CN101343213B - Allyl ether series compound and preparation thereof - Google Patents
Allyl ether series compound and preparation thereof Download PDFInfo
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- CN101343213B CN101343213B CN2008101202556A CN200810120255A CN101343213B CN 101343213 B CN101343213 B CN 101343213B CN 2008101202556 A CN2008101202556 A CN 2008101202556A CN 200810120255 A CN200810120255 A CN 200810120255A CN 101343213 B CN101343213 B CN 101343213B
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- allyl ether
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- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- -1 Allyl ether series compound Chemical class 0.000 title claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 10
- 239000012442 inert solvent Substances 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 5
- 150000003624 transition metals Chemical class 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 3
- 239000000376 reactant Substances 0.000 claims abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 100
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 150000001361 allenes Chemical class 0.000 claims description 7
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012044 organic layer Substances 0.000 claims description 6
- 239000012141 concentrate Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 238000003810 ethyl acetate extraction Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 claims description 3
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- SRNVHCKWYJALIZ-UHFFFAOYSA-N [Au].[N+](=O)(O)[O-].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [Au].[N+](=O)(O)[O-].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 SRNVHCKWYJALIZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 150000001555 benzenes Chemical class 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 150000008282 halocarbons Chemical group 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 abstract 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 239000000047 product Substances 0.000 description 22
- 239000007788 liquid Substances 0.000 description 21
- 238000005160 1H NMR spectroscopy Methods 0.000 description 13
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical compound C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003333 secondary alcohols Chemical class 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003509 tertiary alcohols Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BNFGCJCSBBKXPP-UHFFFAOYSA-N 3-propan-2-yloxyprop-1-enylbenzene Chemical compound CC(C)OCC=CC1=CC=CC=C1 BNFGCJCSBBKXPP-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- BFEAJWAVBUNGEF-UHFFFAOYSA-N C(C)(C)(C)OCC=CC1=CC=C(C=C1)CCCC Chemical compound C(C)(C)(C)OCC=CC1=CC=C(C=C1)CCCC BFEAJWAVBUNGEF-UHFFFAOYSA-N 0.000 description 1
- ZVPJTOVBQHDPOP-UHFFFAOYSA-N C(C)(C)OCC=CC1=CC=C(C=C1)CCCCC Chemical compound C(C)(C)OCC=CC1=CC=C(C=C1)CCCCC ZVPJTOVBQHDPOP-UHFFFAOYSA-N 0.000 description 1
- PQRXREKOKAMJSF-UHFFFAOYSA-N C(CCC)C1=CC=C(C=C1)C=CCOC(C)C Chemical compound C(CCC)C1=CC=C(C=C1)C=CCOC(C)C PQRXREKOKAMJSF-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- BNFGCJCSBBKXPP-RMKNXTFCSA-N [(e)-3-propan-2-yloxyprop-1-enyl]benzene Chemical compound CC(C)OC\C=C\C1=CC=CC=C1 BNFGCJCSBBKXPP-RMKNXTFCSA-N 0.000 description 1
- VDFHYFWUXJGDSX-UHFFFAOYSA-N [N+](=O)([O-])[Au] Chemical compound [N+](=O)([O-])[Au] VDFHYFWUXJGDSX-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- RQGNEYFWHWFECS-UHFFFAOYSA-N amino formate Chemical class NOC=O RQGNEYFWHWFECS-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- WRJWRGBVPUUDLA-UHFFFAOYSA-N chlorosulfonyl isocyanate Chemical compound ClS(=O)(=O)N=C=O WRJWRGBVPUUDLA-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a diallyl oxide compound as well as a preparation method thereof, the diallyl oxide compound has a structure as is shown in a formula (III), and R1 and R2 are respectively selected from hydrogen, and alkyl, phenyl and alkyl having 1 to 50 carbon atoms or phenyl, benzyl and nitrogenous heterocyclic residue substituted by alkoxy, and alkoxy having 1 to 50 carbon atoms independently in the formula (III). The preparation method is as follows: under the action of a transition metal catalyst M(PR3)X, an allene compound as shown in a formula (I) of the reactant and alcohol asshown in a formula (II) are in complete reaction when the temperature is controlled between 35 and 80 DEG C under the condition of presence of promoter protonic acid in an inert solvent, and the diallyl oxide compound shown in the formula (III) is obtained after the post treatment. The compound has broad application prospect, and the preparation method has advantages of mild reaction conditions, simple operation, high reaction yield, good selectivity, low pollution and good promotion and application prospect.
Description
(1) technical field
The present invention relates to allyl ether series compound and preparation method thereof.
(2) background technology
Allyl ether series compound is widely used in fields such as protecting group, polymer monomer or linking agent and photocuring, thermofixation, free radical curable coatings, air-drying property unsaturated polyester coating and flame-retarded resin as the important organic synthesis intermediate of a class.The synthetic method report of relevant allyl ether series compound is more, and for example traditional preparation method is by oxy-compound and allyl group halohydrocarbon condensation reaction synthetic (Liaoning chemical industry, 2001,30 (12), 531~532,552).But synthetic method commonly used can produce a large amount of by products, brings serious contaminate environment, does not also meet atom economy type principle.Therefore, invent a kind of efficient, economic synthetic method and seem very important.
(3) summary of the invention
The matter of utmost importance that the present invention will solve provides a class allyl ether series compound, described allyl ether series compound, and its structure is suc as formula shown in (III):
In the formula (III), R
1, R
2Independently be selected from phenyl, benzyl, the nitrogen heterocyclic ring residue that hydrogen, the alkyl with 1~50 carbon atom, phenyl, alkyl or alkoxyl group replace, alkoxyl group separately with 1~50 carbon atom.
Further, described R
1Independently be selected from phenyl, to butyl phenyl, to amyl group phenyl or p-methoxyphenyl; R
2Independently be selected from the alkyl or the benzyl of 1~5 carbon atom.
Second technical problem that the present invention will solve provide a kind of reaction conditions gentleness, easy and simple to handle, reaction yield is high, selectivity good, pollutes less, has the allyl ether series compound preparation method of better popularizing application prospect.
For addressing the above problem, the preparation method of described allyl ether series compound is as follows: at transition-metal catalyst M (PR
3) under the effect of X, alcohol shown in propadiene compounds shown in the reactant formula (I) and the formula (II), controlled temperature fully reaction between 35~80 ℃ in inert solvent and under the promotor protonic acid existence condition, aftertreatment obtains the allyl ether series compound shown in the formula (III).Reaction equation is as follows:
R in formula (I), the formula (II)
1, R
2Definition R in the cotype (III) respectively
1, R
2Definition, described alcohol can be primary alcohol (primary alconol), secondary alcohol (secondary alcohol) or tertiary alcohol (tertiary alcohol).
M (PR
3) among the X, M is Jinyang ion; PR
3For with the phosphine ligand of Jinyang ion coordination, wherein R
3Be phenyl or butyl; X is a negatively charged ion, and it is one of following that described X is selected from: cl anion, bromine anions, nitric acid negatively charged ion.
Further, the transition-metal catalyst described in the present invention preferably suc as formula (IV) expression nitric acid gold-triphenylphosphine complex compound;
(PPh
3)AuNO
3 (IV)
Reaction of the present invention needs to carry out under promotor protonic acid existence condition, generally adds the vitriol oil or methylsulfonic acid or trifluoromethanesulfonic acid, the preferred vitriol oil.
Described inert solvent is not for interfering the solvent of compound (I) and compound (II) reaction, its boiling point can be 60~250 ℃ of scopes, can be selected from halogenated hydrocarbon, substituted benzene or ether compound, specifically can select for use one of following: methylene dichloride, ethylene dichloride, toluene, chlorobenzene, ether, tetrahydrofuran (THF), dioxane.Be best as solvent wherein with ethers.
The present invention recommends to feed intake amount of substance than propadiene compounds (I): alcohol (II): M (PR
3) X: protonic acid=1:1.0~2.0:0.01~0.05:0.5~2.0.
The consumption of described inert solvent is: with respect to the propadiene compounds of every 1mol, use 0.5~1.0L.
The described reaction times is 2~10 hours.
Aftertreatment of the present invention can be adopted following steps: after reacting completely, dripping an amount of saturated sodium bicarbonate solution to solution does not have the bubble generation, adds water, and use ethyl acetate extraction, merge organic layer, drying, concentrate brown fraction, column chromatography gets the final product allyl ether series compound.
Concrete recommendation is described preparation method carry out according to following steps: under the condition of room temperature, add propadiene compounds (I) and inert solvent in the reactor, under condition of stirring, slowly add alcohol (II), add the nitric acid gold-triphenyl phosphorus complex compound (IV) and vitriol oil subsequently, finish intensification, reacted about 2~10 hours, treat that raw material reaction is complete, reduce to room temperature, dripping an amount of saturated sodium bicarbonate solution to solution does not have the bubble generation, adds water, and uses ethyl acetate extraction, merge organic layer, drying, concentrate brown fraction, column chromatography gets the final product allyl ether series compound.
The allyl ether series compound for preparing in view of the present invention is used in medicine industry field (Archives of Pharmacal Research.2001 as the important physical active substance, 24,271-276), simultaneously prepared allyl ether series compound can be further changes into the amino formate compounds (embodiment 22) of the allyl group replacement of widespread use in protein and polypeptide synthetic with the SULPHURYL CHLORIDE isocyanate reaction according to bibliographical information, therefore preparation method of the present invention has wide application prospect (Tetrahedron, 2001,57,8257-8266; Archives of Pharmacal Research.2001,24,271-276).
The preparation method of allyl ether series compound of the present invention, its key are to have selected for use auriferous compound to make catalyzer, and under the tart condition, reaction generates the compound with allyl ethers structure.Compared with prior art, its advantage is: (1) reaction conditions gentleness, easy to operate, product quality is good, the yield height.(2) to environment-friendly, the basic toxicological harmless of whole process of production produces, to operator also safety.(3) this reaction meets the atom economy principle, the raw material availability height.
(4) embodiment
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Embodiment 1:
(E)-preparation of 1-(3-methoxyl group-1-propenyl) benzene:
With propadiene base benzene (50mg, 0.338mmol), the vitriol oil (33.12mg, 18.0 μ l, 0.338mmol), nitro gold complex ((PPh)
3AuNO
3) (3.5mg, 0.00676mmol), (11.90mg, 15.1 μ l 0.372mmol) 1, mix in the 4-dioxane (1.5mL) methyl alcohol, and 6h is reacted in 70 ℃ of oil bath heating.Add saturated NaHCO
3The aqueous solution (1.0mL) is used ethyl acetate (10mL * 3) extraction then, uses anhydrous sodium sulfate drying, filters, and concentrates, and (sherwood oil: ethyl acetate=20:1), obtain target compound 46.2mg, yield is 72.4% to column chromatography, yellow oily liquid.
1HNMR(500MHz,CDCl
3):δ7.40~7.37(m,2H),7.33~7.29(m,2H),7.25~7.21(m,1H),6.61(d,J=16.0Hz,1H),6.28(dt,J=16.0,6.0Hz,1H),4.09(dd,J=6.0,1.5Hz,2H),3.39(s,3H).
Embodiment 2:
(E)-preparation of 1-(3-methoxyl group-1-propenyl) benzene:
Operation just replaces 1 with tetrahydrofuran (THF) with reference to embodiment 1, and the 4-dioxane obtains target product 40.0mg, and yield is 62.7%, the pale yellow oily liquid body.
Embodiment 3:
(E)-preparation of 1-(3-methoxyl group-1-propenyl) benzene:
Operation just replaces 1 with methylene dichloride with reference to embodiment 1, and the 4-dioxane obtains target product 10.0mg, and yield is 15.7%, the pale yellow oily liquid body.
Embodiment 4:
(E)-preparation of 1-(3-methoxyl group-1-propenyl) benzene:
Operation just replaces 1 with ethylene dichloride with reference to embodiment 1, and the 4-dioxane obtains target product 20.0mg, and yield is 31.3%, the pale yellow oily liquid body.
Embodiment 5:
(E)-preparation of 1-(3-methoxyl group-1-propenyl) benzene:
Operation just replaces 1 with chlorobenzene with reference to embodiment 1, and the 4-dioxane obtains target product 5.0mg, and yield is 7.8%, the pale yellow oily liquid body.
Embodiment 6:
(E)-preparation of 1-(3-methoxyl group-1-propenyl) benzene:
Operation just replaces the vitriol oil with trifluoromethanesulfonic acid with reference to embodiment 1, obtains target product 45.0mg, and yield is 70.5%, the pale yellow oily liquid body.
Embodiment 7:
(E)-preparation of 1-(3-methoxyl group-1-propenyl) benzene:
Operation just replaces the vitriol oil with methylsulfonic acid with reference to embodiment 1, obtains target product 43.0mg, and yield is 69%, the pale yellow oily liquid body.
Embodiment 8:
(E)-preparation of 1-(3-methoxyl group-1-propenyl) benzene:
Operation is with reference to embodiment 1, and just methanol usage is that (23.80mg, 30.2 μ l 0.744mmol), obtain target product 46.0mg, and yield is 72%, the pale yellow oily liquid body.
Embodiment 9:
(E)-preparation of 1-(3-methoxyl group-1-propenyl) benzene:
Operation is with reference to embodiment 1, and just temperature of reaction is a room temperature, obtains target product 3.0mg, and yield is 4.7%, the pale yellow oily liquid body.
Embodiment 10:
(E)-preparation of 1-(3-oxyethyl group-1-propenyl) benzene
Operation just replaces methyl alcohol with ethanol with reference to embodiment 1, replaces 1 with tetrahydrofuran (THF), and the 4-dioxane obtains target product 43.0mg, and yield is 76.8%, the pale yellow oily liquid body.
1HNMR(500MHz,CDCl
3):δ7.40~7.37(m,2H),7.32~7.28(m,2H),7.25~7.21(m,1H),6.60(d,J=16.0Hz,1H),6.30(dt,J=16.0,6.0Hz,1H),4.09(dd,J=6.0,1.5Hz,2H),3.55(q,J=7.0Hz,2H),1.25(t,J=7.0Hz,3H).
Embodiment 11:
(E)-preparation of 1-(3-isopropoxy-1-propenyl) benzene
Operation just replaces methyl alcohol with Virahol with reference to embodiment 1, obtains target product 45.4mg, and yield is 81%, the pale yellow oily liquid body.
1HNMR(500MHz,CDCl
3):δ7.40~7.38(m,2H),7.38~7.28(m,2H),7.25~7.20(m,1H),6.60(d,J=16.0Hz,1H),6.30(dt,J=15.5,6.0Hz,1H),4.13(dd,J=6.0,1.5Hz,2H),3.70(m,1H),1.21(d,J=6Hz,6H).
Embodiment 12:
(E)-preparation of 1-(3-methoxyl group-1-propenyl)-4-anisole:
Operation just replaces propadiene base benzene with 1-methoxyl group-4-propadiene base benzene with reference to embodiment 1, replaces 1 with toluene, and the 4-dioxane obtains target product 50.7mg, and yield is 83.2%, the pale yellow oily liquid body.
1HNMR(400MHz,CDCl
3):δ7.35-7.31(m,2H),6.88-6.83(m,2H),6.55(d,J=16.0Hz,1H),6.15(dt,J=16.0,6.4Hz,2H),4.07(dd,J=6.4,1.5Hz,2H),3.80(s,3H),3.38(s,3H).
Embodiment 13:
(E)-preparation of 1-(3-second methoxyl group-1-propenyl)-4-anisole:
Operation just replaces propadiene base benzene with 1-methoxyl group-4-propadiene base benzene with reference to embodiment 1, and replaces methyl alcohol with ethanol, obtains target product 49.0mg, and yield is 74.5%, the pale yellow oily liquid body.
1HNMR(500MHz,CDCl
3):δ7.33-7.31(m,2H),6.86-6.84(m,2H),6.55(d,J=16Hz,1H),6.17(dt,J=16,6.0Hz,2H),4.11(dd,J=6.0,1.0Hz,2H),3.81(s,3H),3.54(q,J=7.0Hz,2H),1.25(t,J=7.0Hz,3H)
Embodiment 14:
Operation just replaces propadiene base benzene with 1-methoxyl group-4-propadiene base benzene with reference to embodiment 1, and replaces methyl alcohol with Virahol, obtains target product 57.3mg, and yield is 81.2%, the pale yellow oily liquid body.
1HNMR(500MHz,CDCl
3):δ7.33-7.31(m,2H),6.85-6.83(m,2H),6.54?(d,J=15.5Hz,1H),6.17(dt,J=15.5,6.0Hz,2H),4.11(dd,J=6.0,1.5Hz,2H),3.0(s,3H),3.71-3.65(m,1H),1.20(d,J=6.0Hz,6H)
Embodiment 15:
(E)-preparation of 1-(3-benzyloxy-1-propenyl)-4-anisole:
Operation just replaces propadiene base benzene with 1-methoxyl group-4-propadiene base benzene with reference to embodiment 1, and replaces methyl alcohol with phenylcarbinol, obtains target product 69.0mg, and yield is 79.3%, the pale yellow oily liquid body.
1HNMR(500MHz,CDCl
3):δ7.38-7.29(m,7H),6.86-6.84(m,2H),6.57(d,J=16.0Hz,1H),6.20(dt,J=16.0,6.5Hz,2H),4.57(s,2H),4.17(dd,J=6.5,1.5Hz,3H),3.81(s,3H).
Embodiment 16:
(E)-preparation of 1-butyl-4-(3-methoxyl group-1-propenyl) benzene:
Operation just replaces propadiene base benzene with 1-butyl-4-propadiene base benzene with reference to embodiment 1, obtains target product 45.2mg, and yield is 82.7%, the pale yellow oily liquid body.
1HNMR(500MHz,CDCl
3):δ7.29(d,J=8.0Hz,2H),7.12(d,J=8.0Hz,2H),6.57(d,J=16.0Hz,2H),6.23(dt,J=16.0,6.0Hz,1H),4.07(dd,J=6.0,1.5Hz,2H),3.37(s,3H),2.58(t,J=7.5Hz,2H),1.61-1.55(m,?2H),1.57-1.32(m,2H),0.92(t,J=7.5Hz,3H)
Embodiment 17:
(E)-preparation of 1-butyl-4-(3-isopropoxy-1-propenyl) benzene:
Operation just replaces propadiene base benzene with 1-butyl-4-propadiene base benzene with reference to embodiment 1, and replaces methyl alcohol with Virahol, obtains target product 57.6mg, and yield is 85.4%, the pale yellow oily liquid body.
1HNMR(500MHz,CDCl
3):δ7.29(d,J=8.5Hz,2H),7.12(d,J=8.5Hz,2H),6.57(d,J=16.0Hz,2H),6.25(dt,J=16.0,6.5Hz,1H),4.13(dd,J=6.5,1.5Hz,2H),3.71-3.65(m,1H),2.58(t,J=7.5Hz,2H),1.58-1.56(m,2H),1.35-1.29(m,2H),1.20(d,J=6.0Hz,6H),0.92(t,J=7.5Hz,3H)
Embodiment 18:
(E)-preparation of 1-butyl-4-(3-tertiary butyl Oxy-1-propenyl) benzene:
Operation just replaces propadiene base benzene with 1-butyl-4-propadiene base benzene with reference to embodiment 1, and replaces methyl alcohol with the trimethyl carbinol, obtains target product 60.5mg, and yield is 84.6%, the pale yellow oily liquid body.
1HNMR(500MHz,CDCl
3):δ7.29(d,J=8.0Hz,2H),7.10(d,J=8.0Hz,?2H),6.57(d,J=16.0Hz,2H),6.25(dt,J=16.0,6.0Hz,1H),4.06(dd,J=6.0,1.5Hz,2H),2.58(t,J=7.5Hz,2H),1.61-1.54(m,2H),1.36-1.31(m,2H),0.92(t,J=7.2Hz,3H)
Embodiment 19:
(E)-preparation of 1-(3-methoxyl group-1-propenyl)-4-amylbenzene:
Operation just replaces propadiene base benzene with 1-amyl group-4-propadiene base benzene with reference to embodiment 1, obtains target product 53.9mg, and yield is 93.1%, the pale yellow oily liquid body.
1HNMR(500MHz,CDCl
3):δ7.30(d,J=8.5Hz,2H),7.12(d,J=8.5Hz,2H),6.57(d,J=16.0Hz,2H),6.23(dt,J=16.0,6.0Hz,1H),4.06(dd,J=6.0,1.5Hz,2H),3.37(s,3H),2.57(t,J=7.5Hz,2H),1.63-1.56(m,2H),1.34-1.29(m,4H),0.88(t,J=7.0Hz,3H)
Embodiment 20:
(E)-preparation of 1-(3-oxyethyl group-1-propenyl)-4-amylbenzene:
Operation just replaces propadiene base benzene with 1-amyl group-4-propadiene base benzene with reference to embodiment 1, and replaces methyl alcohol with ethanol, obtains target product 60.8mg, yield〉99%, the pale yellow oily liquid body.
1HNMR(500MHz,CDCl
3):δ7.29(d,J=8.0Hz,2H),7.10(d,J=8.0Hz,?2H),6.57(d,J=16.0Hz,2H),6.25(dt,J=16.0,6.0Hz,1H),4.11(dd,J=6.0,1.5Hz,2H),3.53(q,J=7.0Hz,2H),2.57(t,J=7.5Hz,2H),1.63-1.56(m,2H),1.33-1.30(m,4H),1.24(t,J=7.0Hz,3H),0.88(t,J=7.0Hz,3H)
Embodiment 21:
(E)-preparation of 1-(3-isopropoxy-1-propenyl)-4-amylbenzene:
Operation just replaces propadiene base benzene with 1-amyl group-4-propadiene base benzene with reference to embodiment 1, and replaces methyl alcohol with Virahol, obtains target product 60.3mg, and yield is 93%, the pale yellow oily liquid body.
1HNMR(500MHz,CDCl
3):δ7.29(d,J=8.0Hz,2H),7.11(d,J=8.0Hz,2H),6.57(d,J=15.5Hz,2H),6.25(dt,J=15.5,6.0Hz,1H),4.12(dd,J=6.0,1.5Hz,2H),3.71-3.65(m,1H),2.57(t,J=7.5Hz,2H),1.63-1.58(m,2H),1.34-1.29(m,4H),1.20(d,J=6.0Hz,6H),0.88(t,J=7.0Hz,3H)。
Embodiment 22:
In the time of 20 ℃; under nitrogen protection; in order yellow soda ash (0.7155g; 6.75mmol), SULPHURYL CHLORIDE isocyanic ester (0.64g; 4.5mmol), (E)-1-(3-isopropoxy-1-propenyl) benzene (0.528g; 3mmol) join in the anhydrous methylene chloride, stir, and temperature is controlled at about 20 ℃.With the liquid phase monitoring,, add H in the reaction process until reacting completely
2O (10mL) termination reaction with ethyl acetate extraction (10mL * 2), merges organic layer.The sodium sulfite solution of adding 25% and 10% potassium hydroxide solution in organic layer, stirred overnight at room temperature, anhydrous magnesium sulfate drying is used in organic layer saturated common salt water washing afterwards, concentrates.Enriched material is crossed post, uses ethyl acetate drip washing, finally obtains the shielded N-cinnamyl group-carbamic acid isopropyl ester of N, i.e. product B, yield 76%.
Claims (8)
1. the preparation method of an allyl ether series compound is characterized in that described preparation method is as follows: at transition-metal catalyst M (PR
3) under the effect of X, alcohol shown in propadiene compounds shown in the reactant formula (I) and the formula (II), controlled temperature fully reaction between 35~80 ℃ in inert solvent and under the promotor protonic acid existence condition, aftertreatment obtains the allyl ether series compound shown in the formula (III); Described inert solvent is selected from halogenated hydrocarbon, substituted benzene or ether compound; It is one of following that described promotor protonic acid is selected from: the vitriol oil, methylsulfonic acid or trifluoromethanesulfonic acid;
In formula (I), formula (II) or the formula (III), R
1Be selected from hydrogen, have the alkyl, phenyl of 1~50 carbon atom, to butyl phenyl, to amyl group phenyl, p-methoxyphenyl, benzyl, have the alkoxyl group of 1~50 carbon atom; R
2Be selected from alkyl, phenyl, the benzyl with 1~50 carbon atom, alkoxyl group with 1~50 carbon atom;
M (PR
3) among the X, M is Jinyang ion; PR
3For with the phosphine ligand of Jinyang ion coordination, wherein R
3Be phenyl; X is a negatively charged ion, and it is one of following that described X is selected from: cl anion, bromine anions, nitric acid negatively charged ion.
2. the preparation method of allyl ether series compound as claimed in claim 1 is characterized in that described transition-metal catalyst is the nitric acid gold-triphenylphosphine complex compound suc as formula (IV) expression;
(PPh
3)AuNO
3 (IV)。
3. the preparation method of allyl ether series compound as claimed in claim 1, it is one of following to it is characterized in that described inert solvent is selected from: methylene dichloride, ethylene dichloride, toluene, chlorobenzene, ether, tetrahydrofuran (THF), dioxane.
4. as the preparation method of the described allyl ether series compound of one of claim 1~3, the amount of substance that it is characterized in that feeding intake is than propadiene compounds (I): alcohol (II): M (PR
3) X: protonic acid=1: 1.0~2.0: 0.01~0.05: 0.5~2.0.
5. the preparation method of allyl ether series compound as claimed in claim 4 is characterized in that the consumption of described inert solvent is: with respect to the propadiene compounds of every 1mol, use 0.5~1.0L.
6. the preparation method of allyl ether series compound as claimed in claim 1 is characterized in that the described reaction times is 2~10 hours.
7. the preparation method of allyl ether series compound as claimed in claim 1, it is characterized in that described aftertreatment employing following steps: after reacting completely, drip an amount of saturated sodium bicarbonate solution to solution and do not have the bubble generation, add water, and use ethyl acetate extraction, merge organic layer, drying, concentrate brown fraction, column chromatography gets the final product allyl ether series compound.
8. the preparation method of allyl ether series compound as claimed in claim 1 is characterized in that described R
1Independently be selected from phenyl, to butyl phenyl, to amyl group phenyl or p-methoxyphenyl; R
2Independently be selected from the alkyl or the benzyl of 1~5 carbon atom.
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Non-Patent Citations (8)
Title |
---|
Berthiol, Florian |
Berthiol, Florian;et al..Heck reaction of protected allyl alcohols with aryl bromides catalyzed by a tetraphosphanepalladium complex.European Journal of Organic Chemistry.2005,(7),1367-1377. * |
difference in mechanism between hydroalkoxylation and hydroamination.Tetrahedron Letters.2008, |
difference in mechanism between hydroalkoxylation and hydroamination.Tetrahedron Letters.2008,49(33),4908-4911. |
et al..Heck reaction of protected allyl alcohols with aryl bromides catalyzed by a tetraphosphanepalladium complex.European Journal of Organic Chemistry.2005,(7),1367-1377. |
Nishina, Naoko |
Nishina, Naoko;Yamamoto, Yoshinori.Gold-catalyzed intermolecular hydroalkoxylation of allenes difference in mechanism between hydroalkoxylation and hydroamination.Tetrahedron Letters.2008, difference in mechanism between hydroalkoxylation and hydroamination.Tetrahedron Letters.2008,49(33),4908-4911. * |
Yamamoto, Yoshinori.Gold-catalyzed intermolecular hydroalkoxylation of allenes |
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