CN103382153B - Norbornene addition polymerization derivative and its preparation method - Google Patents

Norbornene addition polymerization derivative and its preparation method Download PDF

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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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norbornene derivative
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addition polymerization
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CN103382153A (en
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胡益民
章雨龙
谢海凤
赵全胜
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Anhui Normal University
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Anhui Normal University
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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

A kind of norbornylene addition polymerization derivative and preparation method thereof
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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