CN1112251C - Soluble high-molecular catalyst, synthesizing process and use thereof - Google Patents

Soluble high-molecular catalyst, synthesizing process and use thereof Download PDF

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CN1112251C
CN1112251C CN 01105409 CN01105409A CN1112251C CN 1112251 C CN1112251 C CN 1112251C CN 01105409 CN01105409 CN 01105409 CN 01105409 A CN01105409 A CN 01105409A CN 1112251 C CN1112251 C CN 1112251C
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CN1319453A (en
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唐勇
黄峥峥
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Shanghai Institute of Organic Chemistry of CAS
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Abstract

The present invention provides a soluble polymer catalyst, namely polyethylene glycol supported tellurium (B), arsenic (C) and sulfur (B), and tellurium oxygen, and arsenic oxygen, sulfur oxygen, tellurium salt, arsenic salt, sulfur salt, arsenic ylide, tellurium ylide or sulfur ylide compounds. The catalyst is prepared from reaction products of polyethylene glycol and sulfonic acid halide or other halide, or polyglycol sulfonate products with one end protected by alkoxy groups or halide and metal reagents containing As, Te or S by reaction or prepared by further salt formation, negative ion exchange, ylide formation or oxidation. The catalyst can be used for catalyzing ylide olefination and ylide small cyclization reaction.

Description

A kind of soluble high-molecular catalyst, synthetic method and purposes
Technical field
The invention belongs to a class soluble high-molecular catalyst and a preparation method and use thereof, this specifically catalyst is with solubility high polymer-corresponding soluble high-molecular tellurium of polyethylene glycol load (II), arsenic (III), sulphur (II), tellurium oxygen, arsenic oxygen, sulphur oxygen, tellurium salt, arsenic salt, sulfosalt, arsenic ylide, tellurium ylide, sulphur ylide compound.
Background technology
In recent years, the polymers carrier comes across combinatorial chemistry more and more, (Fruchtel, J.S. in organic synthesis and the catalytic reaction; Jung, G.Angew.Chem., Int.Ed.Engl., 1996,35,17; Thompson, L.S.; Ellman, J.A.Chem.Rev., 1996,96,555.).For insoluble cross-linked polymer carrier, using the solubility polymer support can make to be reflected in the homogeneous phase carries out, and can make reaction reagent or catalyst recovery utilization again, have homogeneous reaction (high reaction activity concurrently, easily follow the tracks of etc.) and solid phase reaction (easily separated, easy purifying etc.) advantage, thereby caused people's attention.Because the polyethylene glycol loaded article of certain molecular weight can be dissolved in DMF, carrene, toluene, acetonitrile etc., and be insoluble to ether, tertbutyl ether, isopropyl alcohol (Zhao, X.Y.; Metz, W.A.; Sieber, F.; Janda, K.D.Tetrahedron Lett., 1998,39,8433.) and cold ethanol.Therefore polyethylene glycol is considered to preferably the solubility polymer support and is applied to (Muther, M. in the organic synthesis; Hagenmaier, H.; Bayer, E.Angew.Chem., Int.Ed.Engl., 1971,10,811.Bayer, E.; Mutter, M.Nature, 1972,237,512.).
Simultaneously, all can be used as catalyst (Shi, L.L.Wang, the W.B. of Ylide reaction according to the little molecule arsenic of reported in literature, tellurium, sulphur compound; Wang, Y.C.; Huang, Y.Z.J.Org.Chem., 1989,54,2028.Huang, Y.Z.; Shi, L.L.; Li, S.W.; Wen, X.Q.J.Chem.Soc., Perkin Trans.I, 1989,2397.Zhou, Z.L.; Shi, L.L.; Huang, Y.Z.Tetrahedron Lett., 1990,31,7657.Li, A.H.; Dai, L.X.; Hou, X.L.J.Chem.Soc., Perkin Trans.I, 1996,9,867.).But these little molecular agents all have certain toxicity, as: arsenic, tellurium compound, and volatile, foul smelling, as: tellurium, sulphur compound.Brought certain potential hazard for their application.
Summary of the invention
The object of the present invention is to provide a class soluble high-molecular catalyst.
Two of purpose of the present invention is to provide the synthetic method of such soluble high-molecular catalyst.
Three of purpose of the present invention is to provide the purposes of such soluble high-molecular catalyst, i.e. the performance-oriented catalyst that reacts as the ylide moral.
The invention provides a class and be used for the catalyzing Ylide olefination, the soluble high-molecular catalyst of the little cyclization of ylide, this catalyst has realized that soluble high-molecular carrier polyethylene glycol is to tellurium (II), arsenic (III), sulphur (II), the load of tellurium oxygen, arsenic oxygen, sulphur oxygen, tellurium salt, arsenic salt, sulfosalt, arsenic ylide, tellurium ylide, sulphur ylide compound, its molecular formula are (C 2H 4O) nA, wherein (C 2H 4O) be the polyethylene glycol structures unit, n is 2-2000, A=(C 2H 4) (MR) 2Or (C 2H 4MR) OR 1, M=M ' or M ' (O), M '=As, Te or S, R 1=C 1-10Alkyl, R=R 2 q, R 2 qCH (R 3) R 4X or R 2 qC (R 3) R 4, R 2=C 1-30Alkyl, C 1-30Contain heteroatomic various alkyl, C 1-30Aryl or C 1-30Substituted aryl, described hetero atom is N, O or S, R 3=H or C 1-10Alkyl, R 4Be electron withdraw group, q equals 1 or 2, X=X ', ClO 4 -Or BF 4 -, X '=I -, Cl -Or Bt -Described electron withdraw group is C 1-20Alkanoyl, aroyl, replacement aroyl, benzenesulfonyl, benzene sulfoxide group, ester group, thiazolinyl, substituted alkenyl, alkene ester group, cyano group, nitro, amide groups, aryl, substituted aryl or its corresponding vinylogy base, wherein the group of above-mentioned replacement can be halogen, low carbon chain alkyl, nitro, silylation etc.Polyethylene glycol structures (C in the described catalyst 2H 4O) nC 2H 4With link to each other with chemical bond between the group that contains arsenic, tellurium or sulphur.
Specifically, catalyst of the present invention can be R 2 qM ' (C 2H 4O) nC 2H 4M ' R 2 q, XR 4(R 3) CH (R 2 q) M ' (C 2H 4O) nC 2H 4M ' (R 2 q) CH (R 3) R 4X, R 4(R 3) C -(R 2 q) M ' +(C 2H 4O) nC 2H 4M ' +(R 2 q) C -(R 3) R 4, R 2 q(O) M ' (C 2H 4O) nC 2H 4M ' is R (O) 2 q, R 1O (C 2H 4O) nC 2H 4M ' R 2 q, R 1O (C 2H 4O) nC 2H 4M ' (R 2 q) CH (R 3) R 4X, R 1O (C 2H 4O) nC 2H 4M ' +(R 2 q) C -(R 3) R 4And R 1O (C 2H 4O) nC 2H 4M ' is R (O) 2 q, R wherein 1, R 2, R 3, R 4, M ', X, n, q as previously mentioned.R wherein 1, R 2, R 3, R 4, M ', X, n, q as previously mentioned.
The synthetic available following formula of this class catalyst is described:
Figure C0110540900061
Concrete synthesis step is as follows:
Under the effect of alkali, a kind of polar solvent, under non-polar solven or the solvent-free existence, in-40 ℃ to 100 ℃ the temperature range, mean molecule quantity is the polyethylene glycol HO (C of 200-5 ten thousand 2H 4O) N+1H or R 1O (C 2H 4O) N+1H and molecular formula are R 5SO 2The acetyl halide compound of X reacts, wherein R 5=C 1-10Alkyl, C 1-10Contain heteroatomic various alkyl, C 1-10Aryl or C 1-10Substituted aryl, as p-methyl benzene sulfonic chloride, benzene sulfonyl chloride, to trifluoro-benzene sulfonic acid chloride, mesyl chloride etc.; Perhaps polyethylene glycol and halogenating agent react, wherein said halogenating agent such as phosphorus tribromide, phosphorus pentabromide, thionyl chloride etc.The mol ratio of described polyethylene glycol and acetyl halide compound or halogenating agent is: 1: 1.0-30.0, reaction a few minutes-72 hour.The molecular formula of the product that obtains is (C 2H 4O) n(C 2H 4OSO 2R 5) 2, (C 2H 4O) n(C 2H 4X ') 2, R 1O (C 2H 4O) nC 2H 4OSO 2R 5Or R 1O (C 2H 4O) nC 2H 4X ', wherein n is 2-2000.Productive rate can reach 100%.The organic base that uses for example contains the amine of lone pair electrons on the N atom, and the inorganic base of use is the mixture etc. of hydroxide, hydride, carbonate, pure alkali, above-mentioned alkali and the aluminium oxide of alkali metal lithium, sodium or potassium for example.Polyethylene glycol is recommended as 1 with the mole dosage ratio of above-mentioned alkali: 1-100.
Compound (C 2H 4O) n(C 2H 4OSO 2R 5) 2, (C 2H 4O) n(C 2H 4X ') 2, R 1O (C 2H 4O) nC 2H 4OSO 2R 5Or R 1O (C 2H 4O) nC 2H 4X ' is R with the on-the-spot molecular formula that generates 2 qThe mol ratio of the compound of M ' Y is 1.0: 1.0-30.0, polar solvent, non-polar solven or solvent-free in the presence of, reaction is 0.5-72 hour in the time of-100 ℃ to 200 ℃, obtains molecular formula and is (C 2H 4O) n(C 2H 4M ' R 2 q) 2Or R 1O (C 2H 4O) nC 2H 4M ' R 2 qCatalyst, wherein Y=ZnX ', MgX ', Na or Li etc.Productive rate can reach more than 80%.Molecular formula is R 2 qThe compound of M ' Y can be made by tellurium powder or mercaptan etc. and alkyl metal cpd reaction, or RMgBr etc.
In the time of-78 ℃ to 100 ℃, (C 2H 4O) n(C 2H 4M ' R 1 q) 2Or R 1O (C 2H 4O) nC 2H 4M ' R 2 qWith molecular formula be R 3(R 4) the halid mol ratio of CHX ' is 1: 1.0-30.0, reacted 0.5-72 hour, obtain molecular formula and be (C 2H 4O) n[C 2H 4M ' (R 2 q) CH (R 3) R 4X '] 2Or R 1O (C 2H 4O) nC 2H 4M ' (R 2 q) CH (R 3) R 4The catalyst of X.
(C 2H 4O) n[C 2H 4M ' (R 2 q) CH (R 3) R 4X '] 2Or R 1O (C 2H 4O) nC 2H 4M ' (R 2 q) CH (R 3) R 4X ' is 1 with the mol ratio of inorganic salts: 1-10, carried out the anion exchange reaction 0.5-72 hour at-78 ℃ to 100 ℃, and obtain molecular formula and be (C 2H 4O) n[C 2H 4M ' (R 2 q) CH (R 3) R 4X] 2Or R 1O (C 2H 4O) nC 2H 4M ' (R 2 q) CH (R 3) R 4The catalyst of X, described inorganic salts are as AgCl0 4, AgBF 4, NaI, KI etc. contain ClO 4 -, BF 4 -Or I -Inorganic salts;
(C 2H 4O) n[C 2H 4M ' (R 2 q) CH (R 3) R 4X] 2Or R 1O (C 2H 4O) nC 2H 4M ' (R 2 q) CH (R 3) R 4The mol ratio 1 of X and alkali: 1-10-78 ℃ to 100 ℃ reactions 0.5-72 hour, obtains molecular formula and is (C 2H 4O) n[C 2H 4M ' +(R 2 q) C -(R 3) R 4] 2Or R 1O (C 2H 4O) nC 2H 4M ' +(R 2 q) C -(R 3) R 4The catalyst of X, described alkali can be the mixtures of alkali-metal hydroxide, hydride, carbonate, pure alkali or above-mentioned alkali and aluminium oxide etc.
(C 2H 4O) n(C 2H 4M ' R 2 q) 2Or R 1O (C 2H 4O) nC 2H 4M ' R 2 qWith oxidant, perhaps R 1O (C 2H 4O) nC 2H 4M ' (R 2 q) C (R 3) R 4Or (C 2H 4O) n[C 2H 4M ' (R 2 q) C (R 3) R 4] 2With the mol ratio of electrophilic reagent be 1: 1-10-78 ℃ to 100 ℃ reactions 0.5-72 hour, obtains molecular formula for (C 2H 4O) n[C 2H 4M ' is R (O) 2 q] 2Or R 1O (C 2H 4O) nC 2H 4M ' is R (O) 2 qCatalyst, described oxidant such as BuCl0, N-chlorosuccinimide etc., described electrophilic reagent is an aldehydes or ketones, for example substituting group is C 1-C 20Alkyl or the aldehydes or ketones of substituted hydrocarbon radical, aryl, substituted aryl, heteroaryl, cycloalkyl or its corresponding vinylogy base.
R wherein 1, R 2, R 3, R 4, X ', X, M ', q, n as previously mentioned.Above-mentioned solvent can be oxolane, toluene, acetonitrile, water, low carbon chain alcohol or N, dinethylformamide etc.The consumption of halide, alkali, oxidant or electrophilic reagent also can increase in the above-mentioned reaction.
(C wherein 2H 4O) n[C 2H 4M ' is R (O) 1 q] 2Or R 1O (C 2H 4O) nC 2H 4M ' is R (O) 2 qReducible again under the effect of reducing agent is (C 2H 4O) n(C 2H 4M ' R 1 q) 2, it is capable of circulation that whole process is become.
Soluble high-molecular catalyst of the present invention can be used as the effective catalyst of Ylide reaction, is used for the catalyzing Ylide olefination, little cyclization of ylide such as epoxidation, Cyclopropanated, aziridine reaction etc.
The present invention has realized solubility arsenic, arsenic oxygen, the arsenic salt compound of soluble high-molecular compound polyethylene glycol load first, tellurium, tellurium oxygen, tellurium salt compound and sulphur, sulphur oxygen, sulfosalt compound reagent synthetic is for the soluble high-molecular reagent of the 5th, the 6th major element synthetic provides an efficient and simple and direct approach.This class reagent can be used as the effective catalyst of Ylide reaction, is applicable to suitability for industrialized production and application.
The specific embodiment
Help further to understand the present invention by following example.
Embodiment 1
Compound (Me (C 6H 4) SO 2-PEG-SO 2(C 6H 4) Me) and preparation
(30 grams, mean molecule quantity is 3000, in carrene 10mmol) (80mL) solution, adds triethylamine (5ml or 50mL, 36mmol or 360mmol) in polyethylene glycol.After mixing, add paratoluensulfonyl chloride (chemical pure) under 0 ℃ (25 restrain, 120mmol) in batches.Behind the stir about 10 minutes, rise to room temperature naturally and stir and to spend the night or reaction one hour under reflux temperature.
Filter fast with thick silica gel (100-200 order), filter residue with washed with dichloromethane for several times.Filtrate merges, and is concentrated into pasty state.(1600mL) separates out white solid in ether.Suction filtration, isopropyl alcohol (200mL) fully washs this solid matter.Obtain 33 gram white powder solids.Productive rate 99%.
1H NMR(CDCl 3)：7.81(d，J＝8.0Hz，4H)；7.35(d，J＝8.0Hz，4H)；4.16(t，J＝4.8Hz，4H)；3.88-3.41(m，≈280H)；2.45(s，6H)。
The same method makes compound (MeSO 2-PEG-SO 2Me).Productive rate 98%.
With toluene is solvent, and triethylamine consumption 100mL (720mmol), paratoluensulfonyl chloride (chemical pure) consumption are 50 grams (240mmol), react 72 hours, and other reaction condition is the same, preparation compound (MeSO 2-PEG-SO 2Me).Productive rate 91%.
Solubilizer not, the triethylamine consumption is 100mL (720mmol), and paratoluensulfonyl chloride (chemical pure) consumption is 50 grams (240mmol), react 3 hours, and other reaction condition is the same, prepares compound (MeSO 2-PEG-SO 2Me).Productive rate 93%.
Replace triethylamine with inorganic base sodium hydride (240mmol), paratoluensulfonyl chloride (chemical pure) consumption is 50 grams (240mmol), reacts 72 hours, and other reaction condition is the same, preparation compound (MeSO 2-PEG-SO 2Me).Productive rate 90%.
1H NMR(CDCl 3)：4.13(t，J＝6.9Hz，4H)；3.91(d，J＝6.9Hz，4H)；3.41-3.88(m，≈280H)；2.94(s，6H)。
Embodiment 2
The preparation of compound (Br-PEG-Br)
Oxolane (80mL) solution in polyethylene glycol (30 grams grind to form fine-powdered, about 10mmol) adds pyridine (29mL or 58ml, 360mmol or 720mmol).After mixing, at 0 ℃ of tetrahydrofuran solution (120mmol) that drips halogenating agent down.Stir about 10 minutes removes ice-water-bath and allows reaction system heat up naturally and stir and spend the night, or in 100 ℃ of reactions 1 hour.
Filter fast with thick silica gel (100-200 order), filter residue with washed with dichloromethane for several times.Filtrate merges, and is concentrated into pasty state.(1600mL) separates out white solid in ether.Suction filtration, isopropyl alcohol (200mL) fully washs this solid matter.
When the halogenating agent in the reaction is phosphorus tribromide, obtain 31.3 gram white powder solids.Productive rate 99%.
1H NMR(CDCl 3)：3.24-3.88(m，≈280H)；
Replace halogenating agent with thionyl chloride, other reaction condition is the same, makes Cl-PEG-Cl.(14.3 grams, 120mmol).Reaction yield: 30.1 grams (98%).
1H NMR(CDCl 3)：3.24-3.88(m，≈280H)
Embodiment 3
The preparation method 1 of the tellurium of polyethylene glycol load (II) compound: in ice-water-bath, the hexane solution (55mmol) of lithium alkylide dropwise is added in 250mL oxolane (the new processing) suspension of 6.1250 grams or 0.6125 gram (48mmol or 4.8mmol) tellurium powder.Stir reaction down.Treat that the tellurium powder disappears, reaction system is cooled to-78 ℃, dropping has been dissolved 10 and has been digested compound Me (C 6H 4) SO 2-PEG-SO 2(C 6H 4) the tetrahydrofuran solution 120mL of Me (3mmol).Keep this temperature, reacted 8 hours.
After reaction finishes, heat up naturally, remove and desolvate.Residue obtained with carrene (40mL) dissolving, diatomite filtration, filtrate is concentrated into pasty state.In ether (2000mL), separate out the white powder solid.
Make the tellurium compound (BuTe-PEG-TeBu) of polyethylene glycol load: 8.4 grams (83%).The lithium reagent of using in the reaction is: and n-BuLi (41.5mL, C=1.33mol/L). 1H NMR(CDCl 3/TMS)δ3.90-3.40(m，≈280H)；2.80(t，J＝7.6Hz，4H)；2.66(t，J＝7.4Hz，4H)；1.75-1.70(m，4H)；1.39-1.36(m，4H)；0.92(t，J＝7.2Hz，6H)。 125Te(CDCl 3/Me 2Te)：200.2PPm。
Make Compound C with quadrat method 20H 41Te-PEG-TeC 20H 41: 9.15 grams (80%).The lithium reagent of using in the reaction is: C 20H 41Li (58mL, hexane solution C=1.0mol/L).
1H NMR(CDCl 3/TMS)δ0.91(s，6H)；0.99-1.60(m，72H)；2.43(t，J＝7.1Hz，4H)；2.56(t，J＝7.0Hz，4H)；3.70-3.26(m，≈284H)。Method 2: in the ethanolic solution of NaTeBu (48 mL, C=1mol/L) in, drip compound MeO-PEG-SO 2(C 6H 4) Me (9.6 grams, oxolane 3mmol) (120mL) solution.Keep this temperature, reacted 8 hours.
After reaction finishes, heat up naturally, remove and desolvate.Residue obtained with carrene (40mL) dissolving, diatomite filtration, filtrate is concentrated into pasty state.In ether (2000mL), separate out the white powder solid.
Make the tellurium compound (MeO-PEG-TeBu) of polyethylene glycol load: 8.2 grams (85%).The lithium reagent of using in the reaction is: and n-BuLi (41.5mL, C=1.33mol/L). 1H NMR(CDCl 3/TMS)δ3.90-3.40(m，≈280H)；3.38(s，3H)；2.80(t，J＝7.6Hz，2H)；2.66(t，J＝7.4Hz，2H)；1.75-1.70(m，2H)；1.39-1.36(m，2H)；0.92(t，J＝7.2Hz，3H)。
Embodiment 4
The preparation of the arsenic of polyethylene glycol load (III) compound
In ice-water-bath, the tetrahydrofuran solution 5mL of the RMgBr that the scene is generated, be added dropwise to dibromide Br-PEG-Br (9.48 grams of above-mentioned polyethylene glycol, 0.003mol) tetrahydrofuran solution 20mL, keep being reflected in ice-water-bath reaction and rise to room temperature naturally after 8 hours and reacted again 12 hours, perhaps reacted 1 hour at 150 ℃.
After reaction finishes, remove and desolvate.Residue obtained with carrene (40mL) dissolving, diatomite filtration, filtrate is concentrated into pasty state.In ether (1500mL), separate out the white powder solid.Productive rate:.
Make the arsenic compound ((C of polyethylene glycol load 6H 5CH 2CH 2) 2As-PEG-As (CH 2CH 2C 6H 5) 2): 8.56 grams (80%).RMgBr used in the reaction is: (C 6H 5CH 2CH 2) 2AsMgCl (17.2 grams, 0.05mol) 1H NMR (CDCl 3/ TMS) δ 7.41-6.86 (m, 20H); (3.80-3.30 m, ≈ 284H); 2.47 (t, J=7.2Hz, 8H); 1.67 (t, J=7.2Hz, 8H); 1.54 (t, J=6.9Hz, 4H).
The same method makes compound ((m-CH 3C 6H 4CH 2CH 2) 2As-PEG-As (CH 2CH 2C 6H 4CH 3-m) 2): 8.38 grams (77%).RMgBr used in the reaction is: (p-CH 3C 6H 4CH 2CH 2) 2AsMgCl (18.6 grams, 0.05mol). 1H NMR(CDCl 3/TMS)δ7.36-6.89(m，16H)；3.82-3.30(m，≈284H)；2.61-2.25(m，8H)；2.23(s，12H)；1.67(t，J＝7.2Hz，8H)；1.64(t，J＝6.9Hz，8H)。
The same method makes compound ((o-NO 2C 6H 4CH 2CH 2) 2As-PEG-As (CH 2CH 2C 6H 4NO 2-o) 2): 8.30 grams (75%).RMgBr used in the reaction is: (o-NO 2C 6H 4CH 2CH 2) 2AsMgCl (20.2 grams, 0.05mol). 1H NMR(CDCl 3/TMS)δ7.81-7.01(m，16H)；3.90-3.20(m，≈284H)；2.59-2.20(m，8H)；1.66(t，J＝6.6Hz，8H)；1.63(t，J＝7.2Hz，8H)。
The same method makes compound ((p-BrC 6H 4CH 2CH 2) 2As-PEG-As (CH 2CH 2C 6H 4Br-p) 2): 8.38 grams (75%).RMgBr used in the reaction is: (o-NO 2C 6H 4CH 2CH 2) 2AsMgCl (21.1 grams, 0.05mol). 1H NMR(CDCl 3/TMS)δ7.71-7.47(m，8H)；7.27-7.05(m，8H)；3.80-3.30(m，≈284H)；2.68-2.28(m，8H)；1.66(t，J＝7.2Hz，8H)；1.64(t，J＝7.0Hz，8H)。
The same method makes compound ((CH 3CH=CHCH 2CH 2) 2As-PEG-As (CH 2CH 2CH=CHCH 3) 2): 7.81 grams (76%).RMgBr used in the reaction is: (CH 3CH=CHCH 2CH 2) 2AsMgCl (13.6 grams, 0.05mol). 1H NMR(CDCl 3/TMS)δ5.64(dq，J＝14.0Hz，7.2Hz，4H)；4.24(dt，J＝14Hz，6.8Hz，4H)；3.72-3.48(m，≈288H)；2.29-1.90(m，8H)；1.67(t，J＝7.2Hz，4H)；1.61(d，J＝7.2Hz，12H)；1.46(t，J＝6.8Hz，8H)。
The same method makes compound ((C 2H 5) 2C=CHCH 2CH 2) 2As-PEG-As (CH 2CH 2CH=C (C 2H 5) 2) 2): 7.83 grams (73%).RMgBr used in the reaction is: ((C 2H 5) 2CH=CHCH 2CH 2) 2AsMgCl (17.9 grams, 0.05mol). 1H NMR(CDCl 3/TMS)δ4.14(t，J＝6.0Hz，4H)；3.70-3.43(m，≈288H)；2.33-1.79(m，8H)；1.67(t，J＝7.2Hz，4H)；1.63(s，24H)；1.61-1.27(m，8H)。
Embodiment 5
The preparation of the sulphur of polyethylene glycol load (II)
In ice-water-bath, (1.27 restrain, and drip the tetrahydrofuran solution 100mL of mercaptan compound (48.0mmol) among oxolane suspension 100mL 52.8mmol) in NaH.Stir reaction down 4 hours.Drip compound MeSO 2-PEG-SO 2Me (9.5 grams, THF 3.0mmol) (120mL) solution.Reaction is spent the night.
After reaction finishes, heat up naturally, remove and desolvate.Residue obtained with carrene (40mL) dissolving, diatomite filtration, filtrate is concentrated into pasty state.In ether (1600mL), separate out the white powder solid.
Make the sulphur compound (CH of polyethylene glycol load 3O (C 2H 4O) 5CH 2CH 2S-PEG-SCH 2CH 2(C 2H 4O) 5OCH 3).Productive rate: 8.5 grams (75%).The mercaptan compound that reacts used is: CH 3O (C 2H 4O) 5CH 2CH 2SH (18.6 grams, 48.0mmol).
Above-mentioned reaction is adopted solvent-free process that various reactants are mixed the back and is ground, and the NaH consumption is that (2.54 grams, 105.6mmol) the used mercaptan compound of reaction is: CH 3O (C 2H 4O) 5CH 2CH 2SH (37.2 grams, 96.0mmol).Reacted 3 hours, and made the sulphur compound (CH of polyethylene glycol load 3O (C 2H 4O) 5CH 2CH 2S-PEG-SCH 2CH 2(C 2H 4O) 5OCH 3).Productive rate: 7.9 grams (70%).
1H NMR(CDCl 3/TMS)δ3.60-3.31(m，≈324H)；3.25(s，6H)；2.54(t，J＝6.8Hz，8H)。
The same method makes (CH 3) 2NC 2H 4OCH 2CH 2S-PEG-SCH 2CH 2OC 2H 4N (CH 3) 2The mercaptan compound of reaction is: (CH 3) 2NC 2H 4OCH 2CH 2SH (15.6 grams, 48 mmol).Productive rate: 7.8 grams (72%). 1H NMR(CDCl 3/TMS)δ3.60-3.25(m，≈324H)；2.73(t，J＝4.8Hz，4H)；2.54(t，J＝7.0Hz，8H)；2.22(s，12H)。
Embodiment 6
The tellurium oxygen of polyethylene glycol load, arsenic oxygen, the preparation of oxygen sulfur compound
(volume ratio: 1/1) 10mL is cooled to 0 ℃, adds t-BuOCl (4.6mmol) will to make the methylene chloride solution of the compound (1.0mmol) of tellurium (II) or arsenic (III) or sulphur (II) by embodiment 3,4 or 5.Reactant liquor was stirring 3 hours below 0 ℃. rise to room temperature naturally.Diatomite filtration, carrene (40mL) washing filter residue.Concentrated solvent is separated out with the 200mL ether to 10mL.Suction filtration gets the corresponding oxide of polyethylene glycol load.
Make tellurium oxygen compound (BuTe (O)-PEG-Te (O) Bu) 3.229 grams (95%) of polyethylene glycol load.
Above-mentioned reaction is adopted solvent-free process that each reactant is mixed the back and is ground, and the consumption of BuOCl is (9.2mmol).Reacted 3 hours, and made tellurium oxygen compound (BuTe (O)-PEG-Te (O) Bu) 3.229 grams (95%) of polyethylene glycol load.
1H NMR(CDCl 3/TMS)δ3.90-3.40(m，≈280H)；2.82(t，J＝7.6Hz，4H)；2.70(t，J＝7.4Hz，4H)；1.80-1.70(m，4H)；1.41-1.38(m，4H)；0.95(t，J＝7.2Hz，6H)。
Make tellurium oxygen compound (MeO-PEG-Te (O) Bu) 3.069 grams (95%) of polyethylene glycol load. 1H NMR(CDCl 3/TMS)δ3.90-3.40(m，≈280H)；3.38(s，3H)；2.82(t，J＝7.6Hz，2H)；2.70(t，J＝7.4Hz，2H)；1.80-1.70(m，2H)；1.41-1.38(m，2H)；0.95(t，J＝7.2Hz，3H)。
In the time of 80 ℃, reacted two hours, other reaction condition is the same, makes the arsenic oxygen compound (C of polyethylene glycol load 6H 5CH 2CH 2) 2As (O)-PEG-As (O) (CH 2CH 2C 6H 5) 2: 2.917 grams (95%). 1H NMR(CDCl 3/TMS)δ7.19-7.09(m，20H)；3.67-3.48(m，≈288H)；2.68(t，J＝10.8Hz，8H)；2.10(t，J＝10.8Hz，8H)；1.91(t，J＝11.0Hz，4H)。
Make the oxygen sulfur compound (CH of polyethylene glycol load 2=CHCH 2O (C 2H 4O) 5CH 2CH 2(O) S-PEG-S (O) CH 2CH 2(C 2H 4O) 5OCH 2CH=CH 2) 2.760 grams (90%). 1H NMR(CDCl 3/TMS)δ5.63(dd，J＝7.0Hz，4.2Hz，4H)；5.41(dd，J＝14Hz，4.2Hz，4H)；4.92-4.30(m，4H)；3.80-3.30(m，≈284H)；2.25-1.80(m，8H)；1.67(t，J＝7.2Hz，4H)；1.47(t，J＝6.0Hz，8H)。
Embodiment 7
The preparation of the salt compound of polyethylene glycol load
The toluene solution 50mL of the tellurium (II) that will make by embodiment 3,4 or 5 or the compound (0.4mmol) of arsenic (III) or sulphur (II) is cooled to-20 ℃, drip halide (0.5mL, 4.8mmol).Reaction is spent the night.
Naturally rise to room temperature or 100 ℃.Concentrated solvent is separated out with the 200mL ether to 10mL.Suction filtration gets tellurium salt, the arsenic salt of corresponding polyethylene glycol load, sulfosalt compound.
Sequence number Reactant 1 BrCH 2 Y Product 1H NMR(δ) Productive rate (%)
1 BuTe- PEG- TeBu BrCH 2 CO 2C 2H 5 [BuTe(C 4H 7O 2)-PEG- Te(C 4H 7O 2)Bu] 2+ 2(Br -) 4.22-4.15(m，4H)；3.95- 3.15(m，≈296H)；1.92(t， J＝7.0Hz，4H)；1.67-1.48 (m，4H)；1.30(t，J＝ 7.0Hz，6H)；0.98(t，J＝ 7.2Hz，6H) 100
PEG- TeCH 3 (CH＝C H) 5CO N(CH 3 )Bu t ONCH 3Bu t)-PEG- Te +(CH 2(CH＝CH) 5CONCH 3Bu t)CH 3 2H)；6.62-6.00(m，16H)； 5.84-5.35(m，2H)；4.00(d， J＝6.6Hz，4H)；3.89- 3.22(m，≈288H)；2.99(s， 6H)；2.22(s，6H).1.15(s， 18H).
1 0 CH 3Te- PEG- TeCH 3 BrCH 2 CN CH 3Te +(CH 2CN)-PEG- Te +(CH 2CN)CH 3]2(Br -) 4.13(s，4H)；3.87-3.21(m， ≈288H)；2.20(s，6H). 100
1 1 CH 3Te- PEG- TeCH 3 BrCH 2 NO 2 [CH 3Te+(CH 2NO 2)-PEG- Te +(CH 2NO 2)CH 3] 2(Br -) 5.23(s，4H)；3.86-3.10(m， ≈288H)；2.21(s，6H). 100
1 2 CH 3Te- PEG- TeCH 3 BrCH 2 SOPh [CH 3Te +(CH 2SOPh)- PEG-Te +(CH 2SOPh)CH 3] 2(Br -) 8.01-7.22(m，10H)； 4.63(s，4H)；3.71-3.21(m， ≈288H)；2.18(s，6H). 100
1 3 CH 3Te- PEG- TeCH 3 BrCH 2 SO 2Ph [CH 3Te +(CH 2SO 2Ph)- PEG- Te +(CH 2SO 2Ph)CH 3] 2(Br -) 7.12-6.81)m，10H)； 4.85(s，4H)；3.77-3.12(m， ≈288H)；2.21(s，6H). 100
1 4 CH 3Te- PEG- TeCH 3 BrCH 2 COPh [CH 3Te +(CH 2COPh)- PEG- Te+(CH 2COPh)CH 3]2( Br -) 7.77-7.31(m，10H)； 4.32(s，4H)；3.80-3.18(m， ≈288H)；2.21(s，6H). 100
1 5 (CH 3) 2A s-PEG- As(CH 3) 2 (CH 3) 3 CCH 2( Br)CH COPh [(CH 3) 2As +((CH 3) 3CCH 2CHCOPh)-PEG- As +((CH 3) 3CCH 2CHCOPh )(CH 3) 2]2(Br -) 1.70-7.11(m，10H)； 5.26(t，J＝7.0Hz，2H)； 3.88-3.20(m，≈288H)； 2.12(s，12H)；1.27(d，J＝ 7.0Hz，4H)；1.20(s，18H). 97
1 6 CH 3Te- PEG- TeCH 3 BrCH 2 COC 6H 4 Cl-p [CH 3Te +(CH 2COC 6H 4Cl- p)-PEG- Te +(CH 2COC 6H 4Cl- 7.39(d，J＝9.0Hz，4H)； 7.56(d，J＝9.0Hz，4H)； 4.22(s，4H)；2.21(s，6H). 100
p)CH 3]2(Br -)
1 7 CH 3S- PEG- SCH 3 BrCH 2 COC 6H 4 CH 3-o [CH 3S +(CH 2COC 6H 4CH 3- o)-PEG- S +(CH 2COC 6H 4CH 3- o)CH 3]2(Br -) 7.66-7.11(m，8H)；4.38(s， 4H)；3.04(s，6H)；2.51(s， 6H). 100
1 8 CH 3Te- PEG- TeCH 3 BrCH 2 COC 6H 4 NO 2-m [CH 3Te +(CH 2COC 6H 4NO 2- m)-PEG- Te+(CH 2COC 6H 4NO 2- m)CH 3]2(Br -) 8.31-7.93(m，6H)；7.67- 7.42(m，2H)；4.27(s，4H)； 2.21(s，6H). 100
1 9 CH 3Te- PEG- TeCH 3 BrCH 2 Ph [CH 3Te +(CH 2Ph)-PEG- Te +(CH 2Ph)CH 3]2(Br -) 7.19-6.83(m，10H)； 4.40(s，4H)；3.80-3.16(m， ≈288H)；2.20(s，6H). 100
2 0 (CH 3) 2A s-PEG- As(CH 3) 2 (CH 3) 3 CCH 2( Br)CH Ph [(CH 3) 2As +((CH 3) 3CCH 2CHPh)-PEG- As +((CH 3) 3CCH 2CHPh)( CH 3) 2]2(Br -) 7.26-6.73(m，10H)；3.90- 3.13(m，≈290H)；2.15(s， 12H)；1.28(d，J＝7.2Hz， 4H)；1.13(s，18H). 98
2 1 (C 6H 5CH 2CH 2) 2As -PEG- As(CH 2C H 2C 6H 5) 2 ClCH 2 C 6H 4Cl -p [(C 6H 5CH 2CH 2) 2As +(CH 2C 6H 4Cl-p-PEG- As +(CH 2C 6H 4Cl- p)(CH 2CH 2C 6H 5) 2] 2(Cl -) 7.34-6.71(m，28H)； 4.10(s，4H)；3.87-3.10(m， ≈304H)； 96
2 2 (CH 3) 2NC 2H 4OC H 2CH 2S- PEG- SCH 2CH 2OC 2H 4N( CH 3) 2 BrCH 2 C 6H 4CH 3-o [(CH 3) 2NC 2H 4OCH 2CH 2S +(CH 2C 6H 4CH3-o)- PEG-S +(CH 2C 6H 4CH3- o)CH 2CH 2OC 2H 4N (CH 3) 2]2(Br -) 7.42-6.67(m，8H)；4.08(s， 4H)；3.80-3.20(m，≈ 312H)；3.12-2.91(m，12H)； 2.48(s，6H)；2.22(s， 12H). 98
2 (CH 3) 2A ICH 2C 6 [(CH 3) 2As +(CH 2C 6H 4NO 2 7.75-7.10(m，8H)；4.06(s， 100
3 s-PEG- As(CH 3) 2 H 4NO 2- m -m)-PEG- As +(CH 2C 6H 4NO 2- m)(CH 3) 2]2(I -) 4H)；3.80-3.20(m，≈ 288H)；2.13(s，12H)； 2.18(s，2H).
2 4 ((CH 3) 2 C＝CH CH 2CH 2) 2 As-PEG -As (CH 2CH 2 CH＝ C(CH 3) 2) 2 BrCH 2 CH＝CH 2 [((CH 3) 2C＝CHCH 2 CH 2) 2As +(CH 2CH＝CH 2) -PEG- As +(CH 2CH＝CH 2)(CH 2CH 2 CH＝C(CH 3) 2) 2]2(Br -) 5.83-5.51(m，2H)； 5.49(dd，J＝14.0Hz， 4.0Hz，2H)；5.18-4.91(m， 4H)；4.88(dd，J＝7.0Hz， 4.0Hz，2H)；3.90-3.10(m. ≈300H)；2.85-2.55(m. 8H)；1.63(s，24H). 100
2 5 (CH 3) 2A s-PEG- As(CH 3) 2 (CH 3) 3 CCH 2( Br)CH CH＝CH 2 [(CH 3) 2As +((CH 3) 3CCH 2 CHCH＝CH 2)-PEG- As +((CH 3) 3CCH 2CHCH＝C H 2)(CH 3) 2]2(Br -) 5.78-5.31(m，2H)； 5.13(dd，J＝14.0Hz， 4.0Hz，2H)；4.78(dd，J＝ 7.0Hz，4.0Hz，2H)；3.81- 3.21(m，≈288H)；3.01- 2.72(m，2H)；2.15(s，6H)； 1.28(d，J＝6.8Hz，4H)； 1.14(s，18H). 100
2 6 CH3S- PEG- SCH 3 BrCH 2 CH＝CH CH 3 [CH 3S +(CH 2CH＝CHCH 3)- PEG- S +(CH 2CH＝CH 2CH 3)CH 3] 2(Br -) 6.20(dt，J＝14.0Hz， 6.6Hz，2H)；5.19(dq，J＝ 14.0Hz，7.4Hz，2H)； 4.03(d，J＝6.6Hz，4H)； 3.82-3.12(m，≈288H)； 2.50(s，6H)；1.97(d，J＝ 7.4Hz，6H). 100
2 7 C 6H 5CH 2C H 2S- BrCH 2 CH＝CH [C 6H 5CH 2CH 2S +(CH 2CH＝C HCH 2C(CH 3) 3)-PEG- 7.21(dt，J＝14.0Hz， 6.6Hz，2H)；7.15-7.03(m， 100
PEG- SCH 2CH 2C 6H 5 CH 2C( CH 3) 3 S +(CH 2CH＝CHCH 2C(CH 3) 3)CH 2CH 2C 6H 5]2(Br -) 10H)；5.20(dt，J＝14.0Hz， 7.2Hz，2H)；3.93(d，J＝ 6.6Hz，4H)；3.87-3.20(m， ≈292H)；2.56(t，J＝ 6.6Hz，4H)；1.93(d，J＝ 7.2Hz，4H).0.89(s，18H).
2 8 CH 3S- PEG- SCH 3 BrCH 2 CH＝CH SiMe 3 [CH 3S +(CH 2CH＝CHSiMe 3)-PEG- S +(CH 2CH＝CHSiMe 3)CH 3]2(Br -) 6.20(dt，J＝14.0Hz， 6.6Hz，2H)；5.65(d，J＝ 14.0Hz，2H)；4.02(d，J＝ 6.6Hz，4H)；3.85-3.21(m， ≈288H)；2.53(s，6H)； 0.07(s，18H). 100
2 9 CH 3CH＝ CHCH 2CH 2S-PEG- SCH 2CH 2 CH＝CHCH 3 BrCH 2 CH＝CH Si((C H 2) 2C( CH 3) 3) 2 [CH 3CH＝ CHCH 2CH 2S +(CH 2CH＝CH Si((CH 2) 2C(CH 3) 3) 2)- PEG-S +(CH 2CH＝CH Si((CH 2) 2C(CH 3) 3) 2)CH 2CH 2CH＝CHCH 3]2(Br -) 6.46(dt，J＝7.4Hz，3.3Hz， 2H)；6.30(d，J＝7.4Hz， 2H)；5.52(dq，J＝14Hz， 7.2Hz，2H)；5.42(dt，J＝ 1 4Hz，7.2Hz，2H)；4.04(d， J＝3.3Hz，4H)；3.70- 3.30(m，≈288H)；2.98(t，J ＝7.2Hz，4H)；2.23- 1.85(m，4H)；1.61(d，J＝ 7.2Hz，6H)；1.38(t，J＝ 6.6Hz，12H)；0.83(t，J＝ 6.6Hz，12H)；0.76(s， 54H). 100
3 0 (CH 3) 2A s-PEG- As(CH 3) 2 BrCH 2 CH＝CH (CH＝C H) 4CH ＝CH 2 [(CH 3) 2As +(CH 2CH＝CH( CH＝CH) 4CH＝CH 2)-PEG- As +(CH 2CH＝CH(CH＝CH) 4CH＝CH 2)(CH 3) 2]2(Br -) 6.85(dd，J＝11.0Hz，14Hz， 2H)；6.80-5.86(m，16H)； 5.28(dd，J＝14.0Hz， 7.0Hz，2H)；5.01(dd，J＝ 7.0Hz，4.0Hz，2H)； 4.87(dt，J＝14.0Hz， 6.6Hz，2H)；2.10(s，12H). 100
3 1 CH 3O- PEG- BrCH 2 CCSiM [CH 3O-PEG- S +(CH 2C≡CSiMe 3)CH 3] 4.33(s，2H)；3.85-3.41(m， ≈286H)；3.38(s，3H)； 100
SCH 3 e 3 (Br -) 2.53(s，3H)；0.07(s，9H).
Reacting 31 in the above table, is solvent with carrene, BrCH 2CCSiMe 3Consumption be that (1.0mL 9.6mmol), reacts after 72 hours, and the productive rate of reaction is 94%.
React 31 in the above table, adopt solvent-free process that reaction reagent is mixed the back and grind BrCH 2CCSiMe 3Consumption be that (1.0mL 9.6mmol), reacts after 3 hours, and the productive rate of reaction is 94%.
Embodiment 8
Splash among the dichloromethane solution 50mL of an inorganic salt compound under the dichloromethane solution 10mL room temperature of the tellurium that will make by embodiment 7, sulphur, arsenic salt compound (0.3mmol).This mixture stirring is spent the night.Make it to carry out the anion exchange.After reaction finished, concentrated solvent was used 200mL to 5mL
Ether is separated out.Suction filtration gets tellurium, sulphur, the arsenic salt compound of the polyethylene glycol load of anion exchange.
Make the tellurium salt compound of polyethylene glycol load: [BuTe (C 4H 7O 2)-PEG-Te (C 4H 7O 2) Bu] 2+2 (BF 4) -: 1.11 grams (100%).Tellurium salt compound used in the reaction is: [BuTe (C 4H 7O 2)-PEG-Te (C 4H 7O 2) Bu] 2+2 (Br) -(1.11 grams, 0.3mmol); Inorganic salt compound is: AgBF 4(0.936 gram, 4.8mmol). 1H NMR(CDCl 3/TMS)δ 4.22-4.15(m，4H)；3.95-3.15(m，≈296H)；1.92(t，J＝7.0Hz，4H)；1.67-1.48(m，4H)；1.30(t，J＝7.0Hz，6H)；0.98(t，J＝7.2Hz，6H)
Make the sulfosalt compound of polyethylene glycol load: [C 6H 5CH 2CH 2S +(CH 2CH=CHCH 2C (CH 3) 3)-PEG-S +(CH 2CH=CHCH 2C (CH 3) 3) CH 2CH 2C 6H 5] 2 (ClO 4) -: 1.11 grams (100%).Tellurium salt compound used in the reaction is: [C 6H 5CH 2CH 2S +(CH 2CH=CHCH 2C (CH 3) 3)-PEG-S +(CH 2CH=CHCH 2C (CH 3) 3) CH 2CH 2C 6H 5] 2 (Br) -(1.10 grams, 0.3mmol); Inorganic salt compound is: AgClO 4(0.996 gram, 4.8mmol). 1H NMR(CDCl 3/TMS)δ7.21(dt，J＝14.0Hz，6.6Hz，2H)；7.15-7.03(m，10H)；5.20(dt，J＝14.0Hz，7.2Hz，2H)；3.93(d，J＝6.6Hz，4H)；3.87-3.20(m，≈292H)；2.56(t，J＝6.6Hz，4H)；1.93(d，J＝7.2Hz，4H).0.89(s，18H)。
Make the arsenic salt compound of polyethylene glycol load: [(CH 3CH=CHCH 2CH 2) 2As +(CH 2CH=CH 2)-PEG-As +(CH 2CH=CH 2) (CH 2CH 2CH=CHCH 3) 2] 2 (I) -: 1.10 grams (98%).Arsenic salt compound used in the reaction is: [(CH 3CH=CHCH 2CH 2) 2As +(CH 2CH=CH 2)-PEG-As +(CH 2CH=CH 2) (CH 2CH 2CH=CHCH 3) 2] 2 (Br) -(1.10 grams, 0.3mmol); Inorganic salt compound is: and NaI (0.72 gram, 4.8mmol). 1H NMR(CDCl 3/TMS)δ6.48-5.83(m，2H)；5.69(dd，J＝14.0Hz，4.0Hz，2H)；5.18-4.91(m，4H)；4.88(dd，J＝4.0Hz，4.0Hz，2H)；3.90-3.10(m.≈300H)；2.85-2.55(m.8H)；1.63(s，24H)。
Embodiment 9
The ylide compound of polyethylene glycol load:
The tetrahydrofuran solution 50mL of the tellurium that will make by embodiment 7, sulphur, arsenic salt compound (0.4mmol) is cooled to-40 ℃, drips potassium tert-butoxide (0.54 gram, tetrahydrofuran solution 20mL 4.8mmol).Keep reacting under this temperature after 8 hours, intensification and stirring are spent the night naturally.
Concentrated solvent is separated out with the 200mL ether to 10mL.Suction filtration gets tellurium, sulphur, the arsenic ylide compound of polyethylene glycol load.
Make the tellurium ylide compd B uTe (C of polyethylene glycol load 4H 6O 2)-PEG-Te (C 4H 6O 2) Bu:1.48 restrains (100%).
Solvent-free process is adopted in above-mentioned reaction, above-mentioned each reactive material is mixed the back grind.The consumption of potassium tert-butoxide is that (1.08 grams 9.6mmol), reacted 3 hours, made the tellurium ylide compd B uTe (C of polyethylene glycol load 4H 6O 2)-PEG-Te (C 4H 6O 2) Bu:1.40 restrains (95%)
1H NMR(CDCl 3/TMS)δ4.17(q，J＝7.2Hz，4H)；6.2(s，2H)，3.90-3.25(m，≈292H)；1.91-1.82(m，4H)；1.47-1.22(m，4H)；1.00(t，J＝7.2Hz，6H)；0.88(t，J＝7.0Hz，6H)。
Make the sulphur ylide compound CH of polyethylene glycol load 3S (CHCH=CH 2)-PEG-S (CHCH=CH 2) CH 3: 1.26 (100%). 1H NMR(CDCl 3/TMS)δ7.42-7.00(m，2H)；6.58-6.54(m，4H)；2.55(s，6H)；3.82-3.10(m，≈290)。
Make the arsenic ylide compound (CH of polyethylene glycol load 3) 2As (CHCN)-PEG-(CHCN) As (CH 3) 2: 1.31 (100%). 1H NMR(CDCl 3/TMS)δ3.95-3.10(m，≈290H)；2.10(s，12H)。
Make the arsenic ylide Compound C H of polyethylene glycol load 3O-PEG-(CHCN) As (CH 3) 2: 1.27 (100%). 1H NMR(CDCl 3/TMS)δ3.95-3.10(m，≈290H)；2.10(s，6H)。

Claims (9)

1. a class is used for the soluble high-molecular catalyst of catalyzing Ylide reaction, and its molecular formula is (C 2H 4O) nA, wherein (C 2H 4O) be the polyethylene glycol structures unit, n is 2-2000, A=(MR) 2Or (MR) OR 1, M=M ' or M ' (O), M '=As, Te or S, R 1=C 1-10Alkyl, R=R 2 q, R 2 qCH (R 3) R 4X or R 2 qC (R 3) R 4, R 2=C 1-30Alkyl, C 1-30Contain heteroatomic various alkyl, C 1-30Aryl or C 1-30Substituted aryl, described hetero atom is N, O or S, R 3=H or C 1-10Alkyl, R 4Be electron withdraw group, q equals 1 or 2, X=X ', ClO 4 -Or BF 4 -, X '=I -, Cl -Or Br -, described electron withdraw group is C 1-20Alkanoyl, aroyl, replacement aroyl, benzenesulfonyl, benzene sulfoxide group, ester group, thiazolinyl, substituted alkenyl, alkene ester group, cyano group, nitro, amide groups, aryl, substituted aryl or its corresponding vinylogy base.
2. according to the described soluble high-molecular catalyst of claim 1, its molecular formula is (C 2H 4O) nC 2H 4(M ' R 2 q) 2Or R 1O (C 2H 4O) nC 2H 4M ' R 2 q, wherein M ', R 1, R 2, q, n according to claim 1.
3. according to the described soluble high-molecular catalyst of claim 1, its molecular formula is Or
Figure C0110540900022
, wherein M ', R 1, R 2, q, n according to claim 1.
4. according to the described soluble high-molecular catalyst of claim 1, its molecular formula is (C 2H 4O) nC 2H 4[M ' (R 2 q) CH (R 3) R 4X] 2Or R 1O (C 2H 4O) nC 2H 4M ' (R 2 q) CH (R 3) R 4X, wherein M ', R 1, R 2, R 3, R 4, q, n according to claim 1.
5. according to the described soluble high-molecular catalyst of claim 1, its molecular formula is (C 2H 4O) nC 2H 4[M ' (R 2 q) C (R 3) R 4] 2Or R 1O (C 2H 4O) nC 2H 4M ' (R 2 q) C (R 3) R 4,, wherein M ', R 1, R 2, R 3, R 4, q, n according to claim 1.
6. according to the synthetic method of the described soluble high-molecular catalyst of claim 1, it is characterized in that under the effect of alkali polyethylene glycol HO (C 2H 4O) N+1H or R 1O (C 2H 4O) N+1H and halid mol ratio are: 1: 1.0-30.0, and reaction a few minutes-72 hour in the time of-40 ℃ to 100 ℃, described halide comprises that molecular formula is R 5SO 2The sulfuryl halide of X and halogenating agent, wherein R 5=C 1-10Alkyl, C 1-10Contain heteroatomic various alkyl, C 1-10Aryl or C 1-10Substituted aryl, described halogenating agent is PBr 3, PBr 5Or SOCl 2, the molecular formula of the product that obtains is (C 2H 4O) nC 2H 4(OSO 2R 5) 2, R 1O (C 2H 4O) nC 2H 4OSO 2R 5, (C 2H 4O) nC 2H 4(X ') 2Or R 1O (C 2H 4O) nC 2H 4X ';
Compound (C 2H 4O) nC 2H 4(OSO 2R 5) 2, R 1O (C 2H 4O) nC 2H 4OSO 2R 5, R 1O (C 2H 4O) nC 2H 4X ' or (C 2H 4O) nC 2H 4(X ') 2The molecular formula that generates with the scene is R 2 qThe mol ratio of the compound of M ' Y is 1.0: 1.0-30.0, reaction is 0.5-72 hour in the time of-100 ℃ to 200 ℃, obtains molecular formula and is (C 2H 4O) n(C 2H 4) (M ' R 2 q) 2Or R 1O (C 2H 4O) nC 2H 4M ' R 2 qCatalyst as claimed in claim 1, wherein Y=ZnX ', MgX ', Na or Li;
(C 2H 4O) n(C 2H 4) (M ' 2 q) 2Or R 1O (C 2H 4O) nC 2H 4M ' R 2 qWith molecular formula be R 3(R 4) the halid mol ratio of CHX ' is 1: 1.0-30.0-78 ℃ to 100 ℃ reactions 0.5-72 hour, obtains molecular formula and is (C 2H 4O) nC 2H 4[M ' (R 2 q) CH (R 3) R 4X '] 2Or R 1O (C 2H 4O) nC 2H 4M ' (R 2 n) CH (R 3) R 4The catalyst as claimed in claim 1 of X ';
(C 2H 4O) nC 2H 4[M ' (R 2 q) CH (R 3) R 4X '] 2Or R 1O (C 2H 4O) nC 2H 4M ' (R 2 q) CH (R 3) R 4X ' is 1 with the mol ratio of inorganic salts: 1-10, carried out the anion exchange reaction 0.5-72 hour at-78 ℃ to 100 ℃, and obtain molecular formula and be (C 2H 4O) nC 2H 4[M ' (R 2 q) CH (R 3) R 4X] 2Or R 1O (C 2H 4O) nC 2H 4M ' (R 2 q) CH (R 3) R 4The catalyst as claimed in claim 1 of X, described inorganic salts are that anion is I -, ClO 4 -Or BF 4 -Inorganic salts;
(C 2H 4O) nC 2H 4[M ' (R 2 q) CH (R 3) R 4X] 2Or R 1O (C 2H 4O) nC 2H 4M ' (R 2 q) CH (R 3) R 4The mol ratio of X and alkali is 1: 1-10-78 ℃ to 100 ℃ reactions 0.5-72 hour, obtains molecular formula and is (C 2H 4O) nC 2H 4[M ' (R 2 q) C (R 3) R 4] 2Or R 1O (C 2H 4O) nC 2H 4M ' (R 2 q) C (R 3) R 4The catalyst as claimed in claim 1 of X;
(C 2H 4O) nC 2H 4(M ' R 2 q) 2Or R 1O (C 2H 4O) nC 2H 4M ' R 2 qWith oxidant, perhaps R 1O (C 2H 4O) nC 2H 4M ' (R 2 q) C (R 3) R 4Or (C 2H 4O) n(C 2H 4) [M ' (R 2 q) C (R 3) R 4] 2With the mol ratio of electrophilic reagent be 1: 1-10-78 ℃ to 100 ℃ reactions 0.5-72 hour, obtains molecular formula for (C 2H 4O) n(C 2H 4O) [M ' (O) R 1 q] 2Or R 1O (C 2H 4O) nC 2H 4M ' is R (O) 2 qCatalyst as claimed in claim 1, described oxidant is BuClO or N-chlorosuccinimide, described electrophilic reagent is an aldehydes or ketones;
R wherein 1, R 2, R 3, R 4, X ', X, M ', q, n according to claim 1.
7. according to the synthetic method of the described soluble high-molecular catalyst of claim 6, it is characterized in that described alkali is the amine that contains lone pair electrons on the mixture of hydroxide, hydride, carbonate, pure alkali, above-mentioned alkali and aluminium oxide of lithium, sodium or potassium or the nitrogen-atoms.
8. according to the purposes of the described soluble high-molecular catalyst of claim 1, it is characterized in that catalyst as Ylide reaction.
9. according to the purposes of the described soluble high-molecular catalyst of claim 1, it is characterized in that catalyst as ylide alkenyl, the little cyclization of ylide.
CN 01105409 2001-02-23 2001-02-23 Soluble high-molecular catalyst, synthesizing process and use thereof Expired - Fee Related CN1112251C (en)

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