asymmetric conjugation diine, includes the following steps：
A, the flower-like nanometer copper oxide of 0.05mmol, 0.15mmol Phens are weighed respectively, and 2mmol potassium hydroxide is put into
In the reaction tube of clean dried, reaction tube is placed in anhydrous and oxygen-free system, vacuumize and is passed through argon gas cycle three times, in argon
Cis--the 1- of 1mmol (2- bromo vinyls) -4- methoxybenzenes, the tertiary fourths of 1.2mmol 1- acetenyls -4- are sequentially added under gas shielded
Base benzene and 3mL diethylene glycol dimethyl ethers are stirred at reflux 20 hours under the conditions of 140 DEG C；
B, stop reaction postcooling to room temperature, with petroleum ether extraction 3 times, each 10mL petroleum ethers, and by gained organic phase
It is dried with anhydrous magnesium sulfate, concentrates, solvent column chromatography for separation is made with petroleum ether and purifies to obtain white solid i.e. 1- tertiary butyls -4-
[4- (4- methoxyphenyls) butane -1,3- diynyl] benzene, yield 80%, fusing point are 88-90 DEG C.
Product structure formula：
1H NMR(300MHz,CDCl3):δ 7.48-7.45 (m, 4H), 7.35 (d, J=8.2Hz, 2H), 6.86 (d, J=
8.6Hz,2H),3.82(s,3H),1.34(s,9H)；
13C NMR(75MHz,CDCl3):δ160.3,152.5,134.1,132.2,125.5,118.9,114.1,113.8,
81.4,79.1,73.5,72.9,55.4,34.9,31.1。
Claims (11)
1. a kind of synthetic method of asymmetric conjugation diine, which is characterized in that the synthetic method includes the following steps：
A, after mixing catalyst with Phen and highly basic, cis- alkene bromine, end-group alkyne and solvent are added in argon atmosphere,
Reaction 20-24h is stirred at reflux under conditions of 140-150 DEG C；
B, product obtains asymmetric conjugation diine by column chromatographic isolation and purification after extraction, drying, concentration；
Cis- alkene bromine in step A, end-group alkyne, catalyst, highly basic, Phen molar ratio be 1：1.2-1.5：0.05-0.1：
2-2.5：0.15-0.2；
Catalyst described in step A is fusiformis nano cupric oxide, copper oxide nano particle, flake nano copper oxide, sea cucumber shape are received
Rice copper oxide or flower-like nanometer copper oxide in any one.
2. the synthetic method of asymmetric conjugation diine according to claim 1, which is characterized in that described in step step A
Cis- alkene bromine structural formula be：
Wherein R1Selected from 4-H, 4-CH3、4-OCH3、3-OCH3、2-OCH3, 4-Cl, 3-Cl, 2-Cl or 4-
CF3In any one.
3. the synthetic method of asymmetric conjugation diine according to claim 1 or 2, which is characterized in that held described in step A
The structural formula of base alkynes is：
Wherein R2Selected from 4-H, 4-CH3、4-OCH3、3-OCH3、2-OCH3、4-Cl、3-Cl、2-Cl、4-
Br、4-F、4-C(CH3)3In any one.
4. the synthetic method of asymmetric conjugation diine according to claim 1, which is characterized in that highly basic described in step A
For any one in sodium hydroxide, potassium hydroxide, sodium tert-butoxide or cesium carbonate.
5. the synthetic method of asymmetric conjugation diine according to claim 1, which is characterized in that solvent described in step A
For any one in diethylene glycol dimethyl ether DGDE, n,N-Dimethylformamide DMF or dimethyl sulfoxide (DMSO) DMSO.
6. being conjugated the synthetic method of diine according to claim 1,2,4 or 5 any one of them asymmetry, which is characterized in that institute
The synthetic method for stating asymmetric conjugation diine, includes the following steps：
A, after mixing 0.05mmol sea cucumber shapes nano cupric oxide, 0.15mmol Phens and 2mmol sodium hydroxides, in argon gas
The cis- alkene bromines of 1mmol are added in atmosphere, 1.2mmol end-group alkynes are stirred at reflux under conditions of 145 DEG C with 3mL DGDE and react
24h；
B, product obtains asymmetric conjugation diine by petroleum ether column chromatographic isolation and purification after extraction, drying, concentration.
7. the synthetic method of asymmetric conjugation diine according to claim 3, which is characterized in that the asymmetric conjugation two
The synthetic method of alkynes, includes the following steps：
A, after mixing 0.05mmol sea cucumber shapes nano cupric oxide, 0.15mmol Phens and 2mmol sodium hydroxides, in argon gas
The cis- alkene bromines of 1mmol are added in atmosphere, 1.2mmol end-group alkynes are stirred at reflux under conditions of 145 DEG C with 3mL DGDE and react
24h；
B, product obtains asymmetric conjugation diine by petroleum ether column chromatographic isolation and purification after extraction, drying, concentration.
8. the synthetic method of asymmetric conjugation diine according to claim 1, which is characterized in that step B is specially：By institute
Product petroleum ether, ethyl acetate extraction are obtained, anhydrous sodium sulfate drying is concentrated under reduced pressure, obtains crude product, is to be unfolded with pure petroleum ether
Agent obtains 1,3- of asymmetry by column chromatography for separation and is conjugated diine.
9. being conjugated the synthetic method of diine according to claim 1,2,4,5,7 or 8 any one of them asymmetry, feature exists
In the structural formula of the asymmetric conjugation diine isWherein R1Selected from 4-H, 4-
CH3、4-OCH3、3-OCH3、2-OCH3, 4-Cl, 3-Cl, 2-Cl or 4-CF3In any one, R2Selected from 4-H, 4-CH3、4-
OCH3、3-OCH3、2-OCH3、4-Cl、3-Cl、2-Cl、4-Br、4-F、4-C(CH3)3In any one.
10. the synthetic method of asymmetric conjugation diine according to claim 3, which is characterized in that the asymmetric conjugation
The structural formula of diine isWherein R1Selected from 4-H, 4-CH3、4-OCH3、3-OCH3、
2-OCH3, 4-Cl, 3-Cl, 2-Cl or 4-CF3In any one, R2Selected from 4-H, 4-CH3、4-OCH3、3-OCH3、2-OCH3、
4-Cl、3-Cl、2-Cl、4-Br、4-F、4-C(CH3)3In any one.
11. the synthetic method of asymmetric conjugation diine according to claim 6, which is characterized in that the asymmetric conjugation
The structural formula of diine isWherein R1Selected from 4-H, 4-CH3、4-OCH3、3-OCH3、
2-OCH3, 4-Cl, 3-Cl, 2-Cl or 4-CF3In any one, R2Selected from 4-H, 4-CH3、4-OCH3、3-OCH3、2-OCH3、
4-Cl、3-Cl、2-Cl、4-Br、4-F、4-C(CH3)3In any one.
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