CN103382153B - Norbornene addition polymerization derivative and its preparation method - Google Patents
Norbornene addition polymerization derivative and its preparation method Download PDFInfo
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- CN103382153B CN103382153B CN201310287154.9A CN201310287154A CN103382153B CN 103382153 B CN103382153 B CN 103382153B CN 201310287154 A CN201310287154 A CN 201310287154A CN 103382153 B CN103382153 B CN 103382153B
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- 238000012644 addition polymerization Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 title abstract description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 17
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 125000005574 norbornylene group Chemical group 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- 238000004440 column chromatography Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 7
- 230000006837 decompression Effects 0.000 claims description 7
- 239000012074 organic phase Substances 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 6
- 125000005605 benzo group Chemical group 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 230000005311 nuclear magnetism Effects 0.000 claims description 4
- 238000010898 silica gel chromatography Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 2
- 125000003518 norbornenyl group Chemical class C12(C=CC(CC1)C2)* 0.000 claims 4
- 229910002666 PdCl2 Inorganic materials 0.000 claims 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims 1
- 150000002848 norbornenes Chemical class 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 7
- 229940125782 compound 2 Drugs 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229940125904 compound 1 Drugs 0.000 description 5
- 150000001993 dienes Chemical class 0.000 description 5
- -1 nitro, carboxyl Chemical group 0.000 description 5
- 238000010499 C–H functionalization reaction Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 0 *OC(C(CCC1)C1=O)=O Chemical compound *OC(C(CCC1)C1=O)=O 0.000 description 3
- 238000005698 Diels-Alder reaction Methods 0.000 description 3
- 101150003085 Pdcl gene Proteins 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 150000001923 cyclic compounds Chemical class 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 238000010719 annulation reaction Methods 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006880 cross-coupling reaction Methods 0.000 description 2
- 238000006352 cycloaddition reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002431 hydrogen Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000007106 1,2-cycloaddition reaction Methods 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- GDDZYAPRXGBEDK-UHFFFAOYSA-N CC(CCC(C)=O)(CCCC1)C1=O Chemical compound CC(CCC(C)=O)(CCCC1)C1=O GDDZYAPRXGBEDK-UHFFFAOYSA-N 0.000 description 1
- OHERZLWVBJCXOF-UHFFFAOYSA-N CC(CCCC1)(CC2)C1=CC2=O Chemical compound CC(CCCC1)(CC2)C1=CC2=O OHERZLWVBJCXOF-UHFFFAOYSA-N 0.000 description 1
- PFQWHUARQDXHHI-UHFFFAOYSA-N CC(CCCC1)(CCC(C2)=O)C12O Chemical compound CC(CCCC1)(CCC(C2)=O)C12O PFQWHUARQDXHHI-UHFFFAOYSA-N 0.000 description 1
- LIVFBXBEOXCELH-UHFFFAOYSA-N COC(=O)C1(CC2=C(C3C4CCC(C4)C3C(=C2C1)C5=CC=CC=C5)C6=CC=CC=C6)C(=O)OC Chemical compound COC(=O)C1(CC2=C(C3C4CCC(C4)C3C(=C2C1)C5=CC=CC=C5)C6=CC=CC=C6)C(=O)OC LIVFBXBEOXCELH-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000010485 C−C bond formation reaction Methods 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 238000005575 aldol reaction Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000003997 cyclic ketones Chemical class 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- UVJHQYIOXKWHFD-UHFFFAOYSA-N cyclohexa-1,4-diene Chemical group C1C=CCC=C1 UVJHQYIOXKWHFD-UHFFFAOYSA-N 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a norbornene addition polymerization derivative and its preparation method. The method comprises the steps of: a. precursor synthesis; b. palladium catalysis; and c. purification. Because of its special structure, the norbornene addition polymerization derivative can have certain application value in the organic synthesis field. The norbornene derivative synthesized in the invention also has certain value in theoretical research.
Description
Technical field
The present invention relates to a kind of norbornylene addition polymerization derivative and preparation method thereof, belong to especially for the synthesis of six-ring.
Background technology
American Medical according to nineteen ninety-five is reported, the clinical medicine more than 80% on American market comprises at least one ring.And in many natural products, ring texture is also one of its essential condition.In view of the special significance of ring compound, how to go to construct ring texture and cause countless organic synthesis man and chemist actively thinks deeply, and drawn some effectively methods.The method of common synthesis of cyclic compound has:
1) intramolecular nucleophilic substitution reaction: open chain compound intramolecular cyclization
By intramolecular S
n2 go to construct ring compound, this kind of method more effectively can synthesize more stable five yuan and six-membered cyclic compound, but paper mill wastewater can affect the carrying out of reaction, and with emulative eliminative reaction, thus the productive rate of reaction is declined, and bring certain trouble to the separation of product.
2) cycloaddition reaction: two or more undersaturated compound forms ring by the restructuring of electronics.Wherein most typical is exactly Diels-Alder reaction:
Diels-Alder reaction be conjugated dienes system and alkene or the addition reaction of acetylene bond initial ring and the reaction of tetrahydrobenzene or 1,4-cyclohexadiene ring system.In this kind of reaction, be called dienophile with the alkene of conjugated dienes effect and alkynes.Electron substituent group of giving on electron-withdrawing substituent (as carbonyl, cyano group, nitro, carboxyl etc.) on dienophile and conjugated dienes has the effect that reaction is accelerated.
Diels-Alder reaction has abundant stereochemistry to present, and has stereoselectivity, stereospecificity and regioselectivity etc. concurrently.When diene and dienophile both have suitable substituting group, when making reaction different position may occur and obtain two kinds of products, it is main in fact only having a kind of.Thisly reacting by conjugated dienes and alkene or alkynes the reaction generating six-ring, is one of means of very important C―C bond formation in organic chemical synthesis reaction, is also one of reaction conventional in modern organic synthesis.
In addition the cycloaddition reaction be applied also has [2+2] cycloaddition reaction, can be used for synthesizing tetra-atomic ring.
3) diekmann condensation reaction: diester issues in alkali effect the reaction that raw intramolecular condensation generates 'beta '-ketoester.
In this reaction, first the alkali in solution capture the α-hydrogen of ester carbonyl group, Formed negative ion, because carbanion is unstable, will another carbonyl carbon of attack, and addition reaction occurs, and alcoxyl negative ion is left away simultaneously.Alkali captures a α-hydrogen more afterwards, irreversibly generates stable enol negative ion, obtains product finally by acid treatment.
4) Robinson's annulation: react in the presence of a base containing the cyclic ketones of active methylene group and a, b-beta-unsaturated carbonyl compounds, forms the ring system of two and six membered ring:
This reaction is divided into two steps, and the first step is Micheal addition reaction, and second step is aldol reaction.When reacting beginning, there is Michael addition in the enolate nucleophilic attack alpha, beta-unsaturated ketone generated by alkali attack carbonyl compound.The product generated carries out intramolecular aldol condensation immediately under basic conditions, obtains Robinson's annulation product.
5) carbon-hydrogen bond activation of metal catalytic synthesizes monocycle or polynuclear compound
The organic synthesis undertaken by carbon-hydrogen bond activation is development in recent years popular domain rapidly.By the activation of C-H bond, effectively can realize the formation of carbon-carbon bond, thus construct the compound of more complicated.Therefore the direct functionalization reaction of C-H bond is owing to having multiple outstanding advantage and very large challenge, is described as " Holy grail of chemistry ", attracts the concern of more and more scientist.And the method the most effectively realizing carbon-hydrogen bond activation is transition metal-catalyzed cross-coupling reaction.As Suzuki reaction, Heck reacts, Domino reaction etc., after deliberation very ripe at present.And in these cross-coupling reactions, palladium catalyst plays vital effect undoubtedly.As follows for example, just by the catalysis of palladium catalyst, in molecule and intermolecular Heck reaction, realize the carbon-hydrogen bond activation of acetylene bond, a step forms three new carbon-carbon bonds, defines new six-ring compound.Inherently save reactions steps, improve the utilization ratio of atom.
The method of several synthesis of cyclic compounds in sum, due to the existence of ring strain, five yuan and hexa-atomicly more easily to synthesize because its ring strain is less.
Norbornylene (NBE) is a kind of important cyclic olefin polymerization monomer, and due to the singularity of its structure, it can carry out polyreaction in three different ways, and it is also different that it reacts the product characteristics obtained.Early start will trace back to the 1950's to the research of cycloolefin catalyzed polymerization, Anderson and Meckling utilized TiCl at that time
4-LiAlR
4system catalyzing N BE polymerization obtain ring-opening polymerization polymer, subsequently to norbornylene research be mostly utilize excessive metalcatalyzing ring-opening polymerization to obtain elastopolymer.Norbornylene addition polymers has excellent electrical property, extremely low water absorbability, good thermostability, higher tension fracture value and low-tension, to metal, there is good adhesive, very strong anti-ultraviolet radiation ability, excellent optical property, in halogenated aryl hydrocarbon, there is good solubility, be widely used in industrial production.At present, having 4 enterprises to achieve norbornene polymerization industrialization in the world, is the Ticona company of Germany, Japanese Zeon company, Mitsui Chemicals, Inc. and JSR company respectively.
The synthesis of norbornene derivative has high value of practical and theory value as can be seen here.
Summary of the invention
The object of the present invention is to provide a kind of norbornylene addition polymerization derivative and preparation method thereof, concrete technical scheme is as follows:
A kind of norbornylene addition polymerization derivative, its structural formula is:
Described R can be hydrogen, straight chained alkyl, branched-chain alkyl, cyano group, amino etc. and its corresponding derivative.
Further, the structural formula of benzo ring butanone is:
Namely described R is hydrogen.
Further, it is polysubstituted norbornylene addition polymerization derivative.
Further, it is the norbornene derivative of efficient synthesis containing six-ring.
The preparation method of above-mentioned norbornylene addition polymerization derivative, comprises the steps:
A. precursor synthesis;
B. palladium chtalyst;
C. purifying.
Further, concrete steps can be: under anhydrous and oxygen-free condition, in the reaction flask of 100 ml, add the reaction substrate of 5 mmol successively, the norbornylene of 7 mmol, the Et of 2 mL
3n, the DMF of 7 mL, the palladium of 2 mol %, reacts 24 h, after reactant is added water washing, be extracted with ethyl acetate, organic phase that sub-argument goes out successively with 5% hydrochloric acid, the solution of potassium carbonate of 5%, saturated common salt water washing, decompression is spin-dried for, and obtains desired product, i.e. norbornene derivative with column chromatography.
Further, step a comprises the steps: under the condition of anhydrous and oxygen-free, by 20 mmol 1,6 diine substrates, 48 mmol
(R=Cl, F, CH3, OCH3, H, CO2Et), 842 mg(1.2 mmol) PdCl
2(PPh)
2with 457.2 g(2.4 mmol) CuI be placed in 150 mL round-bottomed flasks, add the acetonitrile as solvents of about 100 mL; Stir after half an hour, under the condition of ice-water bath, drip or pin note 16.8 mL(120 mmol with constant pressure funnel) triethylamine, reinforced complete, react 10 hours; Remove reaction, be extracted with ethyl acetate; Boil off solvent, all obtain faint yellow solid with silica gel column chromatography separating-purifying, compound 1.
Further, under step b comprises the steps: anhydrous and oxygen-free condition, in the reaction flask of 100 ml, add the reaction substrate of 5 mmol successively, the norbornylene of 7 mmol, the Et of 2 mL
3n, the DMF of 7 mL, the palladium of 2 mol %, reacts 24 h under certain temperature of reaction, after reactant is added water washing, be extracted with ethyl acetate, organic phase that sub-argument goes out successively with 5% hydrochloric acid, the solution of potassium carbonate of 5%, saturated common salt water washing, decompression is spin-dried for, and obtains desired product with column chromatography, compound 2.
Further, after step c comprises the steps: that the crude product of norbornene derivative adds water washing, be extracted with ethyl acetate, isolated organic phase successively uses 5% hydrochloric acid soln, 5% solution of potassium carbonate, saturated common salt water washing, decompression selects dry chromatography to be separated can obtain purified compound 2, i.e. norbornene derivative
Further, in step a, product Compound 1 carries out sign with nuclear-magnetism and determines, or in step c, column chromatography productive rate is about 61%.
Compared with currently available technology, the invention provides a kind of synthetic method of brand-new norbornylene addition polymer, generate a series of new norbornene derivative.Relative to common norbornene compound, norbornene derivative prepared by present method has the existence of carbonyl, and no matter from producing or the angle of theory, ester class all occupies extremely important status, many ester classes are important industrial raw material, produce with very huge quantity, some is spices or important product, and the norbornene derivative therefore synthesized by the present invention still has certain purposes in real life.
Chemically in performance and at various synthetic use, ester class all occupies special critical positions, and often they are beginning raw materials of synthesis.Synthetic work person has a kind of like this understanding, be exactly had an ester group or aldehyde radical in the molecule, this molecule just becomes has lived, molecule is just provided with easily by the position of attack, starting point is made with this position, carry out next step reaction, the norbornene derivative therefore synthesized by the present invention also has certain value in theoretical investigation.
The application prospect of norbornene derivative in organic synthesis field still very widely thus.
Accompanying drawing explanation
Fig. 1 a, Fig. 1 b is norbornylene addition polymerization derivant structure formula
Fig. 2 a, Fig. 2 b is the proton nmr spectra of the embodiment of the present invention
Embodiment
Describe the present invention with reference to the accompanying drawings below, it is a kind of preferred embodiment in numerous embodiments of the present invention.
A kind of norbornene derivative, its structural formula of described norbornene derivative is:
Described R can be hydrogen, straight chained alkyl, branched-chain alkyl, cyano group, amino etc. and its corresponding derivative.
The structural formula of preferred benzo ring butanone is:
Namely described R is hydrogen
Preparation method of the present invention is: the synthesis of a, precursor, b, palladium chtalyst, c, purifying.
Described a, precursor synthesize:
Under the condition of anhydrous and oxygen-free, by 20 mmol 1,6 diine substrates, 48 mmol
(R=Cl, F, CH3, OCH3, H, CO2Et), 842 mg(1.2 mmol) PdCl
2(PPh)
2with 457.2 g(2.4 mmol) CuI be placed in 150 mL round-bottomed flasks, add the acetonitrile as solvents of about 100 mL.Stir after half an hour, under the condition of ice-water bath, drip or pin note 16.8 mL(120 mmol with constant pressure funnel) triethylamine, reinforced complete, react 10 hours.Remove reaction, be extracted with ethyl acetate.Boil off solvent, all obtain faint yellow solid with silica gel column chromatography separating-purifying, compound 1, product nuclear-magnetism carries out sign and determines
Described b, palladium chtalyst are:
Under anhydrous and oxygen-free condition, in the reaction flask of 100 ml, add the reaction substrate of 5 mmol successively, the norbornylene of 7 mmol, the Et of 2 mL
3n, the DMF of 7 mL, the palladium of 2 mol %, reacts 24 h under certain temperature of reaction, after reactant is added water washing, be extracted with ethyl acetate, organic phase that sub-argument goes out successively with 5% hydrochloric acid, the solution of potassium carbonate of 5%, saturated common salt water washing, decompression is spin-dried for, and obtains desired product, compound 2 with column chromatography (ethyl acetate: sherwood oil=1:10).
Compound 1
Compound 1 compound 2
Described c, purifying are:
After the crude product of norbornene derivative adds water washing, be extracted with ethyl acetate, isolated organic phase successively uses 5% hydrochloric acid soln, 5% solution of potassium carbonate, saturated common salt water washing, decompression selects dry chromatography to be separated the compound 2 that can obtain our needs, i.e. norbornene derivative, column chromatography productive rate is about 61%.
In another preferred embodiment, the synthesis of norbornene derivative: as shown in synthetic route:
A, precursor synthesize:
Under the condition of anhydrous and oxygen-free, by 20 mmol 1,6 diine substrates, 48 mmol
(R=Cl, F, CH3, OCH3, H, CO2Et), 842 mg(1.2 mmol) PdCl
2(PPh)
2with 457.2 g(2.4 mmol) CuI be placed in 150 mL round-bottomed flasks, add the acetonitrile as solvents of about 100 mL.Stir after half an hour, under the condition of ice-water bath, drip or pin note 16.8 mL(120 mmol with constant pressure funnel) triethylamine, reinforced complete, react 10 hours.Remove reaction, be extracted with ethyl acetate.Boil off solvent, all obtain faint yellow solid with silica gel column chromatography separating-purifying, compound 1, product nuclear-magnetism carries out sign and determines
Described b, palladium chtalyst are:
Under anhydrous and oxygen-free condition, in the reaction flask of 100 ml, add the reaction substrate of 5 mmol successively, the norbornylene of 7 mmol, the Et of 2 mL
3n, the DMF of 7 mL, the palladium of 2 mol %, reacts 24 h under certain temperature of reaction, obtains norbornene derivative crude product.
C, purifying:
After the crude product of norbornene derivative adds water washing, be extracted with ethyl acetate, isolated organic phase successively uses 5% hydrochloric acid soln, 5% solution of potassium carbonate, saturated common salt water washing, decompression selects dry chromatography to be separated the compound 2 that can obtain our needs, i.e. benzocyclobutane ketone derivatives, column chromatography productive rate is about 61%.
The structure of norbornene derivative is passed through;
1h NMR;
13c NMR; HRMS; IR measures.
Norbornene derivative:
Dimethyl4,9-diphenyl-4a,5,6,7,8,8a-hexahydro-1H-5,8-methanocyclopenta[b]naphthalene-2,2(3H)-dicarboxylate
1H NMR (300 MHz, CDCl
3): δ 7.28-7.37 (m, 10H; Ar-H), 3.80 (s, 6H; -O-CH
3 ), 3.26 (s, 4H; -CH
2-), 2.37-2.41 (t, J = 7.5 Hz, 2H; -CH-), 1.36-1.43 (m, 2H; -CH
2-), 1.25-1.32 (m, 2H; -CH-), 0.88-0.93 (m, 4H; -CH
2-);
13C NMR (75 MHz, CDCl
3): δ 169.43, 131.72, 128.25,128.12, 123.06, 83.92, 83.86, 57.30, 53.15, 52.33, 25.94, 23.87, 20.38 ppm.
FT-IR (KBr): 2955(board), 2374, 1740, 1490, 1435, 1292, 1209, 1072, 756 cm
-1;HRMS (APCI): m/z [M + H]
+ calcd for C
46H
41O
8: 721.2723; found: 721.0302
Above by reference to the accompanying drawings to invention has been exemplary description; obvious specific implementation of the present invention is not subject to the restrictions described above; as long as have employed the various improvement that method of the present invention is conceived and technical scheme is carried out; or directly apply to other occasion, all within protection scope of the present invention without improving.
Claims (1)
1. a preparation method for norbornylene addition polymerization derivative, is characterized in that:
Described norbornylene addition polymerization derivative is benzo ring butanone, and its structural formula is:
The preparation method of described benzo ring butanone comprises the steps:
A. precursor synthesis;
B. palladium chtalyst;
C. purifying;
Wherein, step a comprises the steps: under the condition of anhydrous and oxygen-free, and by 20mmol1,6 diine substrates, structure is
wherein E is COOMe, 48mmol
(R=H), the PdCl2 (PPh) 2 of 842mg (1.2mmol) and the CuI of 457.2mg (2.4mmol) is placed in 150mL round-bottomed flask, adds the acetonitrile as solvents of about 100mL; After stirring half an hour, under the condition of ice-water bath, note the triethylamine of 16.8mL (120mmol) with constant pressure funnel dropping or pin, reinforced complete, react 10 hours; Remove reaction, be extracted with ethyl acetate; Boil off solvent, all obtain faint yellow solid, i.e. reaction substrate with silica gel column chromatography separating-purifying;
Under step b comprises the steps: anhydrous and oxygen-free condition, in the reaction flask of 100ml, add the reaction substrate of 5mmol successively, the norbornylene of 7mmol, the Et of 2mL
3the palladium of the DMF of N, 7mL, 2mol%, reacts 24h under certain temperature of reaction, obtains the crude product of norbornene derivative;
After step c comprises the steps: that the crude product of norbornene derivative adds water washing, be extracted with ethyl acetate, isolated organic phase successively uses 5% hydrochloric acid soln, 5% solution of potassium carbonate, saturated common salt water washing, decompression is spin-dried for column chromatography for separation and can obtains purifying norbornene derivative;
Wherein, in step a, product nuclear-magnetism carries out sign and determines, in step c, column chromatography productive rate is about 61%, and the structure of described norbornene derivative is passed through
1h NMR;
13c NMR; HRMS; IR measures.
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