CN113292589A - Method for tetrahydrofuran ring-opening double-silicification reaction - Google Patents
Method for tetrahydrofuran ring-opening double-silicification reaction Download PDFInfo
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 84
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000007142 ring opening reaction Methods 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims abstract description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 32
- 239000011777 magnesium Substances 0.000 claims description 19
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 17
- 229910052749 magnesium Inorganic materials 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 10
- XQKBFQXWZCFNFF-UHFFFAOYSA-K triiodosamarium Chemical compound I[Sm](I)I XQKBFQXWZCFNFF-UHFFFAOYSA-K 0.000 abstract description 9
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 4
- 150000001340 alkali metals Chemical class 0.000 abstract description 4
- 229910052710 silicon Inorganic materials 0.000 abstract description 4
- 239000010703 silicon Substances 0.000 abstract description 4
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 37
- 239000013067 intermediate product Substances 0.000 description 34
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 20
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 17
- 238000001035 drying Methods 0.000 description 12
- 238000004817 gas chromatography Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000010791 quenching Methods 0.000 description 6
- 230000000171 quenching effect Effects 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000005051 trimethylchlorosilane Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000006227 trimethylsilylation reaction Methods 0.000 description 3
- ZNRDEDGVTFRWQK-UHFFFAOYSA-N 1-silylbutan-1-ol Chemical compound [SiH3]C(CCC)O ZNRDEDGVTFRWQK-UHFFFAOYSA-N 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- -1 alkyl silicon organic compound Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- UAWABSHMGXMCRK-UHFFFAOYSA-L samarium(ii) iodide Chemical compound I[Sm]I UAWABSHMGXMCRK-UHFFFAOYSA-L 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- UPYSACBOPSZOMB-UHFFFAOYSA-N 4-chlorobutoxy(trimethyl)silane Chemical compound C[Si](C)(C)OCCCCCl UPYSACBOPSZOMB-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- PQEPKIZTVSUDSO-UHFFFAOYSA-N [SiH3]OCCCCCl Chemical compound [SiH3]OCCCCCl PQEPKIZTVSUDSO-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- YTJUXOIAXOQWBV-UHFFFAOYSA-N butoxy(trimethyl)silane Chemical compound CCCCO[Si](C)(C)C YTJUXOIAXOQWBV-UHFFFAOYSA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 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
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 1
- QKMNLIDNGUCJIK-UHFFFAOYSA-N trimethyl(4-trimethylsilylbutoxy)silane Chemical compound C[Si](C)(C)CCCCO[Si](C)(C)C QKMNLIDNGUCJIK-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/0827—Syntheses with formation of a Si-C bond
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention provides a method for tetrahydrofuran ring-opening double silicification reaction, which has the following reaction formula:
wherein R is1、R2、R3Each independently selected from methyl, ethyl, isopropyl; the catalyst used in the tetrahydrofuran ring-opening double-silicification reaction is SmI2NaI, KI or ZnI2. According to the method for the ring-opening double silicification reaction of tetrahydrofuran, samarium iodide is used as a catalyst, the reaction condition is mild, and the yield is high; in addition, the one-step method for preparing the bis-silicon-based target product by tetrahydrofuran ring opening has simple operation; in addition, the use of active alkali metal is avoided, and cheap and easily-obtained raw materials and catalysts are used, so that the cost is low; furthermore, samarium iodide and tris (pentafluorophenyl) borane which are used as catalysts can generate synergistic effect, and the promotion effect of 1+1 > 2 is generated on the ring opening disilication reaction of tetrahydrofuran.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a preparation method of an alkyl silicon organic compound.
Background
The ring-opening functionalization of tetrahydrofuran is an efficient route for the synthesis of terminally bifunctional substituted n-butanes (Progress in Heterocyclic Chemistry,2009,20, 152; Inorg. chem.2004,43,4427; J.Am. chem.Soc.2007,129, 1246; Dalton Trans.2013,42,695; Polyhedron 2013,65, 308; J.Chin. chem.Soc.2015,62,703). Wherein tetrahydrofuran is reacted with a chlorosilane to obtain a terminal-functionalized siloxy-protected butane derivative. At high temperatures (130 ℃), chlorotrimethylsilane can cause tetrahydrofuran to undergo a ring-opening reaction to form silyloxybutyl chloride, but the reaction yield is low (12h, 58%) (russ. chem. Bull., int.Ed.2018,67,1621).
The corresponding siloxybutyl chloride can be obtained in high yields at relatively low temperatures (55 ℃) using more sterically hindered tert-butyldimethylsilyl chloride in the presence of an excess of sodium iodide, and the chlorine is converted into other functional groups by reaction with nucleophiles (Synthesis 1988, 56; adv. Synth. Catal.2008,350, 1736). However, this reaction cannot use less sterically hindered trimethylchlorosilane, since the trimethylsiloxy bond is susceptible to hydrolysis to alcohol, giving rise to the opportunity for intramolecular nucleophilic substitution to give tetrahydrofuran again. In the presence of metal oxides such as alumina, titania, or silica, trimethylchlorosilane can cause tetrahydrofuran to undergo ring-opening reactions to form ring-opened mixtures such as trimethylsiloxybutane, trimethylsiloxybutylchloride, etc., with poor reaction selectivity and low reaction efficiency, as well as the problem of hydrolysis of trimethylsiloxy bonds (Synthetic Commun.1982,12,253;).
In the reaction of alkali metal and chlorosilane with tetrahydrofuran as solvent, tetrahydrofuran is detected to have ring opening reaction, the broken C-O bond and trimethylsilyl group react to generate C-Si bond and O-Si bond, respectively, and the product 4-trimethylsiloxybutyl-trimethylsilane is hydrolyzed to obtain 1-silyl n-butanol which is stable because of no electrophilic site and can be separated by conventional means (chem. Eur.J.2020,26,9537; Angew. chem.int.Ed.2014,53,14206; Nature Commun.2012,3,1254). Products of this type can be converted to various di-functionalized butane derivatives by C — Si, but the use of alkali metals increases the operational difficulty and the efficiency and selectivity of the reaction are problems to be solved. Magnesium, trimethylchlorosilane and tetrahydrofuran are heated at reflux for 175 hours to give the hydrolyzate 1-silyln-butanol in 40% yield (j.am. chem. soc.1960,82,6129). However, although the reaction selectively obtains the tetrahydrofuran ring-opening bis-silicon-based product, the reaction conditions are severe, the reaction time is long, and the yield is low.
Therefore, it is necessary to develop a method for tetrahydrofuran ring-opening disilylation reaction with mild reaction conditions and high yield.
Disclosure of Invention
The present invention has been made to solve at least some of the above problems occurring in the prior art, and therefore the present invention provides a method for ring-opening disilylation of tetrahydrofuran, in which the reaction formula of the ring-opening disilylation of tetrahydrofuran is as follows:
wherein R is1、R2、R3Each independently selected from methyl, ethyl, isopropyl; the catalyst used in the tetrahydrofuran ring-opening double-silicification reaction is selected from SmI2NaI, KI and ZnI2One or more of (a). Preferably, R1、R2、R3And is also methyl. More preferably, the catalyst used in the tetrahydrofuran ring-opening double-silicification reaction is SmI2。
In one or more embodiments of the present invention, the temperature of the tetrahydrofuran ring-opening disilication reaction is controlled to be 40-80 ℃.
In one or more embodiments of the present invention, during the reaction of tetrahydrofuran ring-opening disilication, magnesium is further added to the reaction system; preferably, the magnesium is magnesium strip, magnesium grain or magnesium powder; preferably, the magnesium is magnesium powder.
In one or more embodiments of the invention, the molar ratio of the magnesium to the compound shown in the formula 2 is (0.5-2): 1.
In one or more embodiments of the invention, the molar ratio of the compound represented by the formula 1 to the compound represented by the formula 2 is (0.9-1.1): 1. Preferably, the molar ratio of the compound represented by formula 1 to the compound represented by formula 2 is 1: 1.
In one or more embodiments of the invention, the molar ratio of the catalyst to the compound shown in the formula 2 is (0.004-0.009): 1.
In one or more embodiments of the present invention, during the ring-opening double-silicification reaction of tetrahydrofuran, an additive is further added into the reaction system, and the additive is B (C)6F5)3。
In one or more embodiments of the invention, the molar ratio of the additive to the compound shown in formula 2 is (0.005-0.01): 1. Preferably, the molar ratio of the additive to the compound of formula 2 is 0.01: 1.
In the present invention, B (C)6F5)3Is tris (pentafluorophenyl) borane; SmI2Is samarium iodide; THF is tetrahydrofuran; TMSCl is trimethylchlorosilane.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. according to the method for the ring-opening double silicification reaction of tetrahydrofuran, samarium iodide is used as a catalyst, the reaction condition is mild, and the yield is high; in addition, the one-step method for preparing the bis-silicon-based target product by tetrahydrofuran ring opening has simple operation; in addition, the use of active alkali metal is avoided, and cheap and easily-obtained raw materials and catalysts are used, so that the cost is low;
2. according to the method for the tetrahydrofuran ring-opening disilication reaction, the catalyst samarium iodide and the tris (pentafluorophenyl) borane can generate a synergistic effect, and a promotion effect of 1+1 & gt 2 is generated on the tetrahydrofuran ring-opening disilication reaction.
Drawings
FIG. 1 shows the NMR spectrum of the product P' obtained in example 2.
Detailed Description
The scheme of the present invention will be explained below with reference to examples and comparative examples. It will be understood by those skilled in the art that the following examples and comparative examples are illustrative of the present invention only and should not be construed as limiting the scope of the present invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The methods used are conventional methods known in the art unless otherwise specified, and the consumables and reagents used are commercially available unless otherwise specified. Unless otherwise defined, technical and scientific terms used herein have the same meaning as is familiar to those skilled in the art. In addition, any methods or materials similar or equivalent to those described herein can also be used in the present invention.
Example 1: and (3) ring-opening trimethylsilylation reaction of tetrahydrofuran without a catalyst or an additive.
The reaction formula is shown as follows:
the reaction steps are as follows: in a glove box, adding Mg powder (7.9mmol,192Mg), THF (7.9mmol,0.64mL), TMSCl (7.9mmol,1mL) into a 4mL reaction vessel containing magnetons, sealing, transferring to 60 ℃, stirring for reaction for 24h, diluting with DCM, transferring to a 100mL round-bottom flask to obtain a reaction solution containing intermediate product P, calculating the yield of intermediate product P, and measuring the yield of intermediate product P as follows: 1) firstly, preparing a mixture of a standard intermediate product P and an internal standard sample dodecane with a certain molar mass gradient for gas chromatography analysis, and measuring peak areas to obtain a relation curve of peak area ratio and molar mass ratio of P and the internal standard substance, namely an internal standard curve. 2) Dodecane was added as an internal standard to the obtained reaction solution containing the intermediate product P, peak area ratios of the product and the internal standard were measured by gas chromatography, a molar amount of the product was measured by an internal standard curve, and GC yields of the intermediate product P prepared from the compound of formula 1 and the compound of formula 2 were calculated by dividing the molar amount of the product by one-half of the molar amount of the compound of formula 1, whereby the yield of the product P was calculated to be 1%. And adding 20mL of water into the reaction solution containing the intermediate product P, stirring for 1 hour, adding 3M HCl for quenching reaction, mixing organic phases after liquid separation, drying and spin-drying the solvent to obtain a product P', wherein the yield is 0.7%.
Example 2: under the catalysis of samarium iodide as catalyst, the ring opening trimethyl silication of tetrahydrofuran.
The reaction formula is shown as follows:
the reaction steps are as follows: in a glove box, SmI was added to a 4mL reaction vessel containing magnetons2A THF solution (0.064mmol) (0.64mL), Mg powder (7.9mmol,192Mg), TMSCl (7.9mmol,1mL), sealing, transferring to 60 ℃, stirring for reaction for 24h, diluting with DCM, transferring to a 100mL round-bottom flask to obtain a reaction solution containing the intermediate product P, calculating the yield of the intermediate product P, and measuring the yield of the intermediate product P as follows: 1) firstly, preparing a mixture of a standard intermediate product P and an internal standard sample dodecane with a certain molar mass gradient for gas chromatography analysis, and measuring peak areas to obtain a relation curve of peak area ratio and molar mass ratio of P and the internal standard substance, namely an internal standard curve. 2) Dodecane was added as an internal standard to the obtained reaction solution containing the intermediate product P, peak area ratios of the product and the internal standard were measured by gas chromatography, a molar amount of the product was measured by an internal standard curve, and GC yields of the intermediate product P prepared from the compound of formula 1 and the compound of formula 2 were calculated by dividing the molar amount of the product by one-half of the molar amount of the compound of formula 1, whereby the yield of the product P was calculated to be 70%. And adding 20mL of water into the reaction solution containing the intermediate product P, stirring for 1 hour, adding 3M HCl for quenching reaction, combining organic phases after liquid separation, drying and spin-drying the solvent to obtain a product P', wherein the yield is 65%. FIG. 1 shows the NMR spectrum of the product P' obtained in example 2.1H NMR(400MHz,Chloroform-d)δ3.63(t,J＝6.7Hz,2H),1.58(m,2H),1.42–1.27(m,2H),0.54–0.41(m,2H),-0.04(s,9H)。
Example 3: under the catalysis of samarium iodide as catalyst, the ring opening trimethyl silication of tetrahydrofuran.
The reaction formula is shown as follows:
the reaction steps are as follows: in a glove box, SmI was added to a 4mL reaction vessel containing magnetons2A THF solution (0.064mmol) (0.64mL), Mg powder (15.8mmol,384Mg), TMSCl (7.9mmol,1mL), which is sealed and transferred to 40 ℃ for stirring reaction for 24h, then diluted with DCM and transferred to a 100mL round-bottom flask, thus obtaining a reaction solution containing the intermediate product P, and calculating the yield of the intermediate product P, wherein the yield of the intermediate product P is measured by the following method: 1) firstly, preparing a mixture of a standard intermediate product P and an internal standard sample dodecane with a certain molar mass gradient for gas chromatography analysis, and measuring peak areas to obtain a relation curve of peak area ratio and molar mass ratio of P and the internal standard substance, namely an internal standard curve. 2) Dodecane was added as an internal standard to the obtained reaction solution containing the intermediate product P, peak area ratios of the product and the internal standard were measured by gas chromatography, a molar amount of the product was measured by an internal standard curve, and GC yields of the intermediate product P prepared from the compound of formula 1 and the compound of formula 2 were calculated by dividing the molar amount of the product by one-half of the molar amount of the compound of formula 1, whereby the yield of the product P was calculated to be 50%. And adding 20mL of water into the reaction solution containing the intermediate product P, stirring for 1 hour, adding 3M HCl for quenching reaction, combining organic phases after liquid separation, drying and spin-drying the solvent to obtain a product P', wherein the yield is 46%.
Example 4: under the catalysis of samarium iodide as catalyst, the ring opening trimethyl silication of tetrahydrofuran.
The reaction formula is shown as follows:
the reaction steps are as follows: in a glove box, SmI was added to a 4mL reaction vessel containing magnetons2THF solution (0.032mmol) (0.32mL), THF (3.95mmol,0.32mL), Mg powder (3.95mmol,96Mg), TMSCl (7.9mmol,1mL), sealed, transferred to 80 deg.C, stirred to react for 24h, diluted with DCM, transferred to a 100mL round-bottom flask to obtain a reaction solution containing intermediate P, and calculating the intermediate productThe yield of P, the yield of intermediate P, was measured as follows: 1) firstly, preparing a mixture of a standard intermediate product P and an internal standard sample dodecane with a certain molar mass gradient for gas chromatography analysis, and measuring peak areas to obtain a relation curve of peak area ratio and molar mass ratio of P and the internal standard substance, namely an internal standard curve. 2) Dodecane was added as an internal standard to the obtained reaction solution containing the intermediate product P, peak area ratios of the product and the internal standard were measured by gas chromatography, a molar amount of the product was measured by an internal standard curve, and GC yields of the intermediate product P prepared from the compound of formula 1 and the compound of formula 2 were calculated by dividing the molar amount of the product by one-half of the molar amount of the compound of formula 1, whereby the yield of the product P was calculated to be 82%. And adding 20mL of water into the reaction solution containing the intermediate product P, stirring for 1 hour, adding 3M HCl for quenching reaction, combining organic phases after liquid separation, drying and spin-drying the solvent to obtain a product P', wherein the yield is 78%.
Example 5: in the additive B (C)6F5)3Under the action, the ring opening trimethylsilylation reaction of tetrahydrofuran is carried out.
The reaction formula is shown as follows:
the reaction steps are as follows: in a glove box, add B (C) to a 4mL reaction vessel containing magnetons6F5)3(0.079mmol,40Mg), Mg powder (7.9mmol,189.6Mg), THF (7.9mmol,0.64mL), TMSCl (7.9mmol,1mL), sealed, transferred to 60 ℃ to stir for 24h, diluted with DCM, transferred to a 100mL round bottom flask to obtain a reaction solution containing intermediate P, the yield of intermediate P was calculated and measured as follows: 1) firstly, preparing a mixture of a standard intermediate product P and an internal standard sample dodecane with a certain molar mass gradient for gas chromatography analysis, and measuring peak areas to obtain a relation curve of peak area ratio and molar mass ratio of P and the internal standard substance, namely an internal standard curve. 2) Adding dodecane serving as an internal standard into the obtained reaction liquid containing the intermediate product P, and analyzing the product and the internal standard by gas chromatographyPeak area ratio of the compounds, the molar amount of the product measured by an internal standard curve, and the GC yield of the intermediate product P prepared from the compound of formula 1 and the compound of formula 2 calculated by dividing the molar amount of the product by one-half of the molar amount of the compound of formula 1, from which the yield of the product P was calculated to be 0.9%. And adding 20mL of water into the reaction solution containing the intermediate product P, stirring for 1 hour, adding 3M HCl for quenching reaction, combining organic phases after liquid separation, drying and spin-drying the solvent to obtain a product P', wherein the yield is 0.4%.
Example 6: in the presence of catalyst samarium iodide and additive B (C)6F5)3Under the action, the ring opening trimethylsilylation reaction of tetrahydrofuran is carried out.
The reaction formula is shown as follows:
the reaction steps are as follows: in a glove box, add B (C) to a 4mL reaction vessel containing magnetons6F5)3(0.079mmol,40Mg), Mg powder (7.9mmol,189.6Mg), SmI2(0.064mmol) in THF (0.64mL), TMSCl (7.9mmol,1mL), sealed, transferred to 60 ℃ for stirring reaction for 24h, diluted with DCM, transferred to a 100mL round-bottom flask to obtain a reaction solution containing intermediate product P, and the yield of intermediate product P is calculated by the following method: 1) firstly, preparing a mixture of a standard intermediate product P and an internal standard sample dodecane with a certain molar mass gradient for gas chromatography analysis, and measuring peak areas to obtain a relation curve of peak area ratio and molar mass ratio of P and the internal standard substance, namely an internal standard curve. 2) Dodecane was added as an internal standard to the obtained reaction solution containing the intermediate product P, peak area ratios of the product and the internal standard were measured by gas chromatography, a molar amount of the product was measured by an internal standard curve, and GC yields of the intermediate product P prepared from the compound of formula 1 and the compound of formula 2 were calculated by dividing the molar amount of the product by one-half of the molar amount of the compound of formula 1, whereby the yield of the product P was calculated to be 89%. 20mL of water was added to the reaction solution containing intermediate P, and the mixture was stirred for 1 hour and thenAdding 3M HCl for quenching reaction, merging organic phases after liquid separation, drying and spin-drying the solvent to obtain a product P', wherein the yield is 82%.
Although the embodiments and comparative examples of the present invention have been shown and described above, it is understood that the above embodiments and comparative examples are illustrative and not to be construed as limiting the present invention, and those skilled in the art can make changes, modifications, substitutions and alterations to the above embodiments within the scope of the present invention.
Claims (8)
1. The method for the ring-opening double silicification reaction of tetrahydrofuran is characterized in that the reaction formula of the ring-opening double silicification reaction of tetrahydrofuran is as follows:
wherein R is1、R2、R3Each independently selected from methyl, ethyl, isopropyl; the catalyst used in the tetrahydrofuran ring-opening double-silicification reaction is selected from SmI2NaI, KI and ZnI2One or more of (a).
2. The method for ring-opening disilylation reaction of tetrahydrofuran according to claim 1, wherein the temperature of the ring-opening disilylation reaction of tetrahydrofuran is controlled to be 40-80 ℃.
3. The method for ring-opening disilication of tetrahydrofuran according to claim 1, wherein during the ring-opening disilication of tetrahydrofuran, magnesium is further added into the reaction system; preferably, the magnesium is magnesium strip, magnesium grain or magnesium powder; preferably, the magnesium is magnesium powder.
4. The method for ring-opening disilylation of tetrahydrofuran according to claim 3, wherein the molar ratio of said magnesium to said compound represented by formula 2 is (0.5-2): 1.
5. The method for ring-opening disilylation of tetrahydrofuran according to claim 1, wherein the molar ratio of the compound represented by formula 1 to the compound represented by formula 2 is (0.9-1.1): 1.
6. The method for ring-opening disilylation of tetrahydrofuran according to claim 1, wherein the molar ratio of said catalyst to said compound represented by formula 2 is (0.004-0.009): 1.
7. The method for ring-opening disilication of tetrahydrofuran according to claim 1, wherein during the ring-opening disilication of tetrahydrofuran, an additive is further added into the reaction system, wherein the additive is B (C)6F5)3。
8. The method for ring-opening disilylation of tetrahydrofuran according to claim 7, wherein the molar ratio of the additive to the compound represented by formula 2 is (0.005-0.01): 1.
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| CN113929574B (en) * | 2021-10-13 | 2024-02-02 | 中国科学院山西煤炭化学研究所 | Method for preparing butanediol ester compound from tetrahydrofuran compound |
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