CN108164486B - Environment-friendly efficient synthesis method of ether compound - Google Patents

Environment-friendly efficient synthesis method of ether compound Download PDF

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CN108164486B
CN108164486B CN201810182651.5A CN201810182651A CN108164486B CN 108164486 B CN108164486 B CN 108164486B CN 201810182651 A CN201810182651 A CN 201810182651A CN 108164486 B CN108164486 B CN 108164486B
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aldehyde
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silane
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CN108164486A (en
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徐洲
梁婷
米佳佳
翟荣良
石艳芬
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Xuzhou Medical University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • 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
    • C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans

Abstract

The invention discloses a green and efficient synthesis method of an ether compound, which is energy-saving and environment-friendly and comprises the following steps: in a mild reaction system, aldehyde and silane are used as initial raw materials, and efficient preparation of various ethers is realized through reduction-coupling-ether formation reaction under the action of monovalent silver salt and in a solvent-free condition. The synthetic method has the advantages of low catalyst consumption, no solvent, high conversion rate and yield, short reaction time, safety, stability, easy operation, no need of any additional organic solvent for product distillation and purification, environmental protection, high efficiency and the like, can overcome various defects of the prior art, and has good industrial application value.

Description

Environment-friendly efficient synthesis method of ether compound
Technical Field
The invention relates to a synthetic method of an ether compound, in particular to a green efficient synthetic method of a symmetrical ether compound, belonging to the technical field of organic synthesis.
Background
Ethers are very important compounds, play very important roles in organic synthesis and drug synthesis, are also important industrial raw materials, and the search for a simple, efficient and environment-friendly ether synthesis method is the focus of attention of organic chemists. (Angew. chem. int. Ed.,2007,46,298-300.) at present, ether compounds are prepared by a plurality of methods, but the defects of complex synthesis process, large environmental pollution and the like exist generally. The existing ether synthesis methods mainly comprise the following steps:
(1) williamson synthesis comprising: halogenated hydrocarbon, sodium alcoholate and sodium phenolate are used as raw materials to react to obtain corresponding ether, which is a common method for synthesizing symmetrical ether and asymmetrical ether. However, this reaction is disadvantageous for industrial production, and a strong alkali such as sodium or sodium hydrogen is generally required in the reaction, so that this method cannot be selected if the substrate is not alkali-resistant, and in addition, the waste liquid produced by this method contains a strong alkali, which causes serious environmental pollution.
(2) The Ulmann reaction, an important process for the synthesis of diaryl ethers, is usually carried out at elevated temperatures in the presence of copper and cuprous salts. The method has the advantages of higher reaction temperature, complex post-treatment, low conversion rate, and the like, and needs to use stoichiometric copper salt catalyst.
(3) The dehydration reaction of alcohol, which is a common method for synthesizing symmetrical ether, is mainly used for the reaction of primary alcohol into ether, the reaction yield of secondary alcohol is low, and the reaction of tertiary alcohol is easy to eliminate. The other is a Lewis acid catalyzed dehydration reaction, which has the major disadvantage of requiring a large loading of catalyst.
(4) Acid-catalyzed reductive coupling of aldehydes or ketones to silanes, i.e. etherification of aldehydes with strong acids, e.g. trifluoromethanesulfonic acid, and Fe (III)/Me3Lewis acid catalytic systems such as SiCl, Sb (V) OTf and the like. However, such methods require the use of large amounts of organic solvents, and complicated purification means such as column chromatography are required for the post-treatment.
In summary, in the existing ether synthesis methods, either strong acid and strong base are needed for reaction conditions, or the temperature required by the reaction is high, or the required reagents are expensive, or the post-treatment is complicated. The method has the outstanding problems that the existing method has high catalyst consumption and pollutes the environment, and the post-treatment process needs to be purified by column chromatography, thereby consuming time and consuming materials. Therefore, a green, efficient and environment-friendly method for synthesizing ether compounds is urgently needed.
Disclosure of Invention
The invention mainly aims to provide a green and efficient synthesis method of an ether compound to overcome the defects in the prior art. In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a green and efficient synthesis method of an ether compound, which comprises the following steps: aldehyde and silane are used as starting materials, and the ether compound is prepared by reduction-coupling-ether forming reaction under the action of monovalent silver salt and in the solvent-free condition.
Further, the ether compound is shown as the following formula I:
Figure BDA0001589331370000021
wherein R is1，R2，R3Is selected from any one of hydrogen, alkyl, alkoxy, halogen, hydroxyl, ester group and aryl.
In some embodiments, R1，R2，R3＝Me，Et，iPr, n-Bu, F, Cl, Br, I, OMe, but is not limited thereto.
Further, the ether compound is represented by the following formula II:
Figure BDA0001589331370000022
wherein R is selected from alkyl, preferably C4-C12 alkyl.
Further, the ether compound is represented by the following formula III:
Figure BDA0001589331370000023
wherein R is selected from hydrogen, alkyl, alkoxy or halogen atom, and n is 1, 2 or 3. Preferably, R is hydrogen.
Further, the ether compound is represented by formula IV below:
Figure BDA0001589331370000024
wherein n is 0,1 or 2.
In some embodiments, the silver salt comprises Ag2CO3、AgBF4、AgSbF6、AgOAc、CF3COOAg、AgOTf、AgNO3、AgNTf2Any one or a combination of two or more of them, but not limited thereto.
In some embodiments, the aldehyde includes an aliphatic aldehyde (e.g., butyraldehyde), an aromatic aldehyde (e.g., benzaldehyde), or a dialdehyde (e.g., o-phthalaldehyde), but is not limited thereto.
In some embodiments, the silane includes any one of triethylsilane, trimethylsilane, triisopropylsilane, triphenylsilane, diphenylmethylsilane, trimethoxysilane, but is not limited thereto.
In some embodiments, the monovalent silver salt is used in an amount of 0.001% to 20%, preferably 0.05% to 5%, based on the molar amount of the starting material.
In some embodiments, the synthesis method further comprises: after the reaction is finished, the reaction product is purified by a distillation mode.
In some embodiments, the aldehyde to silane molar ratio is 1.0: 1.0-1.0: 1 to 2.0.
In some embodiments, the reaction temperature is from 10 ℃ to 130 ℃, preferably from 10 ℃ to 110 ℃, and particularly preferably from 20 ℃ to 110 ℃, and the reaction time is from 1 minute to 24 hours.
In some embodiments, the method of synthesis specifically comprises: mixing only aldehyde, silane and monovalent silver salt, wherein the molar ratio of aldehyde to silane is 1.0: 1.0-1.0: 1-2.0, the dosage of monovalent silver salt is 0.05% -5% of the molar weight of the initial raw material, the monovalent silver salt reacts for 5 minutes to 24 hours at the temperature of 20-110 ℃, and then the reaction product is purified only by a distillation mode to obtain an ether compound; the silver salt is selected from Ag2CO3、AgBF4、AgSbF6、AgOAc、CF3COOAg、AgOTf、AgNO3、AgNTf2The aldehyde is selected from aliphatic aldehyde, aromatic aldehyde or binary aldehyde, and the silane is selected from any one of triethylsilane, trimethylsilane, triisopropylsilane, triphenylsilane, diphenylmethylsilane and trimethoxy silane.
In some more specific embodiments of the present invention, the general reaction formula of the synthesis method may be represented by any one of formulas (1), (2), and (3):
Figure BDA0001589331370000031
R-CHO in formula (1) may be selected from aromatic aldehydes or aliphatic aldehydes including but not limited to benzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, naphthaldehyde, phenylacetaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, undecanal, dodecanal, octadecanal, cyclohexanal, etc., and R' includes but not limited to triethyl, triphenyl, triethoxy, diphenylmethyl, etc.
N in formula (2) is 1, 2 or 3, including but not limited to malondialdehyde, succindialdehyde, glutaraldehyde, etc.
In the formula (3), R is aromatic ring group, alkyl, hydrogen, halogen and the like, and n is 0,1 or 2.
The silver salt may be selected from AgNTf as the catalyst2,AgOTf,AgNO3,AgBF4,AgSbF6,CF3SO3Ag,AgCH3COOF7And combinations of any one or more of these.
Further, in the synthesis method of the invention, the reaction process does not need any additional organic solvent.
The mechanism of the present invention is described below in conjunction with an exemplary embodiment of the present invention. In the reaction of the embodiment, firstly monovalent silver salt activates a silicon-hydrogen bond through single electron transfer to form a hydrogen radical, then the hydrogen radical performs radical addition on aldehyde to obtain an oxygen radical, the oxygen radical reacts with divalent silver salt to obtain an intermediate int-2, then the condensation reaction is performed on the intermediate int-2 and aldehyde, and finally the hydrogen radical is transferred once to obtain a product ether, so that a catalyst is released. A more intuitive reaction process for this embodiment can be seen in fig. 1.
Compared with the prior art, the invention develops a novel ether synthesis method by using low-dose, cheap and easily-obtained monovalent silver salt catalyst, namely, silane which is cheap and easily-obtained is directly used as a reducing agent to realize the conversion of various aldehydes and dialdehyde into ether, thereby having good industrial application prospect.
Drawings
FIG. 1 is a diagram of a green and efficient synthesis mechanism of an ether compound according to an exemplary embodiment of the present invention.
Detailed Description
The green and efficient synthesis method of the ether compound provided by the invention can effectively solve a plurality of problems existing in the existing synthesis method of the ether compound, and particularly solves the problem of environmental pollution. More specifically, the synthesis method of the present invention comprises: in a mild reaction system, aldehyde and silane are used as initial raw materials, and reduction-coupling-ether forming reaction is carried out under the action of monovalent silver salt and under the solvent-free condition, so that the high-efficiency preparation of various ethers is realized. The synthesis method has the advantages of low catalyst consumption, no solvent, high conversion rate and yield, short reaction time, safety, stability, easy operation, product purification only by distillation, no need of any additional organic solvent, green whole process, environmental protection, high efficiency and the like, and has industrial application value.
The present invention will be further described with reference to the following examples, which are only for illustrating the technical solutions of the present invention and are not to be construed as limiting the present invention.
Example 1: a100 mL round bottom flask was charged with 0.02% AgNTf2(0.01mmol, 3.88mg), benzaldehyde (50mmol, 5.3060g) and triethylsilane (50mmol, 6.0600g), heating the reaction mixture to 80 deg.C, stirring for 70 minutes (the corresponding reaction mechanism can be seen in FIG. 1), and directly distilling under reduced pressure (2mmHg,90 deg.C) to obtain the desired product with a yield of 97%. The structural characterization data for the product dibenzyl ether is consistent with literature (Gellert, Beate A.; Kahlcke, Nils; Feurer, Markus. chemistry-A European Journal,2011,17,43, 12203-:1H NMR(400MHZ,CDCl3):δppm7.31-7.40(m,10H),4.58(s,4H)；13C NMR(100MHZ,CDCl3):δppm 138.2,128.4,127.8,127.6,72.1；IR(cm-1):3050,1420,1380；ESI+calculated for[C14H15O]+:199.2730,found:199.2727。
example 2: a1000 mL round bottom flask was charged with 100ppm of MAGOAc (0.005mmol, 8mg), benzaldehyde (500mmol, 53.0600g) and triethylsilane (500mmol, 60.6000g), heated to 110 deg.C, stirred for 3h, and after completion of the reaction, distilled directly under reduced pressure (2mmHg,90 deg.C) to afford the desired product in 92% yield. The product structure characterization data are the same as in example 1.
Example 3: 1000mL reaction bottle is added with 0.1% AgNTf2(0.5mmol, 0.2g), benzaldehyde (500mmol, 53.06g) and triethylsilane (500mmol, 60.60g) were reacted at 25 ℃ with stirring at room temperature for 2 hours, after completion of the reaction, 50ml of water was added to the reaction flask, liquid-separated, and the organic phase was dried over anhydrous sodium sulfate, and then the organic phase was distilled under reduced pressure (2mmHg,90 ℃) to give the desired product in 86% yield. The product structure characterization data are the same as in example 1.
Example 4: 1% AgBF was added to a 100mL reaction flask in sequence4(0.05mmol, 9.7mg), benzaldehyde (50mmol, 5.3060g) and triphenylsilane (50mmol, 13.6051g) were added thereto, and the mixture was stirred at room temperature for 5 minutes to react, after completion of the reaction, the reaction product was directly distilled under reduced pressure (2mmHg,90 ℃ C.) to obtain the desired product in a yield of 98%. The product structure characterization data are the same as in example 1.
Example 5: 100mL round bottom flask was sequentially charged with 0.02% AgNTf2(0.005mmol, 1.94mg), o-chlorobenzaldehyde (25mmol, 3.5143g) and triethylsilane (26.25mmol, 3.0832g) were heated to 110 ℃ and stirred for 3 hours, after completion of the reaction, the reaction was directly distilled under reduced pressure (1.5mmHg,100 ℃) to give the desired product in 83% yield. Product structure characterization data:1H NMR(400MHZ,CDCl3):δppm 7.24-7.60(m,8H),4.77(s,4H)；13C NMR(100MHZ,CDCl3):δppm 135.9,132.9,129.3,129.0,128.7,126.8,69.8；IR(cm-1):3010,1450,1298；ESI+calculatedfor[C14H13Cl2O]+:267.0343,found:267.0347。
example 6: sequentially adding into a 250ml round-bottom flask0.02% AgOTf (0.01mmol, 2.81mg), m-chlorobenzaldehyde (50mmol, 7.0286g) and triethylsilane (50mmol, 6.1640g) were charged, heated to 130 ℃ and stirred for reaction for 3 hours, after completion of the reaction, 50ml of water was added to the reaction flask, the organic phase was separated, dried over anhydrous sodium sulfate and then distilled under reduced pressure (1mmHg,107 ℃) to give the desired product in 87% yield. The product structural characterization data is consistent with literature (Journal of American chemical society,1954,76, 585-:1H NMR(400MHZ,CDCl3):δppm 7.12-7.21(m,8H),4.43(s,4H)；13C NMR(100MHZ,CDCl3):δppm 129.7,127.9,127.7,125.7,71.5；IR(cm-1):1432,1280；ESI+calculated for[C14H13Cl2O]+:267.0343,found:267.0337。
example 7: a100 mL round bottom flask was charged with 0.02% AgSbF in sequence6(0.005mmol, 2.5mg), p-chlorobenzaldehyde (25mmol, 3.5143g), triethylsilane (26.25mmol, 3.0832g), were mixed well and heated to 110 ℃ with stirring for 2 hours, after completion of the reaction, the desired product was obtained by direct distillation under reduced pressure (1mmHg,102 ℃) in a yield of 80%. The data for the structural characterization of the product are in agreement with the literature (Beilstein Journal of organic Chemistry,2016,12, 2627-2635):1H NMR(400MHZ,CDCl3):δppm 4.51(s,4H),7.22-7.37(m,8H)；13C NMR(100MHZ,CDCl3):δppm71.4,76.7,77.3,128.6,129.0,133.5,136.5；IR(cm-1):3070,1480,1190；ESI+calculated for[C14H13Cl2O]+:267.0343,found:267.0339。
example 8: a100 mL round bottom flask was first charged with 0.5% AgNTf2(0.05mmol, 0.0194g), glutaraldehyde (10mmol, 1.0012g) and triethylsilane (20mmol, 4.6512g) were then added in that order, the reaction mixture was stirred at room temperature for 3 hours, and after completion of the reaction, the product tetrahydropyran was obtained by distillation at 90 ℃ under normal pressure, with a yield of 80%. The structural characterization data of the product tetrahydropyran are in agreement with the literature (Tetrahedron,1989,45,4, 1187-1196):1H NMR(400MHZ,CDCl3):δppm 3.65(d,J1＝4.8HZ,J2＝5.6HZ,4H),1.54-1.65(m,6H)；13C NMR(100MHZ,CDCl3):δppm 23.4,26.6,68.7,38.0,76.7,77.3；IR(cm-1):2980,2870,1457,1090。
example 9: a100 mL round bottom flask was first charged with 0.05% AgNTf2(0.005mmol, 1.94mg), o-phthalaldehyde (10mmol, 1.3413g) and triethylsilane (20mmol, 4.6512g) were added thereto, and the reaction mixture was heated to 60 ℃ and stirred for reaction for 3 hours, after completion of the reaction, the objective product was isolated by distillation under reduced pressure, and 1, 3-dihydrobenzofuran was distilled off at 90 ℃ with a yield of 75%. The spectral data of the product 1, 3-dihydrobenzofuran are in agreement with the literature (Journal of the American chemical Society,1989,111,4, 1465-1473):1H NMR(400MHZ,CDCl3):δppm 5.12(s,4H),7.22-7.29(m,4H)；13C NMR(100MHZ,CDCl3):δppm 73.6,120.9,127.2,139.0。
example 10: a100 mL round bottom flask was charged with 0.001% AgSbF in sequence6(0.005mmol, 2.5mg), n-butyraldehyde (20mmol, 1.4868g) and triethylsilane (21mmol, 2.4665g) were reacted with stirring at room temperature for 1.5 hours, and after completion of the reaction, 20 ml of water was added to the system, followed by liquid separation, drying of the organic phase over anhydrous sodium sulfate, and then distilling off the product at 60 ℃ under normal pressure in a yield of 80%. The product spectral data are consistent with the literature (Dalton Transactions,2016,45,27, 11150-:1HNMR(400MHZ,CDCl3):δppm 3.99(t,J1＝6.4,J2＝6.8,4H),0.89-1.58(m,14H)；13C NMR(100MHZ,CDCl3):δppm 13.9,19.4,31.8,70.6。
example 11: 100mL round bottom flask was sequentially charged with 0.05% AgNTf2(0.005mmol, 1.94mg), phenylacetaldehyde (20mmol, 2.4030g) and triethylsilane (21mmol, 2.4419g), the reaction mixture was heated to 110 ℃ and stirred for 2 hours, after completion of the reaction, the objective product was isolated by distillation under reduced pressure (1mmHg,92 ℃ C.) in a yield of 80%. The product spectral data are in agreement with the literature (Journal of the American Chemical Society,2002,124,46, 13690-:1HNMR(400MHZ,CDCl3):δppm 2.88(t,J 1＝7.6,J2＝3.2,4H),3.66(t,J1＝7.6,J2＝3.2,4H),7.20-7.30(m,10H)；13C NMR(100MHZ,CDCl3):δppm 36.3,71.9,126.1,128.2,128.9,139.0；IR(cm-1):2982,2880,1466,1370,1190；ESI+calculated for[C16H19O]+:227.1436,found:227.1437。
example 12: a250 mL round bottom flask was charged with 0.5% AgNTf2(0.05mmol, 0.0194g), o-bromobenzaldehyde (100mmol, 18.5020g) and diphenylmonomethylsilane (100mmol, 19.8340g) were reacted at 25 ℃ for 20 minutes with stirring, and after completion of the reaction, the objective product was isolated by distillation under reduced pressure (1mmHg,115 ℃) in a yield of 90%. The structural characterization data of the product are consistent with the literature (Dalton Transactions,2016,45,27, 11150-:1H NMR(400MHZ,CDCl3):δppm 4.72(s,4H),7.15-7.58(m,8H)；13C NMR(100MHZ,CDCl3):δppm 72.1,122.7,127.4,129.0,129.1,132.5,137.5；IR(cm-1):1453,1334；ESI+calculated for[C14H13Br2O]+:356.9313,found:356.9311。
example 13: a100 mL round-bottomed flask was charged with 0.05% AgOAc (0.05mmol, 0.08g), 3, 4-dichlorobenzaldehyde (100mmol, 11.2170g), triethylsilane (100mmol, 19.8340g) in this order, stirred at 90 ℃ for 2 hours, and after completion of the reaction, 30mL of water was added, separated, dried over anhydrous sodium sulfate as an organic phase, and then distilled under reduced pressure (2mmHg,113 ℃) to isolate the desired product in 90% yield. The product spectral data are consistent with the literature (Synthesis,2015,47,12, 1749-:1H NMR(400MHZ,CDCl3):δppm 4.49(s,4H),7.17(d,J＝7.6HZ,1H),7.19(d,J＝7.6HZ,1H),7.42-7.46(m,4H)；13C NMR(100MHZ,CDCl3):δppm 71.0,126.8,129.5,130.5,131.8,132.6,138.0；IR(cm-1):1441,1388,1334；ESI+calculated for[C14H11Cl4O]+:336.9536,found:336.9533。
example 14: 100mL round bottom flask was sequentially charged with 0.05% AgNTf2(0.05mmol, 0.0194g), p-phenylbenzaldehyde(100mmol, 11.2170g) and triethylsilane (100mmol, 19.8340g) were reacted at 90 ℃ for 2 hours with stirring, and after completion of the reaction, 30ml of water was added, followed by liquid separation, drying over anhydrous sodium sulfate as an organic phase, and then separation by distillation under reduced pressure (2mmHg,92 ℃ C.) to obtain the objective product. Product spectral data:1H NMR(400MHZ,DMSO-d6):δppm 4.58(s,4H),7.31-7.65(m,18H)13C NMR(100MHZ,DMSO-D6):δppm 72.6,127.2,127.9,128.7,129.5,138.2；IR(cm-1):1490,1136；HRMS(ESI+)m/z[M+Na]+calcd for C26H22ONa+,373.1563；found,373.1593。
example 15: a250 mL round bottom flask was charged with 0.5% AgNTf2(0.05mmol, 0.0194g), cyclohexylformaldehyde (100mmol, 11.2170g) and diphenylmonomethylsilane (100mmol, 19.8340g) were reacted at 30 ℃ for 25 minutes with stirring, and after completion of the reaction, the objective product was isolated by distillation under reduced pressure (1mmHg,100 ℃) in a yield of 88%. The structural characterization data of the product are consistent with the literature (Dalton Transactions,2016,45,27, 11150-:1H NMR(400MHZ,CDCl3):δppm 3.18(d,J＝7.6HZ,4H),0.88-1.76(m,22H)；13C NMR(100MHZ,CDCl3):δppm 25.9,26.7,30.2,38.0,76.7。
example 16: a250 mL round bottom flask was charged with 0.5% AgNTf2(0.05mmol, 0.0194g), n-dodecanal (100mmol, 11.2170g) and diphenylmonomethylsilane (100mmol, 19.8340g) were reacted at 25 ℃ with stirring at room temperature for 20 minutes, and after completion of the reaction, the objective product was isolated by distillation under reduced pressure (1mmHg,100 ℃) in a yield of 88%. Product spectral data were in agreement with the literature ((US5914430,1999, a 1)): h NMR (400 MH)Z,CDCl3):δppm 0.88(t,J1＝7.2,J2＝1.6,6H),1.26(s,36H),1.53-1.59(m,4H),3.39(t,J1＝7.2,J2＝1.6,4H)；13C NMR(100MHZ,CDCl3):δppm 13.9,22.7,26.1,29.4,29.5,29.7,31.8,71.0。
Example 17: a250 mL round bottom flask was charged with 5% AgOAc (0.05mmol, 0.08g), 2-bromo-4-chlorobenzaldehyde (100mmol, 21.9462g) and triethylsilane (100mmol, 19.8340g), in that order, 10 deg.CThe reaction was stirred at room temperature for 25 minutes, and after completion of the reaction, the desired product was isolated by distillation under reduced pressure (1mmHg,112 ℃ C.) in a yield of 80%. Product spectral data:1H NMR(400MHZ,CDCl3):δppm 4.65(s,4H),7.58(s,2H)7.47(d,J＝8.4HZ,2H),7.33(d,J＝1.6HZ,1H),7.31(d,J＝2HZ,1H)；13C NMR(100MHZ,CDCl3):δppm 71.5,124.8,127.9,130.5,132.2,133.6,135.8；IR(cm-1):1473,1434,1386；ESI+calcd for C14H11Br2Cl2O+424.8533；found424.8536.
in short, the method has the advantages of extremely low catalyst consumption reaching one millionth in chemical view, mild reaction conditions, short reaction time, simple operation, easily available reaction raw materials, simple post-treatment, environmental friendliness, energy conservation, environmental friendliness, high product purity, high yield and high application value in industrial and environmental views.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.

Claims (8)

1. A green high-efficiency synthesis method of ether compounds is characterized by comprising the following steps: taking aldehyde and silane as initial raw materials, and preparing an ether compound by reduction-coupling-ether forming reaction under the action of monovalent silver salt and in a solvent-free condition;
the ether compound is shown as the following formula I:
Figure DEST_PATH_IMAGE002
formula I
Wherein R is1，R2，R3Any one selected from hydrogen, alkyl, alkoxy, halogen, hydroxyl, ester group and aryl;
alternatively, the ether compound is represented by the following formula II:
Figure DEST_PATH_IMAGE004
formula II
Wherein R is selected from alkyl;
or, the ether compound is shown as the following formula III:
Figure DEST_PATH_IMAGE006
formula III
Wherein R is selected from hydrogen, alkyl, alkoxy or halogen atom, and n is 1, 2 or 3;
alternatively, the ether compound is represented by formula IV below:
Figure DEST_PATH_IMAGE008
formula IV
Wherein n is 0,1 or 2;
the silver salt is selected from Ag2CO3、AgBF4、AgSbF6、AgOAc、CF3COOAg、AgOTf、AgNO3、AgNTf2Any one or a combination of two or more of them;
the aldehyde is selected from aliphatic aldehyde, aromatic aldehyde and binary aldehyde;
the silane is selected from any one of triethylsilane, trimethylsilane, triisopropylsilane, triphenylsilane, diphenylmethylsilane and trimethoxy silane.
2. The method of synthesis of claim 1, wherein: the amount of the monovalent silver salt is 0.001-5% of the total molar amount of the aldehyde and the silane.
3. The method of synthesis of claim 2, wherein: the dosage of the monovalent silver salt is 0.05-5% of the total molar weight of the aldehyde and the silane.
4. The method of synthesis of claim 1, further comprising: after the reaction is finished, the reaction product is purified by a distillation mode.
5. The method of synthesis according to claim 1, characterized in that: the molar ratio of aldehyde to silane was 1.0: 1.0 to 2.0.
6. The method of synthesis according to claim 1, characterized in that: the reaction temperature is 10-130 ℃, and the reaction time is 1 minute-24 hours.
7. The method of synthesis according to claim 6, characterized in that: the reaction temperature is 20-110 ℃.
8. The method of synthesis of claim 1, comprising: mixing only aldehyde, silane and monovalent silver salt, wherein the molar ratio of aldehyde to silane is 1.0: 1.0-2.0, the dosage of the monovalent silver salt is 0.05% -5% of the total molar weight of aldehyde and silane, the reaction is carried out for 5 minutes to 24 hours at the temperature of 20-110 ℃, and then the reaction product is purified only by a distillation method to obtain the ether compound.
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