CN102989513A - Acidic ionic liquid catalyst, synthesis method thereof, and method for catalyzing microcrystalline cellulose hydrolysis - Google Patents

Acidic ionic liquid catalyst, synthesis method thereof, and method for catalyzing microcrystalline cellulose hydrolysis Download PDF

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CN102989513A
CN102989513A CN201210492993XA CN201210492993A CN102989513A CN 102989513 A CN102989513 A CN 102989513A CN 201210492993X A CN201210492993X A CN 201210492993XA CN 201210492993 A CN201210492993 A CN 201210492993A CN 102989513 A CN102989513 A CN 102989513A
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ionic liquid
microcrystalline cellulose
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acidic ionic
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CN102989513B (en
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马忠华
马敬中
杨秋红
贺梦丽
严新稳
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Huazhong Agricultural University
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Abstract

The invention discloses an acidic ionic liquid catalyst expressed as general formula (I), wherein in the general formula (I), b=1-4; when m=1, X represents BF4, CF3SO3, CF3COO, Cl, HSO4, H2PO4 or p-MeC6H4SO3; when m=3, X represents PW12O40 or PMo12O40; and when m=4, X represents SiW12O40. Furthermore, the invention discloses synthesis of the acidic ionic liquid catalyst and a method for catalyzing microcrystalline cellulose hydrolysis. The acidic ionic liquid catalyst disclosed by the invention has a strong Br phi nsted acidity, and can be used as an efficient catalyst of an organic reaction and for preparing renewable energy sources; metal salt of the acidic ionic liquid catalyst can be applied to a Lewis acid catalysis reaction, or a conducting salt in electrolyte and the like; and according to the method for catalyzing the microcrystalline cellulose hydrolysis disclosed by the invention, comparatively high 5-hydroxymethyl furfural yield and reducing sugar yield are achieved.

Description

A kind of acidic ionic liquid catalysts and the method synthetic and hydrolysis of catalysis microcrystalline cellulose thereof
Technical field
The present invention relates to a kind of acidic ionic liquid catalysts and preparation method thereof, the invention still further relates to a kind of method of acidic ionic liquid catalysts catalysis microcrystalline cellulose hydrolysis.
Background technology
Functionalized ion liquid can strengthen conventional ion liquid greatly as versatility and the scope of application of reaction medium and reaction reagent.Acidic ion liquid can play the effect of catalyst and reaction dissolvent simultaneously as a class of functionalized ion liquid in organic reaction.Metal halide type ionic liquid is the common ionic liquid as Lewis acid, but often to water sensitive (Chem. Rev. 1999,2071; Angew. Chem., Int. Ed. 2000,39,3772; Chem. Commun. 2001,2010), limited its range of application.And Br nsted type acidic ion liquid much has water-resistant stability.
Br nsted type acidic ion liquid is according to structure, can be divided into two classes again: a class be the alkaline heterocycle such as imidazoles, pyridine protonated or with protonated quaternary ammonium salt etc. as cation, the respective acids radical ion is as anion (Adv. Synth. Catal. 2009,351,1939; CN 101209973A, 2008; Green Chem. 2003,5,38); Another kind of is directly acidic functionality to be imported the heterocycles such as imidazoles, pyridine by covalent bond, forms the cation of acid functional group functionalization, and then acidifying obtains ionic liquid (Angew. Chem. Int. Ed. 2009,48,168; Chem. Commun. 2011,47, and 2176; Appl. Catal. A:Gen. 2011,392, and 233).
Acidic functionality imports cationic ionic liquid by the covalent bonding effect, with the anion acting in conjunction, embodies the concerted catalysis effect.For example, Chou seminar report, ionic liquid N-MeC 3H 3N 2 +(CH 2) 4SO 3HHSO 4 -/ CoSO 4(C 3H 3N represents imidazole ring) be used for the hydrolysis of catalysis 4-methyl-2 pentanone system microcrystalline cellulose, the productive rate of hydroxymethylfurans formaldehyde and furtural is respectively 24% and 17%, conversion ratio 84%, and the acidic ion liquid that cation is modified without acid functional group, the best productive rate that obtains is no more than 5%, the highest 19%(Carbohydr. Res. 2011,346,58 of conversion ratio).Anion may play the effect of dissolving cellulos, and the cation link-SO 3H functional group then plays a key effect for the hydrolysis of glycosidic bond.Amarasekara research group is further ionic liquid loaded to SiO with this class 2Be used for catalysis after on the carrier, show still to have the concerted catalysis effect between functionalization cation and the anion, be used for cellulosic hydrolysis, can obtain the highest 67% reducing sugar yield and 26% glucose productive rate, and under the equal conditions, SiO 2The sulfonic acid catalyzes of load, only acquisition is respectively 24% and 11% productive rate (Catal. Commun. 2010,11,1072).
Acidic functionality imports cationic ionic liquid by the covalent bonding effect, when keeping high catalytic activity, also be conducive to catalyst separation, recycle.For example, Wang seminar has at first reported general-SO 3H functional group is connected to the upper highly acidic cation that forms of imidazole ring (MIMPS), pyridine ring (PyPS) and quaternary ammonium salt (TEAPS) by covalent bond, and heteropoly acid (HPA) is anion, synthetic heteropoly acid salt novel ion liquid.Such ionic liquid is in the esterification of catalysis citric acid and butanols, not only show outstanding catalytic activity (the highest 95.4% productive rate) and reaction selectivity (98%), and show the characteristic of a kind of " reaction induced being separated " of uniqueness, it namely is homogeneous catalysis in course of reaction, and in the reaction later stage, catalyst is subjected to the impact of reaction system change of component, from system, separate out gradually, thereby be conducive to catalyst separation, reclaim, recycle (Angew. Chem. Int. Ed. 2009,48,168).Yan seminar has also reported this class ionic liquid successively in ester exchange reaction, also has the catalysis characteristics (Appl. Catal. A:Gen. 2011,392,233) of this " reaction induced being separated ".Again for example, Huang seminar is with [MIMPS] 3PW 12O 40Be used for the dehydration of catalysis fructose, can selectively obtain 5-HMF, maximum output 99.1%, selective 98.8%(Bioresour. Technol. 2012,106,170).
Result of study shows that the acid intensity of acidic ion liquid has influence on catalytic effect.Acid stronger ionic liquid is expected to obtain better catalytic effect.For example, a series of sulfonic acid (SO have detected in Wang seminar 3H) acid strength of functionalized ion liquid, result show, under 110 ℃, and Acidity function H 0Value is between-1.5 ~-3.6, and the Acidity order is consistent (J. Mol. Catal. A:Chem. 2007,264,53) with its activity in acid catalyzed reaction.
The fluoroalkyl sulfimide of enjoying a double blessing is a kind of practicality super acid, and its general formula is:
Figure BDA0000248080421
The intrinsic acidity of fluoroalkyl sulfimide of enjoying a double blessing compares CF 3SO 3H is stronger, and for example, the acid order of some strong acid is: (C 4F 9SO 2) 2NH〉CF 3SO 2NHSO 2C 4F 9(CF 3SO 2) 3CH〉(CF 3SO 2) 2NH〉CF 3SO 3H〉H 2SO 4(Chem. Ztg. 1972,96,582; J. Am. Chem. Soc., 1994,116,3047; Science, 2000,289,72; J. Phys. Chem. A, 2009,113,8421).This superpower acidity is owing to conjugation (delocalization) effect that strong π-the electron acceptor substituting group produces, and strong sucting electronic effect (Inorg. Chem., 1996,35,1918 of perfluoroalkyl; Solid State Sci. 2002,4,1535; Angew. Chem. Int. Ed. 2005,44,5485).This superpower acidity is given the good catalytic activity of fluoroalkyl sulfimide of enjoying a double blessing, and in Development of Novel ultra high efficiency catalyst field, has important commercial application and is worth.Therefore, people are being devoted to carry out synthetic and application study (US 6319428 B1,2001 of novel fluorine sulfimide and derivative thereof always; J. Fluorine Chem. 2004,125, and 1231).For example, Nie of the Central China University of Science and Technology advances material that seminar uses the fluoroalkyl sulfimide functionalization of enjoying a double blessing and ionic liquid as catalyst, be widely used in comprising the organic reactions such as condensation reaction of aromatic nitration, esterification, bis (indolyl) methane, obtain good catalytic effect (J. Mol. Catal. A:Chem. 2005,236,119; J. Mol. Catal. A:Chem. 2007,265,9; Adv. Synth. Catal. 2009,351, and 1939; J. Mol. Catal. A:Chem. 2009,311,46; Synth. Commun. 2012,42, and 506).
As the anion of ionic liquid, research report (CN 101747243 A are being arranged all aspect catalysis and the electrochemical applications with the fluoroalkyl sulfimide of enjoying a double blessing; Adv. Synth. Catal. 2009,351, and 1939), but perfluoroalkyl sulfimide acid functional group is not bonded directly on the heterocycles such as imidazoles or pyridine as the cationic report of ionic liquid.And with respect to sulfonic acid functional group (SO 3H), not only acidity is stronger for the fluoroalkyl sulfimide of enjoying a double blessing, in its structure also with two perfluoroalkyl structures, have larger changeability, when especially the carbon number of perfluoroalkyl reaches 8, will embody obvious fluorine effect (Tetrahedron, 2002,58,4015; Tetrahedron, 2002,58,8345; J. Fluorine Chem. 2009,130, and 98; J. Fluorine Chem. 2010,131, and 111), some special catalytic effects of ionic liquid that this will give the fluoroalkyl sulfimide functionalization of enjoying a double blessing are expected to embodying superior catalytic performance in the reaction system widely.
Summary of the invention
First purpose of the present invention provides a kind of novel acidic ionic liquid catalysts, and its general formula is (I):
Figure BDA0000248080422
In the general formula (I), b=1 ~ 4, n represents straight chain;
During m=1, X=BF 4, CF 3SO 3, CF 3COO, Cl, HSO 4, H 2PO 4, p-MeC 6H 4SO 3During m=3, X=PW 12O 40, PMo 12O 40During m=4, X=SiW 12O 40
Second purpose of the present invention provides the preparation method of above-mentioned acidic ionic liquid catalysts, and the method is with general formula (II) compound and acid reaction:
Figure BDA0000248080423
In the general formula (II), b=1 ~ 4, n represents straight chain;
Described acid is HBF 4, CF 3SO 3H, CF 3COOH, HCl, H 2SO 4, H 3PO 4, p-MeC 6H 4SO 3H, H 3PW 12O 40, H 3PMo 12O 40, H 4SiW 12O 40
Described reaction is to finish with equimolar acid in homogeneous system, uses acetonitrile or water, and perhaps both mixed solvents are as reaction system.
General formula (II) compound is to be obtained by the alkali metal salt of general formula (III) compound and the reaction of formula (IV) compound:
Figure BDA0000248080424
In the general formula (III), b=1 ~ 4, n represents straight chain;
Described alkali metal salt is sodium salt or sylvite;
Reaction condition is: 120 ℃ of lower reactions 24-48 hour.
General formula (III) compound is again with chemical formula n-C bF 2b+1SO 2NH 2The perfluoroalkyl sulfonamide of (the b value is that 1 ~ 4, n represents straight chain) is raw material, makes through following reaction successively:
(1) perfluoroalkyl sulfonyl fluoride or perfluoroalkyl sulfonic acid chloride and the ammonification of ammonification reagent make the perfluoroalkyl sulfonamide, and the general formula of perfluoroalkyl sulfonamide is n-C bF 2b+1SO 2NH 2, the b value is that 1 ~ 4, n represents straight chain.
(2) perfluoroalkyl sulfonamide and potash or sodium carbonate effect as solvent, obtain perfluoroalkyl sulfonamide sylvite or perfluoroalkyl sulfonamide sodium salt with acetonitrile or water, and its general formula is n-C bF 2b+1SO 2NHM, the b value is that 1 ~ 4, n represents straight chain, M is K or Na.
(3) above-mentioned sylvite or sodium salt and chloropropyl sulfonic acid chloride ClCH 2CH 2CH 2SO 2The Cl effect is made washing agent and extractant with acetonitrile, obtains chloropropyl sulfonyl perfluoroalkyl sulfimide sylvite ClCH after concentrating 2CH 2CH 2SO 2NKSO 2-n-C bF 2b+1Or chloropropyl sulfonyl perfluoroalkyl sulfimide sodium salt ClCH 2CH 2CH 2SO 2NNaSO 2-n-C bF 2b+1, the b value is that 1 ~ 4, n represents straight chain.
Perfluoroalkyl sulfonamide n-C in the step (1) bF 2b+1SO 2NH 2(the b value is 1 ~ 4) is that (Inorg. Chem. 1993,32,5007 for employing list of references method; J. Fluorine Chem. 2004,125, and 243), with perfluoroalkyl sulfonyl fluoride or perfluoroalkyl sulfonic acid chloride and liquefied ammonia reaction acquisition under-78 ℃.
Described perfluoroalkyl sulfonamide and potash or sodium carbonate on, the perfluoroalkyl sulfonamide (CF of short chain 3SO 2NH 2) with glassware for drinking water certain compatibility being arranged, can directly react at aqueous phase.
In the course of reaction of described perfluoroalkyl sulfonamide potassium/sodium salt and chloropropyl sulfonic acid chloride, both molar ratios are 1:1.3, make acid binding agent with potash, and acetonitrile is solvent, 55 ℃ of lower reactions 8-12 hour.
Described ClCH 2CH 2CH 2SO 2NMSO 2-n-C bF 2b+1(M=K; Na) with N-methylimidazole course of reaction in; the N-methylimidazole is directly as reaction substrate; do not use other organic solvents; 120 ℃ were reacted 24-48 hour, reacted the excessive acetonitrile of complete usefulness as washing agent, and the KCl accessory substance that produces in the system is separated out; then supernatant liquor is concentrated, obtain 3-(1-methylimidazole) sulfonyl propyl base perfluoroalkyl sulfimide inner salt.
Described inner salt uses wherein equimolar amounts inorganic acid CF in acidization 3SO 3H, CF 3COOH, p-MeC 6H 4SO 3H, HBF 4, H 2SO 4, H 3PO 4, HCl and three kinds of heteropoly acid H 3PW 12O 40, H 3PMo 12O 40, H 4SiW 12O 40Carry out acidifying.The concrete foundation of the solvent that acidifying is adopted is: CF 3SO 3H, CF 3COOH, p-MeC 6H 4SO 3H, HBF 4Be dissolved in CH 3NO 2So, use CH 3NO 2Acidified solvent as these four kinds of acid; And H 2SO 4, H 3PO 4, HCl is water-soluble, utilizes water and CH 3The character that CN dissolves each other uses mixed solvent to realize acidifying; The dissolubility of heteropoly acid in acetonitrile is undesirable, so adopt mixed solvent V CH3CN/ V H2O≈ 2:1 dissolves heteropoly acid, carries out acidification reaction with inner salt again.
The 3rd purpose of the present invention provides a kind of method of catalysis microcrystalline cellulose hydrolysis, the solvent that hydrolysis is used in the method is 1-butyl-3-methylimidazole villaumite, hydrolysis temperature is 80 ~ 120 ℃, the mol ratio of dehydrated glucose unit is 2 ~ 5:1 in the mole dosage of water and the microcrystalline cellulose, used catalyst is acidic ionic liquid catalysts, and its general formula is (I):
In the general formula (I), b=1 ~ 4, n represents straight chain;
During m=1, X=BF 4, CF 3SO 3, CF 3COO, Cl, HSO 4, H 2PO 4, p-MeC 6H 4SO 3During m=3, X=PW 12O 40, PMo 12O 40During m=4, X=SiW 12O 40,
The mole dosage of described acidic ionic liquid catalysts be dehydrated glucose unit in the microcrystalline cellulose mole 10 ~ 50%.
Preferably, the mole dosage of described acidic ionic liquid catalysts be dehydrated glucose unit in the microcrystalline cellulose mole 20%.
Preferably, the mol ratio of dehydrated glucose unit is 3:1 in the mole dosage of water and the microcrystalline cellulose.
Preferably, hydrolysis temperature is 100 ℃.
Ionic-liquid catalyst of the present invention has strong Br nsted acidity, and can be used as the effective catalyst of organic reaction, preparation regenerative resource.Its slaine can be used as the Lewis acid catalyzed reaction, also may be as the conducting salt in the electrolyte etc.The method of catalysis microcrystalline cellulose hydrolysis of the present invention can obtain higher 5-HMF productive rate and reducing sugar yield.
Description of drawings
Fig. 1: the FT IR collection of illustrative plates of chloropropyl sulfonyl perfluoro butyl sulfimide potassium;
Fig. 2: chloropropyl sulfonyl perfluoro butyl sulfimide potassium 1H NMR collection of illustrative plates;
Fig. 3: chloropropyl sulfonyl perfluoro butyl sulfimide potassium 19F NMR collection of illustrative plates;
Fig. 4: the FT IR collection of illustrative plates of chloropropyl sulfonyl trifluoromethanesulp-onyl-onyl imide potassium;
Fig. 5: chloropropyl sulfonyl trifluoromethanesulp-onyl-onyl imide potassium 1H NMR collection of illustrative plates;
The FT-IR collection of illustrative plates of Fig. 6: 3-(1-methylimidazole) sulfonyl propyl base perfluoro butyl sulfimide inner salt;
Fig. 7: 3-(1-methylimidazole) sulfonyl propyl base perfluoro butyl sulfimide inner salt 1H NMR collection of illustrative plates;
Fig. 8: 3-(1-methylimidazole) sulfonyl propyl base perfluoro butyl sulfimide inner salt 19F NMR collection of illustrative plates;
The FT IR collection of illustrative plates of Fig. 9: 3-(1-methylimidazole) sulfonyl propyl base trifluoromethanesulp-onyl-onyl imide inner salt;
Figure 10: 3-(1-methylimidazole) sulfonyl propyl base trifluoromethanesulp-onyl-onyl imide inner salt 1H NMR collection of illustrative plates;
Figure 11: 3-(1-methylimidazole) sulfonyl propyl base perfluoro butyl sulfimide trifluoromethyl sulfonic acid 1H NMR collection of illustrative plates;
Figure 12: 3-(1-methylimidazole) sulfonyl propyl base perfluoro butyl sulfimide phosphotungstate 1H NMR collection of illustrative plates;
Figure 13: 3-(1-methylimidazole) sulfonyl propyl base trifluoromethanesulp-onyl-onyl imide phosphotungstate 1H NMR collection of illustrative plates;
Figure 14: microcrystalline cellulose hydrolysis schematic diagram;
Figure 15: (condition is followed successively by: the mol ratio of reaction substrate and water consumption for the reduced sugar of fluoboric acid 3-(1-methylimidazole) sulfonyl propyl base perfluoroalkyl sulfimide catalysis microcrystalline cellulose hydrolysis and 5-HMF productive rate, catalyst use amount (with respect to the dehydrated glucose unit in the microcrystalline cellulose), hydrolysis temperature);
The 5-HMF productive rate of Figure 16: 3-(1-methylimidazole) sulfonyl propyl base perfluoro butyl sulfimide heteropolyacid salt catalysis microcrystalline cellulose hydrolysis;
Reduced sugar and the 5-HMF productive rate of the acid ionic liquid-catalyzed microcrystalline cellulose hydrolysis of Figure 17: 3-(1-methylimidazole) sulfonyl propyl base perfluoroalkyl sulfimide.
The specific embodiment
The present invention is described in detail below in conjunction with embodiment.
The preparation of embodiment 1:3-(1-methylimidazole) sulfonyl propyl base perfluoro butyl sulfimide trifluoromethyl sulfonic acid may further comprise the steps:
Synthesizing of step 1 perfluoro butyl sulfonamide potassium:
The synthetic reaction route is as follows:
Figure BDA0000248080426
In 50mL single port flask, add successively 5g C 4F 9SO 2NH 2, 12mL water.Dropwise add acetone, until C 4F 9SO 2NH 2Fully dissolving.Add 2.8g K in batches 2CO 3, a large amount of Bubble formations are arranged.Room temperature magnetic agitation 8h.Concentrated desolventizing obtains the brilliant white solid.50 ℃ of oil pumps vacuumize.Add 100mL acetone, 50 ℃ of backflow 1h.Suction filtration, filtrate is concentrated, obtains white solid.75 ℃ of vacuum drying obtain the 4.66g white solid.Productive rate is 83%.
Target product C 4F 9SO 2The characterization data of NHK is as follows:
IR?(KBr,?υ,?cm -1):?3336,?3271?(υ,?-NH-),?1294,?1174(-CF 2CF 2CF 2CF 3),?1356,?1129?(-SO 2-);
ESI-MS:?m/z?(-)?297?[M-K] +.
Synthesizing of step 2 chloropropyl sulfonyl perfluoro butyl sulfimide sylvite:
The synthetic reaction route is as follows:
Figure BDA0000248080427
In the 50mL there-necked flask, add 2g(1.78 mmol) C 4F 9SO 2NHK adds the 30mL acetonitrile, is warming up to 55 ℃ of stirrings and makes it dissolving.Dropwise add 10mL Cl (CH 2) 3SO 2Cl (0.34g, 1.92mmol) solution.Reactant liquor becomes white emulsion at once.Add again 0.57g K 2CO 3, 55 ℃ of reaction 12h.Get white solid after revolving the steaming desolventizing, add the 40mL oxolane, stirring at room is overnight.Remove by filter insoluble matter, filtrate is white emulsion, revolves steaming, obtains faint yellow solid.60 ℃ of vacuum drying 6h obtain dark brown solid, and productive rate is 96%, mp: 200 ℃.
Target product ClCH 2CH 2CH 2SO 2NKSO 2C 4F 9Characterization data is as follows:
IR?(KBr,?υ,?cm -1):?2974(υ as,?CH 2),?2876(υ s,?CH 2),?1446,?1084?(-SO 2NSO 2-),?1320-1140?(-CF 2CF 2CF 2CF 3);
1H?NMR?(DMSO):?3.769-3.737?(t,?2H,?ClCH 2),?3.118-3.082?(t,?2H,?-CH 2CH 2 CH 2 ),?2.138-2.090(m,?2H,?-CH 2 CH 2 CH 2);
19F?NMR?(DMSO):?-80.313~-80.364?(3F,?-CF 3),?-112.828~-112.900?(2F,?-CF 2SO 2-),?-120.942~-120.966?(2F,?-CF 2CF 2 CF 2 CF 3,?-125.593~-125.702?(-CF 2 CF 2 CF 2CF 3).
Synthesizing of step 3 3-(1-methylimidazole) sulfonyl propyl base perfluoro butyl sulfimide inner salt:
The synthetic reaction route is as follows:
Figure BDA0000248080428
In 5mL single port flask, add 0.2g chloropropyl sulfonyl perfluoro butyl sulfimide sylvite, add 3mL N-methylimidazole.Be warming up to 120 ℃ of reaction 48h.Reactant liquor becomes opaque Chinese red by glassy yellow.Reaction finishes to add the 4mL acetonitrile in reactant liquor, has pulverulent solids to occur, and centrifugal, the supernatant liquor decompression distillation obtains yellow solid, and ether fully washs, and 120 ℃ vacuumize 8h.Obtain 0.17g khaki solid, productive rate is 85%.
Target product CH 3-C 3H 3N 2 +-CH 2CH 2CH 2SO 2N -SO 2C 4F 9Characterization data is as follows:
IR?(KBr，υ，cm -1):?3443,?3158,?3091?(υ C-H,?imidazole),?2969?(υ as,?CH 2),?1639,?1582,?1552?(δ C-H,?imidazole),?1450,?1070?(-SO 2NSO 2-),?1325-1129?(-CF 2CF 2CF 2CF 3);
1H?NMR?(DMSO):?9.159?(s,?1H,?imidazole),?7.799-7.731?(d,?2H,?imidazole),?4.325?(t,?2H,?J=6.8?Hz,?CH 2);?3.857?(s,?3H,?N-CH 3),?3.028?(t,?2H,?J=7.6?Hz,?CH 2),?2.264-2.191?(m,?2H,?CH 2).
Synthesizing of step 4 3-(1-methylimidazole) sulfonyl propyl base perfluoro butyl sulfimide trifluoromethyl sulfonic acid:
The synthetic reaction route is as follows:
Figure BDA0000248080429
Get 0.1g 3-(1-methylimidazole) sulfonyl propyl base perfluoro butyl sulfimide inner salt in 5mL single port flask, add the nitromethane solution of stoichiometric trifluoromethane sulfonic acid, 80 ℃ of reaction 6h.Bathe 80 ℃ of temperature, oil pump vacuumizes 6-7h, obtains product.m.?p.:?200℃。
The characterization data of target product is as follows:
1H?NMR?(400?MHz,?DMSO):?δ?3.753?(t,?2H,?J=6.6),?3.100?(t,?2H,?J=7.4),?2.138-2.090?(m,?2H);
ESI-MS:?m/z?(+)?[M+K] +?515.9,?m/z?(-)?[M-K] +?437.9.
The preparation of embodiment 2:3-(1-methylimidazole) sulfonyl propyl base perfluoro butyl sulfimide phosphotungstate may further comprise the steps:
Step 1,2,3 identical with embodiment 1.
Synthesizing of step 4 3-(1-methylimidazole) sulfonyl propyl base perfluoro butyl sulfimide phosphotungstate:
The synthetic reaction route is as follows:
Figure BDA00002480804210
In 10mL single port flask, add successively 0.1498g (0.309mmol) 3-(1-methylimidazole) sulfonyl propyl base perfluoro butyl sulfimide inner salt, the 2mL acetonitrile, 50 ℃ are stirred 10min, and solid all dissolves.Get 0.2965g(0.103mmol) H 3PW 12O 40Be dissolved in 2mL acetonitrile and 1mL water, form white emulsion, without obvious solid.Heteropoly acid solution is added in the flask, form yellow solution, nothing is obviously without solid.50 ℃ of stirring reaction 16h.Reaction finishes, and 75 ℃ concentrated, gets yellow solid.80 ℃, 14mmHg vacuumizes 5h, gets the 0.433g yellow solid.Productive rate is 97%.
The characterization data of target product is as follows:
1H?NMR?(400?MHz,?DMSO):?δ?9.091?(s,?1H),?7.766?(s,?1H),?7.695?(s,?1H),?4.302?(t,?2H,?J=7),?3.840?(s,?3H),?3.010?(t,?2H,?J=7.4),?2.252-2.179?(m,?2H).
The preparation of embodiment 3:3-(1-methylimidazole) sulfonyl propyl base trimethyl fluoride sulfonyl amine phosphotungstate may further comprise the steps:
The preparation of step 1 trimethyl fluoride sulfonyl amine potassium:
The synthetic reaction route is as follows:
In 25mL single port flask, add successively 2.1g CF 3SO 2NH 2, 9mL distilled water, stirring at room 5min, solid all dissolves, and it is muddy that solution shows slightly.Add 2.33g K in batches 2CO 3, just begun to have a large amount of bubbles to emit.Stirring at room 8h.Revolve steaming, remove most of water, bathe 55 ℃ of temperature, 2 mmHg oil pumps vacuumize 1h, remove a small amount of water.Add 40mL acetone stirring at room 12h.Suction filtration, filtrate is concentrated, gets white solid.80 ℃ of vacuum drying 10h.Get the 1.58g white solid, productive rate is 60%.
Target product CF 3SO 2The characterization data of NHK is as follows:
IR?(KBr,?υ,?cm -1):?3480,?983?(υ,?-NH-),?1286,?1196?(-CF 3),?1383,?1082?(-SO 2-).
Synthesizing of step 2 chloropropyl sulfonyl trifluoromethanesulp-onyl-onyl imide sylvite:
The synthetic reaction route is as follows:
In the 50mL there-necked flask, add successively 1.6g CF 3SO 2NHK, 10mL CH 3CN is warming up to 50 ℃ and adds thermal agitation 10min,, solid all dissolves, and solution is muddy.Add the dry K of 0.94g 2CO 3Get 1.97g 3-chloropropyl sulfonic acid chloride and be dissolved in 10mL CH 3CN.Dropwise add in the flask.50 ℃ are stirred 8h.Reaction finishes, and the concentrated acetonitrile of removing adds 55ml THF stirring at room 1h.Centrifugal, the white solid of concentrated supernatant.40 ℃ of vacuum drying 12h get the 1.94g white solid, and productive rate is 69%.
IR?(KBr,?υ,?cm -1):?2992,?2967?(CH 2,?υ as),?2877(CH 2,?υ s),?1313,?1069(-SO 2NSO 2-),?1274,?1196,?1132(-CF 3);? 1H?NMR?(400?MHz,?DMSO):?δ?3.750(t,?2H，?J=6.6),?3.101(t,?2H，J=?7.4),?2.148-2.078(m,?2H);? 19F?NMR?(DMSO):?δ?-77.893(3F,?CF 3).?ESI-MS:?m/z(+)?[M+K] +?365.8，m/z(-)?[M-K] +287.7
Synthesizing of step 3 3-(1-methylimidazole) sulfonyl propyl base trifluoromethanesulp-onyl-onyl imide inner salt:
The synthetic reaction route is as follows:
Figure BDA00002480804213
In 25mL single port flask, add successively 2g chloropropyl sulfonyl trifluoromethanesulp-onyl-onyl imide sylvite, 17mL N-methylimidazole.100 ℃ add thermal agitation 48h.Reaction finishes, and cooling adds the 35mL acetonitrile, has a large amount of solids to separate out, and is centrifugal, gets the supernatant decompression distillation, and adding ether has solid to separate out, ether soxhlet extraction 48h.TLC(ethyl acetate/methanol=7:1) detect the N-methylimidazole except clean.Productive rate is 68%.
IR?(KBr，υ，cm -1):?3441,?3160,?3121(υC-H?imidazole),?2967,?2877?(υ asCH 2),?1658,?1582,?(δ C-H?imidazole),?1325,?1069?(-SO 2NSO 2-),?1274-1132?(-CF 2CF 2CF 2CF 3);? 1H?NMR?(400?MHz,?DMSO):?δ?9.103?(s,?1H),?7.773?(d,?1H,?J=1.6),?7.699?(d,1H,?J=1.6),?4.301(t,?2H,?J=7),?3.843?(s,?3H),?3.014?(t,?2H,?J=7.6),?2.247-2.174?(m,?2H);? 19F?NMR?(DMSO):?δ?-77.796?(3F,?CF 3).?ESI-MS:?m/z(+)?709.1,?373.9
Synthesizing of step 4 3-(1-methylimidazole) sulfonyl propyl base trifluoromethanesulp-onyl-onyl imide phosphotungstate:
Synthetic route is as follows:
In 10mL single port flask, add successively 0.1035g (0.309mmol) 3-(1-methylimidazole) sulfonyl propyl base trifluoromethanesulp-onyl-onyl imide inner salt, the 2mL acetonitrile, 50 ℃ are stirred 10min, and solid all dissolves.Get 0.2965g(0.103mmol) H 3PW 12O 40Be dissolved in 2mL acetonitrile and 1mL water, form white emulsion, without obvious solid.Heteropoly acid solution is added in the flask, form yellow solution, nothing is obviously without solid.50 ℃ of stirring reaction 16h.Reaction finishes, and 75 ℃ concentrated, gets yellow solid.80 ℃, 14mmHg vacuumizes 5h.Productive rate is 95%.
1H?NMR?(400?MHz,?DMSO):?δ?9.089?(s,?1H),?7.765?(s,?1H),?7.691?(s,?1H),?4.298?(t,?2H,?J=7),?3.841?(s,?3H),?3.007?(t,?2H,?J=7.4),?2.245-2.173?(m,?2H).
Embodiment 4: the mensuration of the hydrolysis of presence of acidic ionic liquid catalyst microcrystalline cellulose and reduced sugar and 5-HMF:
Hydrolysis as shown in figure 14.
In vacuum glove box, take by weighing the 1-butyl of about 1.90g-3-methylimidazole villaumite, join in the flask that fills about 0.10g microcrystalline cellulose.Load onto the reflux condensing tube that drying tube is housed, system places oil bath under the reaction temperature, and 1-butyl-3-methylimidazole villaumite is fused into rapidly liquid state, and cellulose all dissolves behind the stirring 3h.In reaction system, add deionized water 33 μ L (mol ratio of cellulose dehydrated glucose unit and water is 1:3), have a small amount of cellulose to separate out, after continuing to stir 10min, the cellulose dissolution of separating out.Then, the acidic ionic liquid catalysts that takes by weighing 20mol% perfluoroalkyl sulfimide functionalization joins reaction system, continue to stir, and the beginning calculating reacting time.The consumption of best water and the acidic ionic liquid catalysts of perfluoroalkyl sulfimide functionalization is calculated as follows (molal weight of dehydrated glucose unit is 162g/mol).
Figure BDA00002480804215
Figure BDA00002480804216
An amount of reactant mixture is taken out in interval certain hour section sampling at every turn, and accurate its quality of weighing, adds 3mL deionized water cancellation reaction, obtains filtrate with the micro porous filtration membrane filtration.Take out 1mL with liquid-transfering gun from filtrate, accurately its quality of weighing is used for follow-up measurement.
With total reducing sugars (TRS) content in the above-mentioned filtrate of spectrophotometry, with high performance liquid chromatography (HPLC) mensuration glucose (GLU) and 5-HMF (5-HMF) concentration wherein.
The acidic ion liquid of perfluoroalkyl sulfimide functionalization described in the invention, be used for the hydrolysis of catalysis microcrystalline cellulose, the dicyandiamide solution that hydrolysis is used is 1-butyl-3-methylimidazole villaumite, the optimum hydrolysis temperature is 100 ℃, the mol ratio of dehydrated glucose unit is 3:1 in best water consumption and the cellulose, and the use amount (with respect to the dehydrated glucose unit in the microcrystalline cellulose) of best acidic ionic liquid catalysts is 20mol%.Under catalytic condition described above, the primary product of microcrystalline cellulose hydrolysis is reduced sugar and 5-HMF.
For example, under above-mentioned optimal conditions, during the ionic liquid-catalyzed microcrystalline cellulose of fluoboric acid 3-(1-methylimidazole) sulfonyl propyl base perfluoroalkyl sulfimide hydrolysis 4h, obtain high-reducing sugar productive rate 57%; Continue hydrolysis to about 11-12h, obtain the highest 5-HMF productive rate, about 23%(Figure 15).In the acidic ionic liquid catalysts of foregoing description, the about 3h of 3-(1-methylimidazole) sulfonyl propyl base perfluoroalkyl sulfimide silicotungstate catalyzing hydrolysis obtains the highest 5-HMF productive rate, about 32%(Figure 16).
The acidic ion liquid of perfluoroalkyl sulfimide functionalization described in the invention is used for the hydrolysis of catalysis microcrystalline cellulose, can be under the condition of gentleness one pot reaction, obtain higher 5-HMF productive rate and reducing sugar yield (Figure 17).

Claims (7)

  1. , a kind of acidic ionic liquid catalysts, general formula is (I):
    Figure FDA0000248080411
    In the general formula (I), b=1 ~ 4, n represents straight chain;
    During m=1, X=BF 4, CF 3SO 3, CF 3COO, Cl, HSO 4, H 2PO 4, p-MeC 6H 4SO 3During m=3, X=PW 12O 40, PMo 12O 40During m=4, X=SiW 12O 40
  2. 2. the synthetic method of acidic ionic liquid catalysts according to claim 1 is characterized in that general formula (II) compound and acid reaction:
    Figure FDA0000248080412
    In the general formula (II), b=1 ~ 4, n represents straight chain;
    Described acid is HBF 4, CF 3SO 3H, CF 3COOH, HCl, H 2SO 4, H 3PO 4, p-MeC 6H 4SO 3H, H 3PW 12O 40, H 3PMo 12O 40, H 4SiW 12O 40
    Described reaction is to carry out in the reaction system of a kind of or two kinds of compositions in acetonitrile, water.
  3. 3. the synthetic method of acidic ionic liquid catalysts according to claim 2 is characterized in that general formula (II) compound is that alkali metal salt and compound (IV) reaction by general formula (III) compound obtains:
    Figure FDA0000248080413
    In the general formula (III), b=1 ~ 4, n represents straight chain;
    Described alkali metal salt is sodium salt or sylvite;
    Reaction condition is: 120 ℃ of lower reactions 24 ~ 48 hours.
  4. 4. the method for catalysis microcrystalline cellulose hydrolysis, it is characterized in that: the solvent that hydrolysis is used is 1-butyl-3-methylimidazole villaumite, hydrolysis temperature is 80 ~ 120 ℃, the mol ratio of dehydrated glucose unit is 2 ~ 5:1 in the mole dosage of water and the microcrystalline cellulose, used catalyst is acidic ionic liquid catalysts, and its general formula is (I):
    Figure FDA0000248080414
    In the general formula (I), b=1 ~ 4, n represents straight chain;
    During m=1, X=BF 4, CF 3SO 3, CF 3COO, Cl, HSO 4, H 2PO 4, p-MeC 6H 4SO 3During m=3, X=PW 12O 40, PMo 12O 40During m=4, X=SiW 12O 40,
    The mole dosage of described acidic ionic liquid catalysts be dehydrated glucose unit in the microcrystalline cellulose mole 10 ~ 50%.
  5. 5. the method for catalysis microcrystalline cellulose according to claim 4 hydrolysis is characterized in that: the mole dosage of described acidic ionic liquid catalysts be dehydrated glucose unit in the microcrystalline cellulose mole 20%.
  6. 6. the method for catalysis microcrystalline cellulose according to claim 4 hydrolysis, it is characterized in that: the mol ratio of dehydrated glucose unit is 3:1 in the mole dosage of water and the microcrystalline cellulose.
  7. 7. the method for catalysis microcrystalline cellulose according to claim 4 hydrolysis, it is characterized in that: hydrolysis temperature is 100 ℃.
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CN105618139B (en) * 2016-03-23 2018-06-29 辽宁石油化工大学 A kind of ligocellulose degradation's method based on molybdenum multi-metal oxygen hydrochlorate
CN105618139A (en) * 2016-03-23 2016-06-01 辽宁石油化工大学 Method for degrading lignocellulose based on molybdenum polyoxometallate
WO2018149212A1 (en) * 2017-02-15 2018-08-23 惠州市大道新材料科技有限公司 Method for preparing pyridine ring sulfonyl imide alkali metal salt
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CN108212212A (en) * 2018-01-29 2018-06-29 中国科学院青岛生物能源与过程研究所 A kind of temperature sensitive acidic ionic liquid and preparation method thereof and the purposes in catalysis microcrystalline cellulose hydrolysis
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