CN111559993A - Preparation method of furan methanol compound - Google Patents
Preparation method of furan methanol compound Download PDFInfo
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- CN111559993A CN111559993A CN202010486443.1A CN202010486443A CN111559993A CN 111559993 A CN111559993 A CN 111559993A CN 202010486443 A CN202010486443 A CN 202010486443A CN 111559993 A CN111559993 A CN 111559993A
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- -1 furan methanol compound Chemical class 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000011831 acidic ionic liquid Substances 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 6
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 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
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 150000001450 anions Chemical class 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Natural products OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 239000011261 inert gas Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 229910052723 transition metal Inorganic materials 0.000 abstract 1
- 150000003624 transition metals Chemical class 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 76
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 19
- 238000005160 1H NMR spectroscopy Methods 0.000 description 19
- 239000007787 solid Substances 0.000 description 9
- 239000012230 colorless oil Substances 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 230000004071 biological effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- GTUVXOOHBUUGBH-UHFFFAOYSA-N furan;methanol Chemical class OC.C=1C=COC=1 GTUVXOOHBUUGBH-UHFFFAOYSA-N 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
- C07D307/80—Radicals substituted by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/92—Naphthofurans; Hydrogenated naphthofurans
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a preparation method of a furan methanol compound, belonging to the field of organic synthesis. The synthesis method comprises the following steps: the compound shown in the formula (I) is subjected to intramolecular ring-opening cyclization reaction under the catalysis of acidic ionic liquid to obtain the furfuryl alcohol compound. The furancarbinol compound is shown as a formula (II). According to the invention, the acidic ionic liquid is used as the catalyst, and transition metal is not used as the catalyst, so that heavy metal residue cannot exist in the product, and the reaction does not need inert gas protection. The invention provides a new way for synthesizing the furan methanol compound.
Description
Technical field
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of a furan methanol compound.
Two background art
Since 1880, furans are commonly used as structural units by chemists in drug synthesis, and thus drugs have biological activities such as antibacterial, insecticidal, antitumor and anti-inflammatory properties. As the compounds have various pharmacological effects, the compounds gradually become one of the hot spots which are continuously concerned by scientists in recent years, and the scientists modify the structures of the compounds to obtain the compounds with better biological activity. Similarly, the furfuryl alcohol compounds and their derivatives have diversified biological activities and have great research value in the fields of medicines, agricultural chemicals, and the like, and thus have received much attention. Although these furfuryl alcohol compounds and their derivatives play an important role in the study of bioactive molecules, examples of ring-opening synthesis by 3, 3-disubstituted oxetanes are rare. The Vanderwal group has reported several examples of ring opening of 3, 3-disubstituted oxetanes with intramolecular oxygen nucleophiles to achieve the synthesis of polysubstituted furancarbinol compounds (Angew. chem. int. Ed.2017,56: 10525-one 10529.). However, the conversion reaction reported requires the use of a stoichiometric amount of trifluoroacetic acid. Therefore, the development of a simple and practical catalytic system for synthesizing the compounds is of great significance.
Disclosure of the invention
The invention aims to provide a preparation method of a furan methanol compound.
The invention provides a furan methanol compound shown in a formula (II),
in the formula, R is alkyl, phenyl or common substituent groups in organic compounds such as substituted phenyl, heterocyclic aryl, naphthyl and the like; r' is hydrogen, alkyl or phenyl.
The catalyst adopted by the preparation method is one of sulfonate type acidic ionic liquids, specifically shown in formula (IV), and accounts for 5% of the mole percentage of the formula (I).
The solvent in the preparation method is any one of toluene, methanol, ethanol, dichloromethane, chloroform, acetone, dichloroethane, benzene, tetrahydrofuran, ethyl acetate, methyl tert-butyl ether and acetonitrile, and specifically is ethanol.
The preparation method of the invention has the reaction time of 1-24 hours and the reaction temperature of-20-100 ℃; the specific reaction time was 6 hours and the reaction temperature was 60 ℃.
The chemical reaction principle on which the invention is based is as follows:
the method provided by the invention adopts a ring-opening cyclization mode to carry out reaction, and the byproduct is only water. The prepared compound contains hydroxyl functional groups, and is easy to derive and modify compounds containing furan structures. Compared with the prior art, the invention has the advantages that: (1) the raw materials and the catalyst have wide sources and are convenient to prepare; (2) expensive metal catalysts are not needed, and heavy metal residues cannot exist in the product; (3) no stoichiometrically strong acids need to be used.
Detailed description of the invention
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The following examples further illustrate the invention in order to provide a better understanding of the invention. The examples do not limit the scope of the invention in any way. Modifications and adaptations of the present invention within the scope of the claims may occur to those skilled in the art and are intended to be within the scope and spirit of the present invention.
In the following examples, the compound having different substituents represented by the formula (I) (0.2mmol), the compound represented by the formula (IV) (5 mol%) and ethanol (0.5ml) were added in this order to a reaction tube, and the reaction temperature was raised to 60 ℃ to effect a reaction. The experiment was stopped after six hours of reaction. Cooling the reaction system, removing the organic solvent by rotary evaporation, and finally carrying out column chromatography by using petroleum ether and ethyl acetate as eluent to obtain the specific corresponding compound (II) by separation.
Example 1
33.1mg,95％yield,white solid.
1H NMR(400MHz,CDCl3)7.67-7.64(m,2H),7.45(s,1H),7.38(t,J＝7.7Hz,2H),7.29-7.25(m,1H),6.70(s,1H),4.60(s,2H),1.63(s,1H).
13C NMR(100MHz,CDCl3)154.79,139.27,130.64,128.66,127.54,127.17,123.79,105.01,56.85.
Example 2
34.6mg,90％yield,white foam.
1H NMR(400MHz,CDCl3)7.64-7.58(m,2H),7.43(s,1H),7.10-7.04(m,2H),6.63(s,1H),4.58(s,2H),1.72(s,1H).
13C NMR(100MHz,CDCl3)162.22(J＝162.2Hz),153.94,139.21,127.22,127.02(J＝3.3Hz),125.56(J＝8.1Hz),115.69(J＝21.8Hz),104.70(J＝11.3Hz),56.76.
Example 3
43.8mg,87％yield,white foam.
1H NMR(400MHz,CDCl3)7.53-7.47(m,4H),7.44(s,1H),6.69(s,1H),4.58(s,2H),1.82(s,1H).
13C NMR(100MHz,CDCl3)153.70,139.54,131.80,129.53,127.33,125.27,121.31,105.57,56.72.
Example 4
33.1mg,83％yield,white solid.
1H NMR(400MHz,CDCl3)7.73-7.70(m,2H),7.66-7.63(m,2H),7.51(d,J＝0.6Hz,1H),6.86(s,1H),4.61(d,J＝2.2Hz,2H),1.74(s,1H).
13C NMR(100MHz,CDCl3)152.65,140.79,134.43,132.58,127.77,123.95,118.86,110.47,108.11,56.58.
Example 5
35.4mg,94％yield,colorless oil.
1H NMR(400MHz,CDCl3)7.55(d,J＝8.2Hz,2H),7.42(s,1H),7.19(d,J＝8.0Hz,2H),6.64(s,1H),4.58(s,2H),2.36(s,3H),1.71(s,1H).
13C NMR(100MHz,CDCl3)155.01,138.88,137.40,129.34,127.98,127.09,123.76,104.29,56.85,21.24.
Example 6
39.6mg,97％yield,colorless oil.
1H NMR(400MHz,CDCl3)7.60-7.55(m,2H),7.40(s,1H),6.92(dd,J＝9.3,2.3Hz,2H),6.56(s,1H),4.57(s,2H),3.83(s,3H),1.74(s,1H).
13C NMR(100MHz,CDCl3)159.13,154.83,138.58,127.10,125.24,123.75,114.11,103.47,56.85,55.28.
Example 7
35.0mg,76％yield,white solid.
1H NMR(400MHz,CDCl3)7.59(d,J＝8.4Hz,2H),7.43-7.39(m,3H),6.50(s,1H),4.59(s,2H),1.91(s,1H),1.34(s,9H).
13C NMR(100MHz,CDCl3)155.00,150.66,138.98,127.98,127.07,125.58,123.62,104.41,56.89,34.63,31.24.
Example 8
42.2mg,90％yield,white solid.
1H NMR(400MHz,CDCl3)7.75(d,J＝8.6Hz,1H),7.41(d,J＝0.7Hz,1H),6.87(s,1H),6.60-6.54(m,2H),4.61(s,2H),3.93(s,3H),3.86(s,3H),1.71(s,1H).
13C NMR(100MHz,CDCl3)160.08,156.56,151.21,137.68,127.00,126.75,113.16,107.94,104.68,98.64,57.04,55.38,55.36.
Example 9
37.2mg,83％yield,white solid.
1H NMR(400MHz,CDCl3)8.13(s,1H),7.86-7.80(m,3H),7.74(dd,J＝8.6,1.6Hz,1H),7.51-7.46(m,3H),6.82(s,1H),4.62(s,2H),1.73(s,1H).
13C NMR(100MHz,CDCl3)154.85,139.50,133.45,132.74,128.39,128.16,127.95,127.72,127.35,126.48,125.98,122.23,122.21,105.64,56.84.
Example 10
51.3mg,86％yield,white solid.
1H NMR(400MHz,CDCl3)7.62(d,J＝1.7Hz,1H),7.47(s,1H),7.13(d,J＝1.6Hz,1H),6.61(s,1H),4.61(s,2H),3.03(t,J＝7.2Hz,2H),1.98(t,J＝7.2Hz,2H),1.80(s,1H),1.37(s,9H),1.29(s,6H).
13C NMR(100MHz,CDCl3)154.93,153.53,150.06,138.66,135.70,126.93,126.30,120.01,118.29,107.25,56.97,43.80,41.34,34.77,31.57,30.30,28.78.
Example 11
24.9mg,76％yield,white foam.
1H NMR(400MHz,CDCl3)7.41-7.38(m,2H),6.58(s,1H),6.55(d,J＝3.3Hz,1H),6.45(dd,J＝3.4,1.8Hz,1H),4.57(s,2H),1.69(s,1H).
13C NMR(100MHz,CDCl3)147.32,146.29,141.91,138.92,126.95,111.33,105.41,105.02,56.70.
Example 12
32.1mg,89％yield,light yellow solid.
1H NMR(400MHz,CDCl3)7.38(s,1H),7.26-7.22(m,2H),7.03(dd,J＝5.0,3.7Hz,1H),6.55(s,1H),4.57(s,2H),1.69(s,1H).
13C NMR(100MHz,CDCl3)150.27,138.75,133.50,127.61,127.21,124.36,122.81,105.00,56.72.
Example 13
35.5mg,78％yield,white solid.
1H NMR(400MHz,CDCl3)7.94(d,J＝7.9Hz,1H),7.40(d,J＝0.7Hz,1H),7.37-7.29(m,3H),7.25-7.22(m,1H),6.57(s,1H),4.62(s,2H),3.81(s,3H),1.69(s,1H).
13C NMR(100MHz,CDCl3)151.60,137.12,137.04,126.76,125.90,124.71,122.21,120.23,120.19,109.51,107.33,102.95,57.01,32.92.
Example 14
24.1mg,86％yield,colorless oil.
1H NMR(400MHz,CDCl3)7.27(s,1H),6.02(s,1H),4.49(s,2H),2.96-2.84(m,1H),1.67(s,1H),1.23(d,J＝6.9Hz,6H).
13C NMR(100MHz,CDCl3)162.83,137.91,125.45,102.95,56.88,27.84,21.00.
Example 15
25.9mg,94％yield,colorless oil.
1H NMR(400MHz,CDCl3)7.21(s,1H),6.00(s,1H),4.47(s,2H),1.90-1.82(m,1H),1.63(s,1H),0.89-0.83(m,2H),0.77-0.72(m,2H).
13C NMR(100MHz,CDCl3)158.44,137.64,125.84,103.61,56.86,8.77,6.53.
Example 16
28.0mg,92％yield,colorless oil.
1H NMR(400MHz,CDCl3)7.23(s,1H),4.48(s,2H),2.58-2.54(m,2H),2.47-2.42(m,2H),1.86-1.79(m,2H),1.77-1.70(m,2H),1.53(s,1H).
13C NMR(100MHz,CDCl3)151.82,137.83,124.50,116.48,55.92,23.16,22.85,22.82,20.53.
Example 17
30.0mg,75％yield,white foam.
1H NMR(400MHz,CDCl3)7.45(d,J＝7.6Hz,1H),7.38(s,1H),7.25-7.17(m,2H),7.15-7.10(m,1H),4.57(s,2H),2.98(t,J＝7.9Hz,2H),2.76(t,J＝8.0Hz,2H),1.82(s,1H).
13C NMR(100MHz,CDCl3)150.77,139.56,134.55,127.94,127.90,126.69,126.58,125.06,119.19,118.61,55.84,28.85,19.41.
Example 18
29.5mg,73％yield,white foam.
1H NMR(400MHz,CDCl3)7.61(dd,J＝8.3,1.0Hz,2H),7.44-7.39(m,3H),7.31-7.26(m,1H),4.60(s,2H),2.72(q,J＝7.6Hz,2H),1.44(s,1H),1.28(t,J＝7.6Hz,3H).
13C NMR(100MHz,CDCl3)149.55,139.32,131.60,128.56,127.09,126.90,125.53,122.16,55.73,17.30,14.85.
Example 19
37.5mg,75％yield,light yellow solid.
1H NMR(400MHz,CDCl3)7.56(s,1H),7.44-7.38(m,7H),7.26-7.21(m,3H),4.48(s,2H),1.61(s,1H).
13C NMR(100MHz,CDCl3)149.60,139.58,133.03,130.83,129.81,128.88,128.30,127.59,127.36,127.19,125.69,121.82,55.57.
Claims (5)
1. A preparation method of a furan methanol compound comprises the following steps: and (3) carrying out intramolecular ring opening cyclization reaction on the compound shown in the formula (I) under the action of an acidic ionic liquid catalyst to obtain the furancarbinol compound. The furancarbinol compound is represented by the formula (II).
R in the formula (I) and the formula (II) is alkyl, phenyl or common substituent groups in organic compounds such as substituted phenyl, heterocyclic aryl, naphthyl and the like; r' is hydrogen, alkyl or phenyl.
2. The method of claim 1, wherein: the acidic ionic liquid is prepared by taking hydrogen sulfate as an anion (HSO 4)-) The quaternary ammonium salt type compound of formula (III).
3. The production method according to claim 1 or 2, characterized in that: the solvent of the ring-opening cyclization reaction is any one of toluene, methanol, ethanol, dichloromethane, chloroform, acetone, dichloroethane, benzene, tetrahydrofuran, ethyl acetate, methyl tert-butyl ether and acetonitrile.
4. The production method according to claims 1 to 3, characterized in that: the reaction time is 1-24 hours, and the reaction temperature is-20-100 ℃.
5. The production method according to claims 1 to 4, characterized in that: the acidic ionic liquid accounts for 1-20% of the compound shown in the formula (I) in mol percentage.
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