CN114605262A - Efficient selective synthesis method of phenyl allyl ether compound - Google Patents
Efficient selective synthesis method of phenyl allyl ether compound Download PDFInfo
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- 238000001308 synthesis method Methods 0.000 title claims abstract description 9
- -1 phenyl allyl ether compound Chemical class 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- POSICDHOUBKJKP-UHFFFAOYSA-N prop-2-enoxybenzene Chemical class C=CCOC1=CC=CC=C1 POSICDHOUBKJKP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000004440 column chromatography Methods 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000012046 mixed solvent Substances 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000003107 substituted aryl group Chemical group 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 238000001311 chemical methods and process Methods 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000002360 preparation method Methods 0.000 claims 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000012043 crude product Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 20
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 239000007810 chemical reaction solvent Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000007872 degassing Methods 0.000 description 5
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
- 238000005937 allylation reaction Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- PHDIJLFSKNMCMI-ITGJKDDRSA-N (3R,4S,5R,6R)-6-(hydroxymethyl)-4-(8-quinolin-6-yloxyoctoxy)oxane-2,3,5-triol Chemical compound OC[C@@H]1[C@H]([C@@H]([C@H](C(O1)O)O)OCCCCCCCCOC=1C=C2C=CC=NC2=CC=1)O PHDIJLFSKNMCMI-ITGJKDDRSA-N 0.000 description 1
- JNPGUXGVLNJQSQ-BGGMYYEUSA-M (e,3r,5s)-7-[4-(4-fluorophenyl)-1,2-di(propan-2-yl)pyrrol-3-yl]-3,5-dihydroxyhept-6-enoate Chemical compound CC(C)N1C(C(C)C)=C(\C=C\[C@@H](O)C[C@@H](O)CC([O-])=O)C(C=2C=CC(F)=CC=2)=C1 JNPGUXGVLNJQSQ-BGGMYYEUSA-M 0.000 description 1
- HIHOEGPXVVKJPP-JTQLQIEISA-N 5-fluoro-2-[[(1s)-1-(5-fluoropyridin-2-yl)ethyl]amino]-6-[(5-methyl-1h-pyrazol-3-yl)amino]pyridine-3-carbonitrile Chemical compound N([C@@H](C)C=1N=CC(F)=CC=1)C(C(=CC=1F)C#N)=NC=1NC=1C=C(C)NN=1 HIHOEGPXVVKJPP-JTQLQIEISA-N 0.000 description 1
- 238000005821 Claisen rearrangement reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- GVOISEJVFFIGQE-YCZSINBZSA-N n-[(1r,2s,5r)-5-[methyl(propan-2-yl)amino]-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](N(C)C(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 GVOISEJVFFIGQE-YCZSINBZSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/317—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
- C07C67/32—Decarboxylation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a high-efficiency selective synthesis method of phenyl allyl ether compounds, belonging to the field of organic synthesis. The method comprises the following steps: under the inert gas atmosphere, sequentially adding hydroxymethyl phenol, GMDVs, a catalyst and a solvent into a reactor, stirring at a certain temperature until the reaction is finished, concentrating the solvent to obtain a crude product, and performing column chromatography separation to obtain the phenyl allyl ether compound. The synthesis method has the advantages of high yield, good chemical selectivity, wide substrate application range, mild reaction conditions, convenient post-treatment and the like. The reaction equation is as follows:
Description
Technical Field
The invention discloses a high-efficiency selective synthesis method of phenyl allyl ether compounds, belonging to the technical field of organic synthesis.
Background
Phenyl allyl ether is a very important organic synthetic intermediate, which can be synthesized as a series of bioactive molecules or natural products (chem. rev.,2003,103,2921.). In addition, phenyl allyl ether compounds are precursors for a number of important reactions, such as the claisen rearrangement.
At present, the synthesis of phenyl allyl ether compounds mostly adopts nucleophilic substitution reaction of phenolic compounds and allyl halides under the action of strong alkali, or allyl reaction of allyl ester, allyl alcohol or other allyl precursors under the catalysis of transition metals (such as palladium). The above method does not show good selectivity when both phenolic hydroxyl group and alcoholic hydroxyl group are present in the reaction substrate. Because the synthesis method of the phenyl allyl ether is limited, the application of the phenyl allyl ether in organic synthesis is greatly limited. Therefore, a new allylation reagent is searched, and the development of a method for constructing phenyl allyl ether compounds with high efficiency and high selectivity is very important.
Disclosure of Invention
The invention aims to overcome the problem that the existing selective synthesis method of phenyl allyl ether compounds is limited, and provides a method for synthesizing phenyl allyl ether compounds with high efficiency and high selectivity.
In order to achieve the purpose, the invention provides a method for synthesizing phenyl allyl ether compounds with high efficiency and high selectivity by using GMDVs as an allylation reagent. The phenyl allyl ether compound has a structure shown in a formula I:
wherein R is1Selected from any one of saturated alkyl, alkoxy and halogen, and is positioned at 4 of benzene ring#、5#、6#One of the positions;
R2all are any one selected from aryl, substituted aryl, saturated alkyl and hydrogen atoms;
the aryl group is phenyl or naphthyl;
the substituent of the substituted aryl is any one of halogen atom, saturated alkyl, alkoxy and aryl;
sequentially adding hydroxymethyl phenol, GMDVs, a catalyst and a solvent into a reactor under an inert gas atmosphere, and stirring at a certain temperature until the reaction is finished; the chemical process is shown in a reaction formula II:
the catalyst is selected from palladium tetratriphenylphosphine (Pd (PPh)3)4) Palladium acetate, tris (dibenzylideneacetone) dipalladium (Pd)2(dba)3) Any one of them.
The solvent is any one of dichloromethane, tetrahydrofuran, ethyl acetate, ethanol, acetonitrile, acetone, N-dimethylformamide and 1, 4-dioxane.
The molar ratio of the hydroxymethyl phenol to the GMDVs to the catalyst is 1.0 (1.0-2.0) to 0.01-0.1.
The reaction time is 1-24 h.
The reaction temperature is 0-60 ℃.
After the reaction, the mixed solvent of petroleum ether and ethyl acetate is used for column chromatography separation.
The invention has the beneficial effects that: the high-efficiency selective synthesis method of the phenyl allyl ether compound provided by the invention is scientific and reasonable, and has the following remarkable advantages compared with the traditional method:
(1) the selective allylation of phenolic hydroxyl can be realized by using GMDVs as an allylation reagent;
(2) the reaction yield is high, the operation is simple, the condition is mild, the product is easy to separate, and the method is suitable for large-scale production;
(3) the substrate has wide application range and can be used for carrying out diversified synthesis on the phenyl allyl ether compounds.
Drawings
FIG. 1 is an NMR spectrum of a compound (3a) prepared in example 1;
FIG. 2 is an NMR spectrum of compound (3b) prepared in example 2;
FIG. 3 is an NMR spectrum of compound (3c) prepared in example 3;
FIG. 4 is an NMR spectrum of compound (3d) prepared in example 4;
FIG. 5 is an NMR spectrum of compound (3e) prepared in example 5.
Detailed Description
The method of the present invention is described herein by way of specific examples, but the present invention is not limited thereto, and any modifications, equivalents, improvements, etc. made within the technical spirit of the present invention should be included within the scope of the present invention.
Example 1:
the reaction equation is as follows:
compound 1a (5mmol), GMDVs (7.5mmol), Pd (PPh)3)4(0.25mmol) was sequentially added to the reactor under an inert gas atmosphere, 50 ml of anhydrous tetrahydrofuran was added thereto, followed by degassing and reaction at room temperature for 12 hours. After the reaction is finished, the reaction solvent is dried by spinning, and the pure 3a is obtained by chromatography with a mixed solvent of petroleum ether and ethyl acetate with the volume ratio of 8: 1. The yield of 3a was 78%.
The nuclear magnetic data for 3a are as follows:
1H NMR(500MHz,CDCl3)δ7.50(d,J＝2.5Hz,1H),7.36-7.22(m,10H),7.19(t,J＝7.5Hz,1H),6.61(d,J＝9.0Hz,1H),6.04(dd,J＝9.5,4.5Hz,1H),5.03(s,1H),4.99(s,1H),4.37-4.28(m,2H),3.82-3.74(m,1H),3.62(d,J＝2.5Hz,3H),2.89-2.74(m,2H),2.47-2.36(m,1H)ppm.
13C NMR(125MHz,CDCl3)δ173.66,154.45,142.63,141.32,138.18,134.40,134.29,131.13,130.45,128.72,128.31,127.84,127.55,127.50,126.50,114.87,114.80,113.43,71.27,71.20,71.13,52.14,49.98,36.29ppm.
example 2
The reaction equation is as follows:
will combine withSubstance 1b (5mmol), GMDVs (7.5mmol), Pd2(dba)3(0.25mmol) was sequentially added to the reactor under an inert gas atmosphere, 50 ml of anhydrous tetrahydrofuran was added thereto, followed by degassing and reaction at room temperature for 12 hours. After the reaction is finished, the reaction solvent is dried in a spinning mode, and the pure 3b is obtained by using mixed solvent column chromatography of petroleum ether and ethyl acetate in the volume ratio of 5: 1. The yield of 3b was 70%.
Nuclear magnetic data for 3b are as follows:
1H NMR(500MHz,CDCl3)δ7.40-7.33(m,2H),7.33-7.22(m,7H),7.17(t,J＝7.5Hz,1H),7.13(d,J＝8.5Hz,1H),6.46(dd,J＝8.5,2.0Hz,1H),6.40(d,J＝1.5Hz,1H),6.03(t,J＝6.0Hz,1H),5.09(s,1H),5.00(s,1H),4.42-4.30(m,2H),3.84-3.74(m,4H),3.62(d,J＝4.0Hz,3H),2.94-2.80(m,2H),2.51-2.39ppm.
13C NMR(125MHz,CDCl3)δ173.74,173.69,160.22,156.64,143.55,141.58,138.28,128.74,128.70,128.09,127.84,127.48,127.01,126.39,124.90,124.82,114.80,114.76,104.51,104.48,99.68,71.69,71.56,70.96,55.35,52.10,49.95,49.94,36.43ppm.
example 3
The reaction equation is as follows:
the compound 1c (5mmol), GMDVs (7.5mmol) and Pd (PPh)3)4(0.25mmol) was sequentially added to the reactor under an inert gas atmosphere, 50 ml of anhydrous ethyl acetate was added thereto, followed by degassing and reaction at room temperature for 12 hours. After the reaction is finished, the reaction solvent is dried by spinning, and the pure 3c is obtained by using mixed solvent column chromatography of petroleum ether and ethyl acetate with the volume ratio of 8: 1. The yield of 3c was 73%.
Nuclear magnetic data for 3c are as follows:
1H NMR(500MHz,CDCl3)δ7.58-7.52(m,2H),7.50(dd,J＝8.0,2.0Hz,2H),7.46-7.38(m,4H),7.37-7.29(m,2H),7.28-7.20(m,6H),6.97(t,J＝7.5Hz,1H),6.79(d,J＝8.0Hz,1H),6.17-6.09(m,1H),5.09(s,1H),5.00(s,1H),4.46-4.33(m,2H),3.89-3.78(m,1H),3.59(d,J＝5.0Hz,3H),3.02(dd,J＝14.5,5.5Hz,1H),2.97-2.86(m,1H),2.56-2.47(m,1H)ppm.
13C NMR(125MHz,CDCl3)δ173.74,173.68,155.55,142.41,141.67,140.90,139.97,138.26,132.13,132.04,128.70,128.67,127.90,127.89,127.80,127.49,127.12,127.05,126.94,126.90,121.04,114.74,114.67,111.74,71.81,71.68,70.95,52.09,50.01,36.53,36.49ppm.
example 4
The reaction equation is as follows:
the compound 1d (5mmol), GMDVs (7.5mmol), Pd (PPh)3)4(0.25mmol) was added to the reactor in sequence under an inert gas atmosphere, 50 ml of anhydrous tetrahydrofuran was added, and then, degassing was performed, and the reaction was performed at 0 ℃ for 12 hours. After the reaction is finished, the reaction solvent is dried in a spinning mode, and the pure 3d is obtained by using mixed solvent column chromatography of petroleum ether and ethyl acetate with the volume ratio of 8: 1. The yield of 3d was 74%.
Nuclear magnetic data for 3d are as follows:
1H NMR(500MHz,CDCl3)δ7.86(d,J＝7.5Hz,1H),7.82-7.68(m,3H),7.53-7.38(m,3H),7.34-7.16(m,7H),6.94(t,J＝7.5Hz,1H),6.79(d,J＝8.0Hz,1H),6.28(dd,J＝10.0,5.0Hz,1H),5.09(s,1H),5.00(s,1H),4.45-4.35(m,2H),3.90-3.75(m,1H),3.58(d,J＝4.5Hz,3H),3.13(dd,J＝22.0,5.0Hz,1H),3.00-2.82(m,1H),2.64-2.41(m,1H)ppm.
13C NMR(125MHz,CDCl3)δ173.74,173.68,155.68,155.66,141.65,141.64,140.66,140.64,138.25,133.21,132.70,132.13,132.04,128.70,128.10,128.07,128.03,127.81,127.79,127.57,127.47,125.89,125.63,124.98,124.95,121.05,121.03,114.77,114.69,111.76,77.25,77.00,76.75,71.87,71.71,70.99,70.98,52.10,52.09,50.02,36.60,36.54ppm.
example 5
The reaction equation is as follows:
compound 1e (5mmol), GMDVs (7.5mmol), Pd (PPh)3)4(0.25mmol) was sequentially added to the reactor under an inert gas atmosphere, 50 ml of anhydrous tetrahydrofuran was added thereto, followed by degassing and reaction at room temperature for 2 hours. After the reaction is finished, the reaction solvent is dried in a spinning mode, and the pure 3e is obtained by using mixed solvent column chromatography with the volume ratio of petroleum ether to ethyl acetate being 3: 1. The yield of 3e was 57%.
Nuclear magnetic data for 3e are as follows:
1H NMR(500MHz,CDCl3)δ7.35-7.19(m,7H),6.94(t,J＝7.5Hz,1H),6.78(d,J＝8.5Hz,1H),5.18(s,1H),5.05(s,1H),4.71(d,J＝6.0Hz,2H),
4.52-4.41(m,2H),3.91(dd,J＝9.5,6.5Hz,1H),3.63(s,3H),3.00(dd,J＝14.5,9.0Hz,1H),2.58(dd,J＝15.0,6.5Hz,1H),2.48(t,J＝6.0Hz,1H)ppm.
13C NMR(125MHz,CDCl3)δ173.79,156.28,141.67,138.30,129.29,128.86,128.81,128.72,127.81,127.51,120.86,114.70,111.25,77.25,77.00,76.75,70.72,61.87,52.12,50.06,36.77ppm.
from the above examples, it can be seen that according to the method for synthesizing phenyl allyl ether compounds by using GMDVs of the present invention, diversified products can be obtained with high efficiency and high selectivity under mild conditions.
Claims (7)
1. A high-efficiency selective synthesis method of phenyl allyl ether compounds is provided, wherein the phenyl allyl ether compounds have a structure shown in a formula I:
wherein R is1Selected from any one of saturated alkyl, alkoxy and halogen, and is positioned at 4 of benzene ring#、5#、6#One of the positions;
R2any one selected from aryl, substituted aryl, saturated alkyl and hydrogen atom;
the aryl group is phenyl or naphthyl;
the substituent of the substituted aryl is any one of halogen atom, saturated alkyl, alkoxy and aryl;
the method comprises the following steps: sequentially adding hydroxymethyl phenol, GMDVs, a catalyst and a solvent into a reactor under an inert gas atmosphere, and stirring at a certain temperature until the reaction is finished; the chemical process is shown in a reaction formula II:
2. the preparation process according to claim 1, wherein the catalyst is selected from palladium tetratriphenylphosphine (Pd (PPh)3)4) Palladium acetate, tris (dibenzylideneacetone) dipalladium (Pd)2(dba)3) Any one of them.
3. The production method according to claim 1, wherein the solvent is any one selected from dichloromethane, tetrahydrofuran, ethyl acetate, ethanol, acetonitrile, acetone, N-dimethylformamide, and 1, 4-dioxane.
4. The method of claim 1, wherein the molar ratio of the hydroxymethylphenol to the GMDVs to the catalyst is 1.0 (1.0-2.0) to 0.01-0.1.
5. The process according to claim 1, wherein the reaction time is 1 to 24 hours.
6. The production method according to claim 1, wherein the reaction temperature is 0 to 60 ℃.
7. The preparation process according to claim 1, wherein the column chromatography is carried out using a mixed solvent of petroleum ether and ethyl acetate.
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