CN101429135A - Br<Phi>nsted acid compound containing amide group, preparation and uses thereof - Google Patents
Br<Phi>nsted acid compound containing amide group, preparation and uses thereof Download PDFInfo
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- CN101429135A CN101429135A CN 200810236684 CN200810236684A CN101429135A CN 101429135 A CN101429135 A CN 101429135A CN 200810236684 CN200810236684 CN 200810236684 CN 200810236684 A CN200810236684 A CN 200810236684A CN 101429135 A CN101429135 A CN 101429135A
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Abstract
The invention provides a Br phi nsted acidic chemical compound containing amide groups. The chemical structural formula of the compound is shown on the right, wherein R1 is H or alkyl or phenyl containing 1 to 6 carbon atoms; R2 is the H or the alkyl containing 1 to 2 carbon atoms; R3 is the H or the alkyl containing 1 to 2 carbon atoms; X<-> represents an anionic group of Br phi nsted acidic HX. A synthesis method comprises a step of preparing the Br phi nsted acidic chemical compound containing amide groups from an amide chemical compound and Br phi nsted acid through neutralization reaction at a temperature between 0 and 100 DEG C. the synthesis method is simple and low in cost. The Br phi nsted acidic chemical compound containing amide groups can be used as a catalyst of esterification reaction and applied to esterification reaction, and has the advantages that the compound is high in conversion rate, high in selectivity, high in universality, simple in process, friendly to environment and the like, and a catalyst layer (containing water) can be repeatedly recycled for more than 20 times (can be unlimitedly used in theory) through simple water removal.
Description
Technical field
The present invention relates to phosphinylidyne-containing amine group
Acidic cpd and preparation method thereof, with and application in synthetic ester, belong to organic chemistry filed.
Background technology
Organic carboxylic ester chemical industry and medical aspect be a kind of important product and intermediary, the market analyst points out, to maintain the healthy momentum of growth in future in whole world ethyl acetate and butylacetate market, particularly in the U.S., owing to prepared the coating that does not contain atmospheric polluting material, promoted the flourish of ester industry greatly.In coatings industry, ethyl acetate is commonly used to replace methylethylketone, and butylacetate not only can be used for replacing methylethylketone (butanone), and in addition it can also replace isobutyl ketone, dimethylbenzene or toluene.The esterification process of prior art adopts mineral acid to realize as catalyzer mostly.But need to use a large amount of organic solvents, and the remaining spent acid in reaction back all can cause environmental pollution.
The method of tradition synthesizing ester is to be raw material with carboxylic acid or acid anhydrides and alcohols, this is a balanced reaction, if react with equimolar raw material, after reaching balance, have only 2/3 mole carboxylic acid and alcohol to be converted into ester, in order to improve the transformation efficiency of ester, adopt excessive carboxylic acid or alcohol usually, perhaps adopt constantly the ester or the water that produce are removed.These two kinds of methods are all made catalyzer with the vitriol oil at present, this technology is the production technique of domestic extensive employing at present, although cheap, the active advantages of higher that with the vitriol oil is that catalyzer has, but this method is unsatisfactory, some deficiency below main the existence: oxidisability, the dehydration property of (1) vitriol oil can cause a series of side reaction, as esterification, charing, make and contain sulfuric ester, ether, unsaturated compound etc. in the by product, thereby brought difficulty for the recovery refining and raw material of product; (2) vitriol oil has intensive corrodibility, etching apparatus; (3) discharging of a large amount of spent acid and reaction generation sulfurous gas can cause serious environmental pollution.Therefore change the catalyzer of esterification, the method for seeking new synthetic ester becomes the focus of current research.Because the raw material acid of esterification and alcohol are cheap and easy to get, thereby be the most frequently used method of synthetic ester.But esterification is a balance, in order to improve the transformation efficiency of reactant, often passes through to strengthen the amount of a certain reactant, or removes certain resultant in the reaction system (normally water also can be ester sometimes).In addition, the speed of esterification is very slow, often needs just can reach balance for a long time.For example, do not having under the condition of catalyzer, moles such as ester acid and methyl alcohol react down for 40 ℃ and can't reach balance in 49 days.
In order to improve the speed of esterification, people have been developed multiple catalysis technique, comprise physics catalysis, biocatalysis and chemical process catalysis etc.Comparatively speaking, chemical catalyst is still the main means of esterification catalytic.And mineral acids such as the vitriol oil, phosphoric acid, tosic acid are widely used in industry and research because it is cheap, catalytic efficiency is high.But, problem such as these catalyzer can bring also that side reaction is many, etching apparatus, waste discharge pollute, the scientific worker is seeking new catalyzer efficiently to replace these inorganic acid catalysts always both at home and abroad, has developed strong-acid ion exchange resin, zeolite molecular sieve, Lewis acid, solid heteropoly acid and super acids etc. in succession.But the employed catalyzer of the method for above-mentioned synthetic ester is synthetic complicated, and still needs a large amount of organic solvents, and the transformation efficiency of esterification is not high, aftertreatment more complicated etc.To accelerating state's lactone industrial development extremely important realistic meaning is arranged so study novel, efficient, green catalyzer.
The inventor finds a class phosphinylidyne-containing amine group
Acidic cpd.This compound is stable to water and air, has stronger acidity, can replace mineral acid and be applied to both can be used as catalyzer in traditional acid catalyzed reaction, can be used as reaction medium again, can also have broad application prospects as spe medium simultaneously.
Summary of the invention
The object of the present invention is to provide a class phosphinylidyne-containing amine group
Acidic cpd and its production and application, the gained compound can make the transformation efficiency of esterification and selectivity height, technology simple as the catalyzer of esterification, and environmentally friendly.
The present invention solves this technical problem by following scheme: phosphinylidyne-containing amine group
Acidic cpd, its chemical structural formula is:
(I)
R wherein
1For H or contain the alkyl or phenyl of 1～6 carbon atom; R
2For H or contain the alkyl of 1～2 carbon atom; R
3For H or contain the alkyl of 1～2 carbon atom.X
-Representative
The anionic group of acid HX.
Preferably, R
1Be selected from hydrogen, methyl, ethyl, propyl group, butyl, amyl group or hexyl; R
2, R
3Independently be selected from hydrogen, methyl or ethyl.
Above-mentioned negatively charged ion X
-Be selected from BF
4 -, PF
6 -, HCOO
-, CH
3COO
-, ClCH
2COO
-, CF
3COO
-, CH
3CH
2COO
-, Cl
-, Br
-, I
-, CH
3SO
3 -, CF
3SO
3 -, NO
3 -, SO
4 2-, HSO
4 -, H
2PO
4 -, HPO
4 2-, PO
4 3-, CH
3CHOHCOO
-, C
6H
5COO
-, C
6H
4OHCOO
-, C
6H
5CH
2COO
-In a kind of.
The present invention also provides above-mentioned phosphinylidyne-containing amine group
The preparation method of acidic cpd: reaction medium or do not have reaction medium in the presence of, amide compound with
Acid process neutralization reaction under 0～100 ℃ makes phosphinylidyne-containing amine group
Acidic cpd, wherein amide compound is
R in the formula
1For H or contain the alkyl or phenyl of 1～6 carbon atom; R
2For H or contain the alkyl of 1～2 carbon atom; R
3For H or contain the alkyl of 1～2 carbon atom.
Above-mentioned amide compound with
The mol ratio of acid is between 3:1 and the 1:3.
Described neutralization reaction is carried out in the presence of reaction medium, and reaction medium is selected from benzene, toluene, hexanaphthene or water.
Above-mentioned phosphinylidyne-containing amine group
Acidic cpd is as the application of catalyzer in esterification of esterification.
Employing formula (I) phosphinylidyne-containing amine group
Acidic cpd is as the catalyzer and the reaction medium of esterification, put into reaction vessel with aliphatic or aromatic acid and straight chain alcohol or branched-chain alcoho, under agitation, be heated to 10～180 ℃ of reactions 2～24 hours, reaction finishes and leaves standstill, gravity settling is told catalyst layer (moisture) and product ester layer, and high conversion (90～99%) and highly selective (100%) obtain esterification products; Described lipid acid is acetate, propionic acid, butyric acid, valeric acid, oxalic acid, Ba Dousuan, lactic acid, propanedioic acid, Succinic Acid, lauric acid, palmitinic acid, oleic acid or stearic acid; Aromatic acid is phenylformic acid, P-hydroxybenzoic acid, Whitfield's ointment, chloro-benzoic acid or styracin; Straight chain alcohol or branched-chain alcoho are methyl alcohol, ethanol, ethylene glycol, propyl alcohol, Virahol, glycerol, butanols, isopropylcarbinol, amylalcohol, primary isoamyl alcohol, hexanol, isohexyl alcohol, enanthol, iso-heptanol, octanol, isooctyl alcohol, decyl alcohol or lauryl alcohol.
Above-mentioned esterification skeleton symbol is:
Above-mentioned phosphinylidyne-containing amine group
The consumption mol ratio of acidic cpd and aliphatic or aromatic acid and straight chain alcohol or branched-chain alcoho is 0.1～1:2～5:2～6 part; Described temperature of reaction is 10～180 ℃, reacts 2～24 hours.
Above-mentioned catalyst layer can (can unrestrictedly use) more than 20 times in theory through simply dewatering in the recirculation use.
The present invention and traditional catalyst and reaction process relatively have the following advantages:
1. catalyzer is synthetic simple, with low cost, and bio-compatibility is good, environmental friendliness;
2. catalyst system is simple, and deionization liquid does not add other solvent and catalyzer outward;
3. directly dehydration in the reaction process does not need to add other dewatering agent;
4. separation is simple, purity is high;
5. catalyzer can recycle;
6. can high conversion, highly selective synthesizing ester compound in environmental friendliness medium ionic liquid;
7. universality is good.Saturated fatty acid, unsaturated fatty acids, α-alcohol acid, diprotic acid, aromatic acid, substituted aroma acid etc. can high conversion ground and primary alconol, secondary alcohol generate corresponding ester.
Embodiment
The following examples can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.
Embodiment 1
Taking by weighing methane amide 4.5 grams (0.1mol) is dissolved in the benzene, 4 ℃ of stirrings slowly drip methanesulfonic 9.6 grams (0.1mol) down, dripped off in 30 minutes, continued stirring reaction 4 hours at 4 ℃, heating, vacuum removes benzene, obtains white solid, is methane amide methane sulfonates product, fusing point (m.p): 41～44 ℃, productive rate 97%.
1H-NMR(300MHz，D
2O)：δ，ppm：2.84(s，3H)，7.00(s，3H)，9.60(s，1H).
MS(ESI)：m/z＝46.0(M
+).
Embodiment 2
Take by weighing ethanamide 5.9 grams (0.2mol), 0 ℃ of stirring slowly drips sulfuric acid 19.2 grams (0.2mol) down, drips off in 3 hours, at room temperature continued stirring reaction 5 hours, promptly obtain white solid ethanamide hydrosulfate product, fusing point (m.p): 82～85 ℃, productive rate 100%.
1H-NMR(300MHz，D
2O)：δ，ppm：2.10(s，1H)，2.32(s，3H)，7.05(s，3H).
MS(ESI)：m/z＝60.1(M
+).
Embodiment 3
Take by weighing hexanamide 11.5 grams (0.1mol), 20 ℃ of stirrings slowly drip the aqueous solution of phosphatase 79 .8 gram (0.1mol) down, dripped off in 30 minutes, continued stirring reaction 2 hours at 40 ℃, heating, vacuum removes and anhydrates, and promptly obtains hexanamide dihydrogen phosphate product, is white solid, fusing point (m.p): 76～78 ℃, productive rate 98%.
1H-NMR(300MHz，D
2O)：δ，ppm：0.96(m，3H)，1.29-1.33(m，4H)，1.62(m，2H)，2.00(s，2H)，2.40(m，2H)，7.00(s，3H).
MS(ESI)：m/z＝116.2(M
+).
Embodiment 4
Take by weighing succimide 9.9 grams (0.1mol), 20 ℃ of stirrings slowly drip hydroiodic acid HI 0.1mol down, drip off in 30 minutes, continued stirring reaction 2 hours at 50 ℃, heating, vacuum removes and anhydrates, and promptly obtains succimide iodized salt solid product, fusing point (m.p): 56～57 ℃, productive rate 99%.
1H-NMR(300MHz，D
2O)：δ，ppm：2.73(s，4H)，7.06(s，2H).
MS(ESI)：m/z＝100.1(M
+).
Embodiment 5
Take by weighing maleimide 9.7 grams (0.1mol), 50 ℃ of stirrings slowly drip Mono Chloro Acetic Acid 0.1mol down, drip off in 30 minutes, continue stirring reaction 2 hours at 50 ℃, promptly obtain maleimide chloracetate solid product, fusing point (m.p): 53～56 ℃, and productive rate 99%.
1H-NMR(300MHz，D
2O)：δ，ppm：4.49(s，2H)，7.00(s，2H)，7.05(s，2H).
MS(ESI)：m/z＝98.1(M
+).
Embodiment 6
Take by weighing N, N-dimethyl formamide 7.4 grams (0.1mol), 30 ℃ of stirrings slowly drip the aqueous solution of formic acid 4.6 grams (0.1mol) down, drip off in 30 minutes, continue stirring reaction 2 hours at 40 ℃, heating, vacuum removes and anhydrates, promptly obtain N, N-dimethyl formamide formate product is white solid, fusing point (m.p): 46～48 ℃, productive rate 99%.
1H-NMR(300MHz，D
2O)：δ，ppm：2.93(s，6H)，7.21(s，1H)，9.58(s，1H)，9.61(s，1H).
MS(ESI)：m/z＝74.1(M
+).
Embodiment 7
Take by weighing N, N-diethylformamide 10.1 grams (0.1mol), 70 ℃ of stirrings slowly drip the benzole soln of phenol formic acid 0.1mol down, dripped off in 30 minutes, and continued stirring reaction 2 hours at 70 ℃, heating, vacuum is removed benzene, promptly obtain N, N-diethylformamide phenol formate solid product, fusing point (m.p): 121～123 ℃, productive rate 99%.
1H-NMR(300MHz，D
2O)：δ，ppm：1.56(m，6H)，2.43(m，1H)，3.37(m，4H)，6.92(m，2H)，7.00(s，1H)，7.64(m，2H)，9.60(s，1H).
MS(ESI)：m/z＝102.1(M
+)
Embodiment 8
Take by weighing N, N-N,N-DIMETHYLACETAMIDE 8.7 grams (0.1mol), 70 ℃ of stirrings slowly drip the benzole soln 30mL of acetate 6.0 grams (0.1mol) down, drip off in 30 minutes, continue stirring reaction 2 hours at 100 ℃, heating, vacuum is removed benzene, promptly obtain N, N-N,N-DIMETHYLACETAMIDE acetate product is white solid, fusing point (m.p): 68～69 ℃, productive rate 99%.
1H-NMR(300MHz，D
2O)：δ，ppm：2.22(m，6H)，2.88(m，6H)，7.00(s，1H).
MS(ESI)：m/z＝88.1(M
+).
Embodiment 9
Take by weighing N, N-amide dimethyl butyrate 12.1 grams (0.1mol), 20 ℃ of stirrings slowly drip the aqueous solution of fluoroboric acid 0.1mol down, dripped off in 30 minutes, and continued stirring reaction 2 hours at 80 ℃, heating, vacuum removes and anhydrates, promptly obtain N, N-amide dimethyl butyrate a tetrafluoro borate solid product, fusing point (m.p): 46～47 ℃, productive rate 99%.
1H-NMR(300MHz，D
2O)：δ，ppm：0.96(m，3H)，1.67(m，2H)，2.43(m，2H)，2.90(s，6H)，7.01(s，1H).
MS(ESI)：m/z＝116.2(M
+).
Embodiment 10
Take by weighing N, N-diethyl butyramide 12.1 grams (0.1mol), 20 ℃ of stirrings slowly drip the aqueous solution of nitric acid 0.1mol down, dripped off in 30 minutes, and continued stirring reaction 2 hours at 90 ℃, heating, vacuum removes and anhydrates, promptly obtain N, N-amide dimethyl butyrate a tetrafluoro borate solid product, fusing point (m.p): 43～45 ℃, productive rate 99%.
1H-NMR(300MHz，D
2O)：δ，ppm：0.96(m，3H)，1.67(m，2H)，2.43(m，2H)，2.90(s，6H)，7.01(s，1H).
MS(ESI)：m/z＝116.2(M
+).
Embodiment 11
Take by weighing N, N-dimethyl hexanamide 14.3 grams (0.1mol), 20 ℃ of stirrings slowly drip the aqueous solution of phosphofluoric acid 0.1mol down, dripped off in 30 minutes, and continued stirring reaction 2 hours at 60 ℃, heating, vacuum removes and anhydrates, promptly obtain N, N-dimethyl hexanamide hexafluorophosphate solid product, fusing point (m.p): 87～89 ℃, productive rate 99%.
1H-NMR(300MHz，D
2O)：δ，ppm：0.96(m，3H)，1.67(m，2H)，2.43(m，2H)，2.90(s，6H)，7.01(s，1H).
MS(ESI)：m/z＝144.2(M
+).
Embodiment 12
Take by weighing N, N-dimethyl hexanamide 14.3 grams (0.1mol), 60 ℃ of stirrings slowly drip the solution of phosphoric acid 0.1mol down, dripped off in 30 minutes, and continued stirring reaction 2 hours at 80 ℃, heating, vacuum removes and anhydrates, promptly obtain N, N-dimethyl hexanamide dihydrogen phosphate solid product, fusing point (m.p): 72～74 ℃, productive rate 100%.
1H-NMR(300MHz，D
2O)：δ，ppm：0.96(m，3H)，1.29-1.33(m，4H)，1.62(m，2H)，2.00(s，2H)，2.40(m，2H)，2.90(s，6H)，7.00(s，1H).
MS(ESI)：m/z＝144.2(M
+).
Embodiment 13
Take by weighing N-methyl succimide 11.3 grams (0.1mol), 20 ℃ of stirrings slowly drip 36% hydrochloric acid 0.1mol down, dripped off in 30 minutes, continued stirring reaction 2 hours at 100 ℃, heating, vacuum removes and anhydrates, promptly obtain N-methyl succimide hydrochloride solid product, fusing point (m.p): 91～93 ℃, productive rate 99%.
1H-NMR(300MHz，D
2O)：δ，ppm：2.73(m，4H)，2.86(m，3H)，7.06(s，1H).
MS(ESI)：m/z＝114.1(M
+).
Embodiment 14
Take by weighing N-ethyl succimide 12.7 grams (0.1mol), 40 ℃ of stirrings slowly drip the toluene solution 30mL of trifluoromethanesulfonic acid 15.0 grams (0.1mol) down, dripped off in 30 minutes, continued stirring reaction 2 hours at 60 ℃, heating, vacuum is removed toluene, promptly obtain N-hexyl succimide fluoroform sulphonate solid product, fusing point (m.p): 57～58 ℃, productive rate 99%.
1H-NMR(300MHz，D
2O)：δ，ppm：1.61(t，3H)，2.73(m，4H)，2.84(s，3H)，3.37(m，2H)，7.00(s，1H).
MS(ESI)：m/z＝128.1(M
+).
Embodiment 15
Take by weighing N-methyl maleimide 11.1 grams (0.1mol), 20 ℃ of stirrings slowly drip the solution of lactic acid 0.1mol down, dripped off in 30 minutes, continued stirring reaction 2 hours at 50 ℃, heating, vacuum removes and anhydrates, and promptly obtains N, N-diethyl butyramide nitrate solid product, fusing point (m.p): 63～65 ℃, productive rate 100%.
1H-NMR(300MHz，D
2O)：δ，ppm：1.32(t，3H)，2.00(d，1H)，4.26(m，1H)，7.00(s，1H)，7.05(m，2H).
MS(ESI)：m/z＝112.1(M
+)
Embodiment 16
Take by weighing N-ethyl maleimide 12.5 grams (0.1mol), 60 ℃ of stirrings slowly drip the cyclohexane solution 30mL of phenylformic acid 12.2 grams (0.1mol) down, dripped off in 30 minutes, continued stirring reaction 2 hours at 100 ℃, heating, vacuum is removed hexanaphthene, promptly obtain N-ethyl maleimide benzoate solid product, fusing point (m.p): 114～115 ℃, productive rate 99%.
1H-NMR(300MHz，D
2O)：δ，ppm：1.60(m，3H)，3.74(m，2H)，7.04(m，1H)，7.10(s，2H)，7.45-7.60(m，3H)，7.81(m，2H).
MS(ESI)：m/z＝126.0(M
+).
Embodiment 17
Take by weighing benzamide 12.1 grams (0.1mol), 60 ℃ of stirrings slowly drip the cyclohexane solution 30mL of trifluoroacetic acid 11.4 grams (0.1mol) down, dripped off in 30 minutes, continued stirring reaction 2 hours at 60 ℃, heating, vacuum is removed hexanaphthene, promptly obtain benzamide trifluoroacetate solid product, fusing point (m.p): 86～87 ℃, productive rate 100%.
1H-NMR(300MHz，D
2O)：δ，ppm：7.00(s，3H)，7.45-7.60(m，3H)，7.81(s，2H).
MS(ESI)：m/z＝122.1(M
+).
Embodiment 18
Take by weighing N, N-diethylbenzene methane amide 15.0 grams (0.1mol), 60 ℃ of stirrings slowly drip the benzole soln 30mL of toluylic acid 13.61 grams (0.1mol) down, dripped off in 30 minutes, and continued stirring reaction 4 hours at 80 ℃, heating, vacuum is removed benzene, promptly obtain N, N-diethylbenzene formamide benzene acetate solid product, fusing point (m.p): 106～107 ℃, productive rate 99%.
1H-NMR(300MHz，D
2O)：δ，ppm：2.90(s，6H)，3.66(s，2H)，7.00(s，1H)，7.05-7.15(m，5H)，7.45-7.55(m，3H)，7.80(m，2H).
MS(ESI)：m/z＝122.1(M
+).
Embodiment 19
Restrain N-methyl succimide formate and 28.49 gram stearic acid and 7.49 gram propyl carbinols with 5 and put into reaction flask, stir, heating, controlled temperature is 80 ℃, reacts 4 hours, reaction solution leaves standstill, gravity settling is told the esterification products n-butyl stearate by separatory, through stratographic analysis, transformation efficiency 95%, selectivity are 100%.After dewatering, the catalyzer of lower floor recycles.
Embodiment 20
Restrain methane amide mesylates and 12.09 gram acetic acid and 33.2 gram lauryl alcohols with 7.4 and put into reaction flask, stir, controlled temperature is 10 ℃, reacts 6 hours, reaction solution leaves standstill, and gravity settling is told esterification products acetic acid lauryl by separatory, through stratographic analysis, transformation efficiency 96%, selectivity is 100%.After dewatering, the catalyzer of lower floor recycles.
Embodiment 21
Restrain N-methyl maleimide vitriol and 12.09 gram acetic acid and 8.82 gram primary isoamyl alcohol with 7.4 and put into reaction flask, stir, controlled temperature is 70 ℃, reacted 3 hours, reaction solution leaves standstill, gravity settling, tell the esterification products isoamyl acetate by separatory, through stratographic analysis, transformation efficiency 98%, selectivity is 100%.After dewatering, the catalyzer of lower floor recycles.
Embodiment 22
With 10 gram N, N-diethylformamide hydrobromate and 14.8 gram n Propanoic acids and 10.20 gram n-hexyl alcohols are put into reaction flask, stir, controlled temperature is 140 ℃, reacts 5 hours, reaction solution leaves standstill, gravity settling is told the just own ester of esterification products n Propanoic acid by separatory, through stratographic analysis, transformation efficiency 99%, selectivity are 100%.After dewatering, the catalyzer of lower floor recycles.
Embodiment 23
8 restrain oneself amidophosphoric acid salt and 14.8 gram n Propanoic acids and 26.9 gram isooctyl alcohol are put into reaction flask, stir, controlled temperature is 160 ℃, reacts 4 hours, reaction solution leaves standstill, and gravity settling is told the different monooctyl ester of esterification products n Propanoic acid by separatory, through stratographic analysis, transformation efficiency 97%, selectivity is 100%.After dewatering, the catalyzer of lower floor recycles.
Embodiment 24
With 6 gram N, N-amide dimethyl butyrate a tetrafluoro borate and 18.9 gram lactic acid and 11.62 gram iso-heptanols are put into reaction flask, stir heating, controlled temperature is 120 ℃, reacted 5 hours, reaction solution leaves standstill, gravity settling, tell esterification products lactic acid isocyanate by separatory, through stratographic analysis, transformation efficiency 97%, selectivity is 100%.After dewatering, the catalyzer of lower floor recycles.
Embodiment 25
Restrain ethanamide lactic acid salts and 22.49 gram Ba Dousuans and 7.9 gram methyl alcohol with 5 and insert in the reaction flask, stir, controlled temperature is 30 ℃, reacts 6 hours, reaction solution leaves standstill, and gravity settling is told the esterification products methyl crotonate by separatory, through stratographic analysis, transformation efficiency 97%, selectivity is 100%.After dewatering, the catalyzer of lower floor recycles.
Embodiment 26
Restraining N-ethyl succimide fluoroform sulphonates and 22.49 gram Ba Dousuans and 26 gram n-Octanols with 20 inserts in the reaction flask, stir, heating, controlled temperature is 100 ℃, reacts 8 hours, reaction solution leaves standstill, gravity settling is told esterification products Ba Dousuan n-octyl by separatory, through stratographic analysis, transformation efficiency 93%, selectivity are 100%.After dewatering, the catalyzer of lower floor recycles.
Embodiment 27
With 15 gram N, N-N,N-DIMETHYLACETAMIDE salt vitriol and 9.9 gram oxalic acid and 9.29 gram ethanol are put into reaction flask, stir heating, controlled temperature is 60 ℃, reacted 4 hours, reaction solution leaves standstill, gravity settling, tell the esterification products oxalic acid diethyl ester by separatory, through stratographic analysis, transformation efficiency 99%, selectivity is 100%.After dewatering, the catalyzer of lower floor recycles.
Embodiment 28
Restrain maleimide hexafluorophosphates and 11.81 gram Succinic Acid and 13.02 gram decyl alcohol with 15 and put into reaction flask, stir, heating, controlled temperature is 160 ℃, reacts 6 hours, reaction solution leaves standstill, gravity settling is told esterification products Succinic Acid didecyl ester by separatory, through stratographic analysis, transformation efficiency 90%, selectivity are 100%.After dewatering, the catalyzer of lower floor recycles.
Embodiment 29
With 12 gram N, N-diethylformamide hydrochloride and 20 gram lauric acid and 7.9 gram methyl alcohol are inserted in the reaction flask, stir heating, controlled temperature is 40 ℃, reacted 10 hours, reaction solution leaves standstill, gravity settling, tell the esterification products Laurate methyl by separatory, through stratographic analysis, transformation efficiency 93%, selectivity is 100%.After dewatering, the catalyzer of lower floor recycles.
Embodiment 30
Restrain N-methyl maleimide nitrate and 10.21 gram valeric acids and 6.6 gram Virahols with 11 and put into reaction flask, stir, controlled temperature is 50 ℃, reacted 6 hours, reaction solution leaves standstill, gravity settling, tell the esterification products isopropyl isovalerate by separatory, through stratographic analysis, transformation efficiency 96%, selectivity is 100%.After dewatering, the ionic liquid of lower floor recycles.
Embodiment 31
Restrain benzamide propionic salts and 22.84 gram palmitinic acids and 9.21 gram glycerol with 11 and put into reaction flask, stir, controlled temperature is 180 ℃, reacted 8 hours, reaction solution leaves standstill, gravity settling, tell esterification products palmitinic acid glycerol three esters by separatory, through stratographic analysis, transformation efficiency 92%, selectivity is 100%.After dewatering, the ionic liquid of lower floor recycles.
Embodiment 32
With 6 gram N, N-diethyl acetamide hydrobromate and 14.8 gram styracins and 11.62 gram enanthol are inserted in the reaction flask, stir heating, controlled temperature is 80 ℃, reacted 24 hours, reaction solution leaves standstill, gravity settling, tell the esterification products n-heptyl cinnamate by separatory, through stratographic analysis, transformation efficiency 96%, selectivity is 100%.After dewatering, the catalyzer of lower floor recycles.
Embodiment 33
Restraining ethanamide phosphoric acid salt and 14.8 gram styracins and 6.21 gram ethylene glycol with 12 inserts in the reaction flask, stir, heating, controlled temperature is 160 ℃, reacts 18 hours, reaction solution leaves standstill, gravity settling is told esterification products styracin ethylene glycol diester by separatory, through stratographic analysis, transformation efficiency 90%, selectivity are 100%.After dewatering, the catalyzer of lower floor recycles.
Embodiment 34
Restrain methane amide vitriol and 15.69 gram chloro-benzoic acids and 7.49 gram propyl carbinols with 18 and put into reaction flask, stir, heating, controlled temperature is 130 ℃, reacts 12 hours, reaction solution leaves standstill, gravity settling is told the positive butyl ester of esterification products m-chlorobenzoic acid, through stratographic analysis, transformation efficiency 91%, selectivity are 100%.After dewatering, the catalyzer of lower floor recycles.
Embodiment 35
With 16 gram N, N-dimethyl hexanamide hexafluorophosphate and 13.89 gram Whitfield's ointments and 7.41 gram isopropylcarbinols are put into reaction flask, stir heating, controlled temperature is 120 ℃, reacted 14 hours, reaction solution leaves standstill, gravity settling, tell the esterification products isonefolia, through stratographic analysis, transformation efficiency is 93%, and selectivity is 100%.After dewatering, the catalyzer of lower floor recycles.
Embodiment 36
Restrain N-ethyl succimide vitriol and 13.89 gram P-hydroxybenzoic acid and 10.21 gram isohexyl alcohols with 15 and put into reaction flask, stir, heating, controlled temperature is 140 ℃, reacts 12 hours, reaction solution leaves standstill, gravity settling is told the positive butyl ester of esterification products P-hydroxybenzoic acid, through stratographic analysis, transformation efficiency is 94%, and selectivity is 100%.After dewatering, the catalyzer of lower floor recycles.
Embodiment 37
Restrain N-methyl succimide phosphoric acid salt and 12.29 gram phenylformic acid and 3.2 gram methyl alcohol with 16 and put into reaction flask, stir, heating, controlled temperature is 50 ℃, reacts 6 hours, reaction solution leaves standstill, gravity settling is told the esterification products methyl benzoate, through stratographic analysis, transformation efficiency is 97%, and selectivity is 100%.After dewatering, the ionic liquid of lower floor recycles.
Embodiment 38
Restrain maleimide chloracetates and 12.29 gram phenylformic acid and 13.9 gram isooctyl alcohol with 12 and put into reaction flask, stir, heating, controlled temperature is 150 ℃, reacts 5 hours, reaction solution leaves standstill, gravity settling is told the different monooctyl ester of esterification products phenylformic acid, through stratographic analysis, transformation efficiency is 90%, and selectivity is 100%.After dewatering, the ionic liquid of lower floor recycles.
Embodiment 39
Restrain N-ethyl maleimide benzoates and 12.29 gram phenylformic acid and 18.63 gram lauryl alcohols with 27 and put into reaction flask, stir, heating, controlled temperature is 180 ℃, reacts 20 hours, reaction solution leaves standstill, gravity settling is told the different monooctyl ester of esterification products phenylformic acid, through stratographic analysis, transformation efficiency is 90%, and selectivity is 100%.After dewatering, the ionic liquid of lower floor recycles.
Claims (10)
1, phosphinylidyne-containing amine group
Acidic cpd, its chemical structural formula is:
R wherein
1For H or contain the alkyl or phenyl of 1～6 carbon atom; R
2For H or contain the alkyl of 1～2 carbon atom; R
3For H or contain the alkyl of 1～2 carbon atom, X
-Representative
The anionic group of acid HX.
2, compound as claimed in claim 1 is characterized in that: R
1Be selected from hydrogen, methyl, ethyl, propyl group, butyl, amyl group or hexyl; R
2, R
3Independently be selected from hydrogen, methyl or ethyl.
3, compound as claimed in claim 1 or 2 is characterized in that: negatively charged ion X
-Be selected from BF
4 -, PF
6 -, HCOO
-, CH
3COO
-, ClCH
2COO
-, CF
3COO
-, CH
3CH
2COO
-, Cl
-, Br
-, I
-, CH
3SO
3 -, CF
3SO
3 -, NO
3 -, SO
4 2-, HSO
4 -, H
2PO
4 -, HPO
4 2-, PO
4 3-, CH
3CHOHCOO
-, C
6H
5COO
-, C
6H
4OHCOO
-, C
6H
5CH
2COO
-In a kind of.
4, claim 1 described phosphinylidyne-containing amine group
The preparation method of acidic cpd is characterized in that: amide compound with
Acid process neutralization reaction under 0～100 ℃ makes phosphinylidyne-containing amine group
Acidic cpd, wherein amide compound is
R in the formula
1For H or contain the alkyl or phenyl of 1～6 carbon atom; R
2For H or contain the alkyl of 1～2 carbon atom; R
3For H or contain the alkyl of 1～2 carbon atom.
5, preparation method as claimed in claim 4 is characterized in that: amide compound with
The mol ratio of acid is between 3:1 and the 1:3.
6, as claim 4 or 5 described preparation methods, it is characterized in that: described neutralization reaction is carried out in the presence of reaction medium, and reaction medium is selected from benzene, toluene, hexanaphthene or water.
7, claim 1 or 2 described phosphinylidyne-containing amine groups
Acidic cpd is as the application of catalyzer in esterification of esterification.
8, according to the described application of claim 7, it is characterized in that: adopt phosphinylidyne-containing amine group as claimed in claim 1 or 2
Acidic cpd is as the catalyzer and the reaction medium of esterification, put into reaction vessel with aliphatic or aromatic acid and straight chain alcohol or branched-chain alcoho, under agitation, be heated to 10～180 ℃ of reactions 2～24 hours, reaction finishes and leaves standstill, gravity settling is told catalyst layer and product ester layer, obtains esterification products; Described lipid acid is acetate, propionic acid, butyric acid, valeric acid, oxalic acid, Ba Dousuan, lactic acid, propanedioic acid, Succinic Acid, lauric acid, palmitinic acid, oleic acid or stearic acid; Aromatic acid is phenylformic acid, P-hydroxybenzoic acid, Whitfield's ointment, chloro-benzoic acid or styracin; Straight chain alcohol or branched-chain alcoho are methyl alcohol, ethanol, ethylene glycol, propyl alcohol, Virahol, glycerol, butanols, isopropylcarbinol, amylalcohol, primary isoamyl alcohol, hexanol, isohexyl alcohol, enanthol, iso-heptanol, octanol, isooctyl alcohol, decyl alcohol or lauryl alcohol.
9, as claim 7 or 8 described application, it is characterized in that: phosphinylidyne-containing amine group
The consumption mol ratio of acidic cpd and aliphatic or aromatic acid and straight chain alcohol or branched-chain alcoho is 0.1～1:2～5:2～6; Described temperature of reaction is 10～180 ℃, reacts 2～24 hours.
10, as claim 7 or 8 described application, it is characterized in that: catalyst layer by dehydration, and is reusable.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102698802A (en) * | 2012-05-28 | 2012-10-03 | 江南大学 | Organic heteropoly hybrid catalyst for esterification reaction and preparation method thereof |
| CN102952058A (en) * | 2011-08-30 | 2013-03-06 | 海洋王照明科技股份有限公司 | Maleimide ionic liquid, and preparation method and application thereof |
| CN110981721A (en) * | 2019-12-25 | 2020-04-10 | 浙江建业化工股份有限公司 | Method for continuously producing n-propyl acetate |
| CN111302936A (en) * | 2020-03-31 | 2020-06-19 | 辽宁石化职业技术学院 | Preparation method of dibutyl phthalate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100398517C (en) * | 2005-06-17 | 2008-07-02 | 广东工业大学 | substituted pyrrolidone synthesized ion liquid and its synthesis method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952058A (en) * | 2011-08-30 | 2013-03-06 | 海洋王照明科技股份有限公司 | Maleimide ionic liquid, and preparation method and application thereof |
| CN102952058B (en) * | 2011-08-30 | 2015-05-06 | 海洋王照明科技股份有限公司 | Maleimide ionic liquid, and preparation method and application thereof |
| CN102698802A (en) * | 2012-05-28 | 2012-10-03 | 江南大学 | Organic heteropoly hybrid catalyst for esterification reaction and preparation method thereof |
| CN110981721A (en) * | 2019-12-25 | 2020-04-10 | 浙江建业化工股份有限公司 | Method for continuously producing n-propyl acetate |
| CN111302936A (en) * | 2020-03-31 | 2020-06-19 | 辽宁石化职业技术学院 | Preparation method of dibutyl phthalate |
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