CN103864727A - Preparation of novel epichlorohydrin tetramer and reaction between novel epichlorohydrin tetramer and formaldehyde derivatives - Google Patents

Preparation of novel epichlorohydrin tetramer and reaction between novel epichlorohydrin tetramer and formaldehyde derivatives Download PDF

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CN103864727A
CN103864727A CN201410064080.7A CN201410064080A CN103864727A CN 103864727 A CN103864727 A CN 103864727A CN 201410064080 A CN201410064080 A CN 201410064080A CN 103864727 A CN103864727 A CN 103864727A
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straight chain
tetramer
formula
replacement
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张大永
苏金月
蒋晟
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China Pharmaceutical University
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China Pharmaceutical University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/28—Ethers with hydroxy compounds containing oxirane rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
    • C07D303/24—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds
    • C07D303/26—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds having one or more free hydroxyl radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

Abstract

The invention relates to a preparation method of a novel compound namely an epichlorohydrin tetramer and a reaction between the epichlorohydrin tetramer and formaldehyde derivatives. Epichlorohydrin is an industrial raw material which is cheap and easily available; by taking water and an organic solvent as a solvent, epichlorohydrin can generate self-condensation at room temperature in the presence of a strong base and a phase transfer catalyst to obtain a novel epichlorohydrin tetramer. The tetramer can react with the formaldehyde derivatives after reacting with the strong base, so that a series of propargyl glycidyl ether derivatives can be obtained. The first-step reaction is mild in condition and simple in operation, and provides new clues for new uses in exploring epichlorohydrin in the future. The second-step reaction is a preliminary attempt of the application of the novel tetramer, and provides a new method for preparing the propargyl glycidyl ether derivatives at the same time.

Description

The novel tetrameric preparation of epoxy chloropropane and with the reacting of formaldehyde derivatives
Technical field
The present invention relates to the compound of a class novelty---the tetrameric preparation of epoxy chloropropane and with the reacting of formaldehyde derivatives, obtain novel alkynyl Racemic glycidol ether compound.The invention belongs to synthetic organic chemistry new reaction field.
Background technology
Epoxy chloropropane is a kind of important Organic Chemicals and fine chemistry industry chlorine consuming products, mainly for the production of fine chemical products such as epoxy resin, synthetic glycerine, chlorohydrin rubbers.It is strong that the epoxy resin making taking it as raw material has cohesiveness, the feature such as resistant to chemical media burn into shrinking percentage is low, chemical stability good, excellent in cushion effect and dielectric properties are excellent, has a wide range of applications in industries such as coating, tackiness agent, strongthener, cast material and electronic shell stampings.In addition, also can be used for the multiple products such as synthetic glycerine, nitroglycerine explosive, glass reinforced plastic, electrical isolation product, tensio-active agent, medicine, agricultural chemicals, coating, sizing material, ion exchange resin, softening agent, (contracting) glycerol derivative, chlorohydrin rubber, as the solvent of cellulose ester, resin, ether of cellulose, for the production of chemical stabilizer, chemical dyestuff and water conditioner etc.
Epoxy chloropropane is inexpensive with it, be easy to get and the chemical property of himself has purposes widely in multiple fields, in the process of exploring the existing purposes of epoxy chloropropane, synthesize a class novel cpd---the epoxy chloropropane tetramer taking epoxy chloropropane as substrate, through further experiment, we find that this tetramer can also react with formaldehyde derivatives, has proposed the present invention thus.
Epoxy chloropropane is tetrameric synthesizes the new purposes of exploring from now on epoxy chloropropane provides new clue.The epoxy chloropropane tetramer is to one of novel tetramer application preliminary trial with reacting of formaldehyde derivatives, and a kind of novel method of preparing proyl glycidyl ether derivatives is also provided simultaneously.
Summary of the invention
The present invention is taking epoxy chloropropionate alkyl compound as raw material, it is characterized in that taking water and ORGANIC SOLVENT MIXTURES as solvent, and in the situation that highly basic and quaternary ammonium salt-type phase transfer catalyst exist, room temperature is reacted, and can obtain epoxy chloropropane tetramerization compound.
The above epoxy chloropropionate alkyl compound, has the general structure shown in general formula (I):
Figure BSA0000101373040000011
Wherein R 1for the straight chain of H, C1～C8 or the replacement of straight chain or non-substituted alkyl, cycloalkyl, aryl, substituted arene base.
Wherein R 2for the straight chain of H, C1～C5 or the replacement of straight chain or non-substituted alkyl, cycloalkyl, aryl, substituted arene base.
Wherein R 3for the straight chain of H, C1～C5 or the replacement of straight chain or non-substituted alkyl.
Above-described organic solvent is normal hexane, toluene, methylene dichloride, chloroform, ether, tetrahydrofuran (THF).
Above-described highly basic is sodium hydroxide, potassium hydroxide, cesium hydroxide.
The above epoxy chloropropane tetramerization compound, has the general structure shown in general formula (II):
Figure BSA0000101373040000021
Wherein R 1for the straight chain of H, C1～C8 or the replacement of straight chain or non-substituted alkyl, cycloalkyl, aryl, substituted arene base.
Wherein R 2for the straight chain of H, C1～C5 or the replacement of straight chain or non-substituted alkyl, cycloalkyl, aryl, substituted arene base.
Wherein R 3for the straight chain of H, C1～C5 or the replacement of straight chain or non-substituted alkyl.
The part epoxy chloropropionate alkanes tetramer that we have synthesized sees the following form:
Numbering R 1 R 2 R 3
S-1 -H -H -H
S-2 -H -CH 3 -H
S-3 -H -Ph -H
S-4 -H -Pr -H
The present invention find epoxy chloropropionate alkyl compound the tetramer can with the derivatives reaction of the formaldehyde of structure as shown in general formula (III), concrete reaction scheme: the tetramer is dissolved in anhydrous tetrahydro furan or anhydrous diethyl ether, be cooled to-78 DEG C, add highly basic, after-78 DEG C of reaction 1h, add formaldehyde derivatives, maintain this temperature, stopped reaction after reaction 3h, can obtain the compound of structure as shown in general formula (IV) through aftertreatment:
Figure DEST_PATH_GSB0000124856820000022
Wherein R 1for the straight chain of H, C1～C8 or the replacement of straight chain or non-substituted alkyl, cycloalkyl, aryl, substituted arene base.
Wherein R 2for the straight chain of H, C1～C5 or the replacement of straight chain or non-substituted alkyl, cycloalkyl, aryl, substituted arene base.
Wherein R 3for the straight chain of H, C1～C5 or the replacement of straight chain or non-substituted alkyl.
Wherein R 5for by nitro, OR 6, trifluoromethyl, F, Cl, Br, R 6one replaces or polysubstituted aryl, benzo are saturated, unsaturated heterocycle or condensed-nuclei aromatics base.
Wherein R 6for the straight chain of C1～C5 or the replacement of straight chain or non-substituted alkyl, aryl.
Wherein the highly basic in this reaction can be n-Butyl Lithium, the tertiary butyl, diisopropylamine lithium.
The portion of product that the epoxy chloropropane tetramer that we have synthesized reacts with formaldehyde derivatives sees the following form:
Figure DEST_PATH_GSB0000124856820000031
embodiment
In order to understand better the present invention, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment 1
Figure BSA0000101373040000041
Operation scheme one:
By epoxy chloropropionate alkyl compound (20mmol), tetrabutyl potassium sulfocyanate (0.17mg, 0.5mmol), 17mL normal hexane adds rear stirring at room temperature 5min successively.And in backward reaction solution, drip slowly 50% sodium hydroxide ((4g, 100mm0l)) solution, and after stirring at room temperature 0.5h, in reaction solution, add sodium hydrate solid (4g, 100mmol), under room temperature, stir and spend the night.At 0 DEG C of reaction solution, drip 10mL thin up, ethyl acetate extracted organic phase, merges organic phase, saturated sodium-chloride washing, and anhydrous sodium sulfate drying, column chromatography purification, obtains sterling.
1. epoxy chloropropane (S-1):
By above-mentioned basic operational steps, can there is self condensation in epoxy chloropropane (1.85g, 20.0mmol), gets final product to obtain colorless oil target compound (0.73g, 60%) through dilution, extraction, dry, column chromatography. 1H?NMR(400MHz，CDCl 3)δ6.24(dt，J=13.2，1.6Hz，2H)，6.03-5.97(m，2H)，4.07-3.97(m，4H)，3.74(dd，J=11.6，6.8Hz，2H)，3.35(m，2H)，3.15-3.11(m，2H)，2.79-2.77(m，2H)，2.63-2.58(m，1H)； 13C?NMR(125MHz，CDCl 3)δ129.6，121.4，70.8，69.2，50.6，44.0.HRMS(ESI)：calcd?for?calcd?for?C 12H 18O 5[M+H] +243.1227；found243.1128.
2. methyl epichlorohydrin (S-2):
By above-mentioned basic operational steps, can there is self condensation in methyl epichlorohydrin (2.13g, 20mmol), gets final product to obtain colorless oil target compound (0.52g, 35%) through dilution, extraction, dry, column chromatography. 1H?NMR(400MHz，CDCl 3)δ6.09(q，J=1.2Hz，2H)，3.99-3.91(m，4H)，3.50(d，J=10.8Hz，2H)，3.33(d，J=10.8Hz，2H)，2.72(d，J=4.8Hz，2H)，2.62(d，J=4.2Hz，2H)，1.79(d，J=1.3Hz，6H)，1.36(s，6H)； 13C?NMR(125MHz，CDCl 3)δ135.4，115.8，73.78，73.1，55.8，51.3，18.3，14.2.MS(ESI)：calcd?for?calcd?for?C 16H 26O 5[M-H]-297；found297.
3. phenyl epoxy chloropropane (S-3):
By above-mentioned basic operational steps, can there is self condensation in phenyl epoxy chloropropane (3.37g, 20mmol), gets final product to obtain colorless oil target compound (0.37g, 25%) through dilution, extraction, dry, column chromatography. 1H?NMR(400MHz，CDCl 3)δ7.38-7.27(m，20H)，6.37(s，2H)，4.31(s，4H)，4.05(d，J=11.6Hz，2H)，3.79(d，J=11.6Hz，2H)，3.05(d，J=5.2Hz，2H)，2.76(d，J=5.6Hz，2H). 13C?NMR(125MHz，CDCl 3)δ138.8，135.6，128.4，128.3，128.2，128.0，127.9，126.1，117.2，73.8，72.2，59.0，53.0.MS(ESI)：calcd?for?calcd?for?C 36H 34O 5[M+Na] +569；found569.
4. propyl group epoxy chloropropane (S-4):
By above-mentioned basic operational steps, can there is self condensation in propyl group epoxy chloropropane (2.69g, 20mmol), gets final product to obtain colorless oil target compound (0.616g, 30%) through dilution, extraction, dry, column chromatography. 1H?NMR(400MHz，CDCl 3)δ6.10(s，2H)，4.00-3.92(m，4H)，3.55(d，J=11.2Hz，4H)，3.36(d，J=11.2Hz，4H)，2.66(dd，J=10.8，4.4Hz，2H)，2.21(t，J=7.2Hz，4H)，1.52-1.37(m，12H)，0.93(t，J=7.2Hz，12H)； 13C?NMR(125MHz，CDCl 3)δ139.3，116.1，72.5，71.8，58.4，50.1，34.0，30.3，20.3，18.0，14.2，14.0.MS(ESI)：calcd?for?calcd?for?C 24H 42O 5[M-H]-409；found409.
Embodiment 2
Figure BSA0000101373040000051
Operation scheme two:
By the tetramer (242mg, 1mmol) be dissolved in 10mL anhydrous tetrahydro furan, in bathing as for cryogenic thermostat, be cooled to-78 DEG C, slowly drip 1.2mL normal-butyl (2.5mmol/L in hexane), at this temperature, continue reaction 1h, drip the derivative of formaldehyde, continue reaction 3h stopped reaction.Add saturated ammonium chloride cancellation, ethyl acetate extraction, merges organic phase, saturated sodium-chloride washing, and dry, column chromatography obtains product.
The fluoro-3-methyl of 1.4-hydroxyl-4-[(4-) phenyl] fourth-2-alkynyl glycidyl ether (J-1)
Operate by such scheme two, the tetramer (S-1) (242mg, 1mmol) and the fluoro-3-tolyl aldehyde of 4-(415mg, 3.0mmol) are-78 DEG C of reactions, obtain colorless oil product, yield 69% through extraction, washing, dry, column chromatography. 1H?NMR(400MHz，CDCl 3)δ7.36-7.30(m，2H)，6.99(t，J=8.8Hz，1H)，5.45(s，1H)，4.31(t，J=16.0Hz，2H)，3.85(d，J=11.2Hz，1H)，3.49-3.44(m，1H)，3.18(s，1H)，2.81(s，1H)，2.63(s，1H)，2.40(s，1H)，2.29(s，3H)； 13C?NMR(125MHz，CDCl 3)δ161.20(d，J=245Hz)，135.85(d，J=3.75Hz)，129.80(d，J=5Hz)，125.59(d，J=8.75Hz)，125.08(d，J=17.5Hz)，115.04(d，J=22.5Hz)，86.49，82.26.70.50，63.90，58.74，50.58，44.25，14.52(d，J=35Hz)；HRMS(ESI)：calcd?for?C 14H 15FO 3[M+Na] +273.0897；found273.0899.
2.4-hydroxyl-4-[(3,5-difluoro) phenyl] fourth-2-alkynyl glycidyl ether (J-2)
Operate the tetramer (S-1) (242mg, 1mmol) and 3 by such scheme two, 5-difluorobenzaldehyde (427mg, 3.0mmol)-78 DEG C of reactions, obtain colorless oil product, yield 54% through extraction, washing, dry, column chromatography. 1H?NMR(400MHz，CDCl 3)δ7.06(d，J=7.2Hz，2H)，6.76(t，J=8.8，1H)，5.47(s，1H)，4.30(s，2H)，3.86(d，J=11.2，1H)，3.47-3.42(m，1H)，3.18(s，1H)，2.83-2.78(m，2H)，2.63(m，1H). 13C?NMR(125MHz，CDCl 3)?δ162.97(dd，J=246，12.5Hz)，144.28(t，J=8.75Hz)，109.40(dd，J=20，6.25Hz)，103.52(t，J=25Hz)，85.5，82.7，70.58(d，J=1.25Hz)，63.3，58.6，50.6，44.2.HRMS(ESI)：calcdfor?C 13H 12F 2O 3[M+Na] +277.0647；found277.0648.
3.4-hydroxyl-4-[(2-chlorine) phenyl] fourth-2-alkynyl glycidyl ether (J-3)
Operate by such scheme two, the tetramer (S-1) (242mg, 1mmol) and 2-chlorobenzaldehyde (415mg, 3.0mmo1) are-78 DEG C of reactions, obtain colorless oil product, yield 59% through extraction, washing, dry, column chromatography. 1H?NMR(400MHz，CDCl 3)δ7.73(d，J=7.6Hz，1H)，7.38(d，J=7.6Hz，1H)，7.34-7.28(m，2H)，5.86(s，1H)，4.34-4.26(m，2H)，3.83(d，J=11.6Hz，1H)，3.50-3.44(m，1H)，3.17(s，1H)，2.80(t，J=4.8Hz，1H)，2.66-2.62(m，2H)； 13C?NMR(125MHz，CDCl 3)δ137.8，132.5，129.6，129.5，128.1，127.2，85.6，81.9，70.3，61.6，58.7，50.5，44.3；HRMS(ESI)：calcdfor?C 13H 13ClO 3[M+Na] +275.0445；found275.0446.
The bromo-4-chlorine of 4.4-hydroxyl-4-[(2-) phenyl] fourth-2-alkynyl glycidyl ether (J-4)
Operate by such scheme two, the tetramer (S-1) (242mg, 1mmol) and the bromo-4-chlorobenzaldehyde of 2-((660mg, 3.0mmol)) are-78 DEG C of reactions, obtain colorless oil product, yield 58% through extraction, washing, dry, column chromatography. 1H?NMR(400MHz，CDCl 3)δ7.73(s，1H)，7.48(d，J=8.4Hz，1H)，7.18(d，J=8.4Hz，1H)，5.76(s，1H)，4.29(s，4H)，3.85(d，J=11.2Hz，1H)，3.49-3.43(m，1H)，3.18(s，1H)，2.82(t，J=4.8Hz，1H)，2.78(s，1H)，2.64(s，1H)； 13C?NMR(125MHz，CDCl 3)δ141.1，134.0，129.8，128.4，120.1，85.0，82.5，70.48，63.5，58.7，50.6，44.3；HRMS(ESI)：calcd?for?C 13H 12BrClO 3[M+Na] +352.9551；found352.9553.
The bromo-5-trifluoromethyl of 5.4-hydroxyl-4-[(3-) phenyl] fourth-2-alkynyl glycidyl ether (J-5)
Operate by such scheme two, the tetramer (S-1) (242mg, 1mmol) and the bromo-5-trifluoromethylated benzaldehyde of 3-(760mg, 3.0mmol) are-78 DEG C of reactions, obtain colorless oil product, yield 45% through extraction, washing, dry, column chromatography. 1H?NMR(400MHz，CDCl 3)δ7.87(s，1H)，7.73(s，2H)，5.54(s，1H)，4.32(s，2H)，3.88(d，J=11.6，1H)，3.46-3.42(m，1H)，3.19(s，1H)，2.83((d，J=4.8Hz，1H)，2.75(s，1H)，2.65-2.63(m，1H)； 13CNMR(125MHz，CDCl 3)δ143.5，133.0，132.52(q，J=32.5Hz)，128.20(q，J=3.75Hz)，122.82，122.10(q，J=3.75Hz)，123.0(q，J=271Hz)，85.3，83.3，70.68，63.09，58.64，50.62，44.17.HRMS(ESI)：calcd?for?C 14H 12BrF 3O 3[M+Na] +386.9814；found386.9816.
6.4-hydroxyl-4-[(4-methoxyl group) phenyl] fourth-2-alkynyl glycidyl ether (J-6)
Operate by such scheme two, the tetramer (S-1) (242mg, 1mmol) and 4-methoxybenzaldehyde (408mg, 3.0mm01) are-78 DEG C of reactions, obtain colorless oil product, yield 55% through extraction, washing, dry, column chromatography. 1H?NMR(400MHz，CDCl 3)δ7.45(d，J=8.0Hz，2H)，6.90(d，J=8.0Hz，2H)，5.46(s，1H)，4.31(t，J=17.2Hz，2H)，?3.81(s，3H)，3.48(q，J=6.0Hz，1H)，3.18(s，1H)，2.81(t，J=4.2Hz，1H)，2.64-2.62(m，1H)，2.38(s，1H)； 13C?NMR(125MHz，CDCl 3)δ159.4，133.1，127.8，113.7，87.1，81.3，70.2，63.6，58.6，55.0，50.3，44.0；HRMS(ESI)：calcd?for?C 14H 16O 4[M+Na] +271.0941；found271.0943.
7.4-hydroxyl-4-[(2-bromine) phenyl] fourth-2-alkynyl glycidyl ether (J-7)
Operate by such scheme two, the tetramer (S-1) (242mg, 1mmol) and 2-bromobenzaldehyde (550mg, 3.0mmol) are-78 DEG C of reactions, obtain colorless oil product, yield 44% through extraction, washing, dry, column chromatography. 1HNMR(400MHz，CDCl 3)δ7.74(d，J=8.0Hz，1H)，7.56(d，J=8.0Hz，1H)，7.36(t，J=7.6Hz，1H)，7.20(t，J=7.6Hz，1H)，5.83(s，1H)，4.29(t，J=16.8Hz，2H)，3.83(d，J=11.2Hz，1H)，3.50-3.44(m，1H)，3.17(s，1H)，2.80(t，J=4.8Hz，1H)，2.76(d，J=4.2Hz，1H)，2.63(s，1H); 13C?NMR(125MHz，CDCl 3)δ139.3，133.0，129.9，128.4，127.9，122.5，85.5，82.3，70.4，64.0，58.7，50.6，44.3.HRMS(ESI)：calcd?for?C 13H 13BrO 3[M+Na] +318.9940；found318.9941.
The bromo-2-naphthyl of 8.4-hydroxyl-4-[1-] fourth-2-alkynyl glycidyl ether (J-8)
Operate by such scheme two, the tetramer (S-1) (242mg, 1mmol) and the bromo-2-naphthaldehyde of 1-(705mg, 3.0mmol) are-78 DEG C of reactions, obtain colorless oil product, yield 56% through extraction, washing, dry, column chromatography. 1HNMR(400MHz，CDCl 3)δ8.34(d，J=8.4Hz，1H)，7.86-7.83(m，3H)，7.62(t，J=7.6Hz，1H)，7.55(t,J=7.6Hz，1H)，6.19(s，1H)，4.34-4.25(m，2H)，3.83(d，J=11.2，1H)，3.50-3.44(m，1H)，3.17(m，1H)，2.79(m，2H)，2.62(m，，1H)； 13C?NMR(125MHz，CDCl 3)δ137.4，134.4，132.2，128.4，128.2，127.7，127.6，127.0，124.9，122.7，85.9，82.4，70.4，64.9，58.8，50.6，44.3.HRMS(ESI)：calcd?for?C 17H 15BrO 3[M+Na] +369.0097；found369.0094.
The bromo-3-methoxyl group of 9.4-hydroxyl-4-[(4-) phenyl] fourth-2-alkynyl glycidyl ether (J-9)
Operate by such scheme two, the tetramer (S-1) (242mg, 1mmol) and the bromo-m-methoxybenzaldehyde of 4-(645mg, 3.0mmol) are-78 DEG C of reactions, obtain colorless oil product, yield 52% through extraction, washing, dry, column chromatography. 1H?NMR(400MHz，CDCl 3)δ7.72(s，1H)，7.43(d，J=8.4Hz，1H)，6.89(d，J=8.4，1H)，5.44(s，1H)，4.31(s，2H)，3.90(s，3H)，3.86(d，J=11.6Hz，1H)，3.49-3.45(m，1H)，3.19(s，1H)，2.82(s，1H)，2.64(s，1H)，2.34(s，1H)； 13C?NMR(101MHz，CDCl 3)δ156.3，134.4，131.9，126.9，112.2，112.1，86.3，82.8，70.7，63.7，58.8，56.5，50.5，44.3；HRMS(ESI)：calcd?for?C 14H 15BrO 4[M+Na] +349.0046；found349.0047.
10.4-hydroxyl-4-[(2,3-dimethoxy) phenyl] fourth-2-alkynyl glycidyl ether (J-10)
Operate the tetramer (S-1) (242mg, 1mmol) and 2 by such scheme two, 3-dimethoxy benzaldehyde (415mg, 3.0mmol)-78 DEG C of reactions, obtain colorless oil product, yield 55% through extraction, washing, dry, column chromatography. 1H?NMR(400MHz，CDCl 3)7.10-7.15(m，2H)，6.92(d，J=7.6Hz，1H)，5.66(d，J=7.2Hz，1H)，4.29(t，J=?17.6Hz，2H)，3.96(s，3H)，3.88(s，3H)，3.82(d，J=11.2Hz，1H)，3.48(q，J=5.6Hz，1H)，3.16(s，1H)，3.07(d，J=7.2Hz，1H)，2.80(s，1H)，2.62(s，1H)； 13C?NMR(125MHz，CDCl 3)δ152.6，146.5，134.3，124.2，119.4，112.9，86.9，81.4，70.3，61.1，61.1，58.8，55.8，50.5，44.3.HRMS(ESI)：calcd?for?C 15H 18O 5[M+Na] +301.1046；found301.1048.
11.4-hydroxyl-4-[(4-benzyloxy) phenyl] fourth-2-alkynyl glycidyl ether (J-11)
Operate by such scheme two, the tetramer (S-1) (242mg, 1mmol) and 4-benzyloxy phenyl aldehyde (415mg, 3.0mmol) are-78 DEG C of reactions, obtain colorless oil product, yield 48% through extraction, washing, dry, column chromatography. 1H?NMR(400MHz，CDCl 3)7.31-7.46(m，7H)，6.99-6.96(dd，J=8.8，2.0Hz，2H)，5.46(s，1H)，5.08(s，2H)，4.31(s，2H)，3.84(d，J=11.2，1H)，3.48(dd，J=11.2,5.9Hz，1H)，3.16-3.19(m，1H)，2.80-2.82(m，1H)，2.62-2.64(m，1H)，2.24(s，1H)； 13C?NMR(125MHz，CDCl 3)δ158.9，136.8，132.9，128.6，128.0，128.0，127.40，115.0，86.7，82.1，70.5，70.1，64.2，58.8，50.6，44.3；HRMS(ESI)：calcd?for?C 20H 20O 4[M+Na] +347.1254；found347.1251.
12.4-hydroxyl-4-(5-bromo-1,3-benzodioxole-2-yl) fourth-2-alkynyl glycidyl ether (J-12)
Operate the tetramer (S-1) (242mg, 1mmol) and 6-bromo-3 by such scheme two, 4-methylene-benzene formaldehyde (680mg, 3.0mmol)-78 DEG C of reactions, obtain colorless oil product, yield 47% through extraction, washing, dry, column chromatography. 1H?NMR(400MHz，CDCl 3)δ7.03(d，J=8.4Hz，1H)，6.67(d，J=8.4Hz，1H)，6.06(s，2H)，5.80(d，J=9.2Hz，1H)，4.31-4.22(m，2H)，3.80(dd，J=11.2，3.2Hz，1H)，3.51-3.46(m，1H)，3.18-3.14(m，1H)，3.05(d，J=9.2Hz，1H)，2.80(dd，J=4.8，4.8Hz，1H)，2.63-2.60(m，1H) 13C?NMR(125MHz，CDCl 3)δ147.6，146.1，125.8，122.2，112.5，109.4，102.2，84.8，81.6，70.3，61.5，58.7，50.5，44.4；HRMS(ESI)：calcd?for?C 14H 13BrO 5[M+Na] +363；found363。

Claims (9)

1. a compounds---epoxy chloropropane is tetrameric synthetic, it is characterized in that: taking epoxy chloropropionate alkyl compound as raw material, the mixture of water and organic solvent is solvent, the in the situation that of highly basic and quaternary ammonium salt-type phase transfer catalyst existence, room temperature is reacted, and obtains the epoxy chloropropane tetramer.
2. by the tetrameric synthetic method of epoxy chloropropane claimed in claim 1, it is characterized in that: described epoxy chloropropionate alkyl compound, has the general structure shown in general formula (I):
Figure FSA0000101373030000011
In formula, R 1for the straight chain of H, C1～C8 or the replacement of straight chain or non-substituted alkyl, cycloalkyl, aryl, substituted arene base;
In formula, R 2for the straight chain of H, C1～C5 or the replacement of straight chain or non-substituted alkyl, cycloalkyl, aryl, substituted arene base;
In formula, R 3for the straight chain of H, C1～C5 or the replacement of straight chain or non-substituted alkyl.
3. by the tetrameric synthetic method of epoxy chloropropane claimed in claim 1, it is characterized in that: described organic solvent is normal hexane, toluene, methylene dichloride, chloroform, ether, tetrahydrofuran (THF).
4. by the tetrameric synthetic method of epoxy chloropropane claimed in claim 1, it is characterized in that: described highly basic is sodium hydroxide, potassium hydroxide, cesium hydroxide.
5. by the tetrameric synthetic method of epoxy chloropropane claimed in claim 1, it is characterized in that: described epoxy chloropropane tetramerization compound, has the general structure shown in general formula (II):
Figure FSA0000101373030000012
In formula, R 1for the straight chain of H, C1～C8 or the replacement of straight chain or non-substituted alkyl, cycloalkyl, aryl, substituted arene base;
In formula, R 2for the straight chain of H, C1～C5 or the replacement of straight chain or non-substituted alkyl, cycloalkyl, aryl, substituted arene base;
In formula, R 3for the straight chain of H, C1～C5 or the replacement of straight chain or non-substituted alkyl.
The tetramer of epoxy chloropropionate alkyl compound can with the derivatives reaction of formaldehyde, it is characterized in that: the tetramer is dissolved in anhydrous tetrahydro furan or anhydrous diethyl ether, be cooled to-78 DEG C, add highly basic, after-78 DEG C of reaction 1h, add formaldehyde derivatives, maintain this temperature, stopped reaction after reaction 3h, can obtain proyl glycidyl ether derivatives through aftertreatment.
7. the method for reacting with formaldehyde derivatives by the tetramer claimed in claim 6, is characterized in that: described highly basic be n-Butyl Lithium,
Tert-butyl lithium, lithium diisopropylamine.
8. the method for reacting with formaldehyde derivatives by the tetramer claimed in claim 6, is characterized in that: the derivative of formaldehyde is structure
Compound as shown in general formula (III):
Figure FSA0000101373030000021
In formula, R 5for by nitro, OR 6, trifluoromethyl, F, Cl, Br, R 6one replaces or polysubstituted aryl, benzo are saturated, unsaturated heterocycle or condensed-nuclei aromatics base;
In formula, R 6for the straight chain of C1～C5 or the replacement of straight chain or non-substituted alkyl, aryl.
9. the method for reacting with formaldehyde derivatives by the tetramer claimed in claim 6, is characterized in that: described proyl glycidyl ether derivatives is the compound of structure as shown in general formula (IV):
Figure FSA0000101373030000022
In formula, R 1for the straight chain of H, C1～C8 or the replacement of straight chain or non-substituted alkyl, cycloalkyl, aryl, substituted arene base;
In formula, R 2for the straight chain of H, C1～C5 or the replacement of straight chain or non-substituted alkyl, cycloalkyl, aryl, substituted arene base;
In formula, R 3for the straight chain of H, C1～C5 or the replacement of straight chain or non-substituted alkyl;
In formula, R 5for by nitro, OR 6, trifluoromethyl, F, Cl, Br, R 6one replaces or polysubstituted aryl, benzo are saturated, unsaturated heterocycle or condensed-nuclei aromatics base;
In formula, R 6for the straight chain of C1～C5 or the replacement of straight chain or non-substituted alkyl, aryl.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101663286A (en) * 2007-05-08 2010-03-03 三菱瓦斯化学株式会社 Process for producing tetraglycidylamino compound

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Publication number Priority date Publication date Assignee Title
CN101663286A (en) * 2007-05-08 2010-03-03 三菱瓦斯化学株式会社 Process for producing tetraglycidylamino compound

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A.U. FRANCIS ET AL.: "Structural characterization of hydroxyl terminated polyepichlorohydrin obtained using boron trifluoride etherate and stannic chloride as initiators", 《EUROPEAN POLYMER JOURNAL》 *
A.U. FRANCIS ET AL.: "Structural characterization of hydroxyl terminated polyepichlorohydrin obtained using boron trifluoride etherate and stannic chloride as initiators", 《EUROPEAN POLYMER JOURNAL》, vol. 39, 28 February 2003 (2003-02-28), pages 831 - 841, XP004409008, DOI: doi:10.1016/S0014-3057(02)00302-6 *
LUN-ZHI DAI ET AL.: "A Gold(I)-Catalyzed Intramolecular Reaction of Propargylic/Homopropargylic Alcohols with Oxirane", 《CHEM.EUR.J》 *
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