CN101429135B - 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 PDF

Info

Publication number
CN101429135B
CN101429135B CN 200810236684 CN200810236684A CN101429135B CN 101429135 B CN101429135 B CN 101429135B CN 200810236684 CN200810236684 CN 200810236684 CN 200810236684 A CN200810236684 A CN 200810236684A CN 101429135 B CN101429135 B CN 101429135B
Authority
CN
China
Prior art keywords
acid
alcohol
reaction
phosphinylidyne
esterification
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN 200810236684
Other languages
Chinese (zh)
Other versions
CN101429135A (en
Inventor
周晓海
徐飞
张海波
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuhan University WHU
Original Assignee
Wuhan University WHU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wuhan University WHU filed Critical Wuhan University WHU
Priority to CN 200810236684 priority Critical patent/CN101429135B/en
Publication of CN101429135A publication Critical patent/CN101429135A/en
Application granted granted Critical
Publication of CN101429135B publication Critical patent/CN101429135B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention provides an 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 acidic HX. A synthesis method comprises a step of preparing the acidic chemical compound containing amide groups from an amide chemical compound and acid through neutralization reaction at a temperature between 0 and 100 DEG C. the synthesis method is simple and low in cost. The 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

Br*nsted acidic cpd of phosphinylidyne-containing amine group and its preparation method and application
Technical field
The present invention relates to phosphinylidyne-containing amine group
Figure G200810236684XD00012
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, greatly promoted the flourish of ester industry.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 remaining spent acid all can cause environmental pollution after the reaction.
The method of tradition synthesizing ester is as raw material take carboxylic acid or acid anhydrides and alcohols, this is a balanced reaction, if react with equimolar raw material, after reaching balance, only have 2/3 mole Carboxylic acid and alcohol to be converted into ester, in order to improve the transformation efficiency of ester, usually adopt excessive carboxylic acid or alcohol, 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 technique is the production technique of at present domestic extensive employing, although take cheap as catalyzer has, the active advantages of higher of the vitriol oil, 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, such 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 strong 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 it is 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, 40 ℃ of lower reactions of mole such as ester acid and methyl alcohol can't reach balance in 49 days.
In order to improve the speed of esterification, people have been developed multiple catalysis technique, comprise physical catalyze, biocatalysis and chemical process catalysis etc.Comparatively speaking, chemical catalyst is still the Main Means of esterification catalytic.And the 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, the problem such as these catalyzer can bring also that side reaction is many, etching apparatus, waste discharge pollute, the scientific worker is seeking new efficient catalyzer to replace these inorganic acid catalysts always both at home and abroad, has in succession developed strong-acid ion exchange resin, zeolite molecular sieve, Lewis acid, solid heteropoly acid and super acids etc.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
Figure G200810236684XD00021
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 again reaction medium, can also as spe medium, have broad application prospects simultaneously.
Summary of the invention
The object of the present invention is to provide a class phosphinylidyne-containing amine group
Figure G200810236684XD00022
Acidic cpd and its preparation method and application, the gained compound can make the transformation efficiency of esterification as the catalyzer of esterification and selectivity is high, technique is simple, and environmentally friendly.
The present invention is by this technical problem of following solution: phosphinylidyne-containing amine group
Figure G200810236684XD00023
Acidic cpd, its chemical structural formula is:
Figure G200810236684XD00024
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
Figure G200810236684XD00025
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
Figure G200810236684XD00031
The preparation method of acidic cpd: reaction medium or do not have reaction medium in the presence of, amide compound with
Figure G200810236684XD00032
Acid process neutralization reaction under 0~100 ℃ makes phosphinylidyne-containing amine group
Figure G200810236684XD00033
Acidic cpd, wherein amide compound is
Figure G200810236684XD00034
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
Figure G200810236684XD00035
The mol ratio of acid is between 3: 1 and 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
Figure G200810236684XD00036
Acidic cpd is as the application of catalyzer in esterification of esterification.
Employing formula (I) phosphinylidyne-containing amine group
Figure G200810236684XD00037
Acidic cpd is as 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, react complete leaving 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 acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, β-crotonic acid, 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:
Figure G200810236684XD00038
Above-mentioned phosphinylidyne-containing amine group
Figure G200810236684XD00039
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 parts; 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. Direct 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, alpha hydroxy 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, slowly drip methanesulfonic 9.6 grams (0.1mol) under 4 ℃ of stirrings, dripped off in 30 minutes, continued stirring reaction 4 hours at 4 ℃, heating, vacuum obtains white solid except benzene, 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), slowly drip sulfuric acid 19.2 grams (0.2mol) under 0 ℃ of stirring, dripped off in 3 hours, at room temperature continued stirring reaction 5 hours, namely 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), slowly drip the aqueous solution that phosphatase 79 .8 restrains (0.1mol) under 20 ℃ of stirrings, dripped off in 30 minutes, continued stirring reaction 2 hours at 40 ℃, heating, vacuum namely obtains hexanamide dihydrogen phosphate product except anhydrating, and 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), slowly drip hydroiodic acid HI 0.1mol under 20 ℃ of stirrings, dripped off in 30 minutes, continued stirring reaction 2 hours at 50 ℃, heating, vacuum is except anhydrating, namely obtain 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), slowly drip Mono Chloro Acetic Acid 0.1mol under 50 ℃ of stirrings, dripped off in 30 minutes, continued stirring reaction 2 hours at 50 ℃, namely obtain maleimide chloracetate solid product, fusing point (m.p): 53~56 ℃, 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, dinethylformamide 7.4 grams (0.1mol), slowly drip the aqueous solution that formic acid 4.6 restrains (0.1mol) under 30 ℃ of stirrings, dripped off in 30 minutes, continued stirring reactions 2 hours at 40 ℃, heating, vacuum is except anhydrating, namely obtain DMF formate product, be 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), the slow benzole soln that drips phenol formic acid 0.1mol under 70 ℃ of stirrings, dripped off in 30 minutes, and continued stirring reaction 2 hours at 70 ℃, heating, vacuum is removed benzene, namely 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), slowly drip the benzole soln 30mL that acetic acid 6.0 restrains (0.1mol) under 70 ℃ of stirrings, dripped off in 30 minutes, continued stirring reactions 2 hours at 100 ℃, heating, vacuum is removed benzene, namely obtain N,N-dimethylacetamide acetate product, be 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), the slow aqueous solution that drips fluoroboric acid 0.1mol under 20 ℃ of stirrings, dripped off in 30 minutes, and continued stirring reaction 2 hours at 80 ℃, heating, vacuum is except anhydrating, namely 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), the slow aqueous solution that drips nitric acid 0.1mol under 20 ℃ of stirrings, dripped off in 30 minutes, and continued stirring reaction 2 hours at 90 ℃, heating, vacuum is except anhydrating, namely 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), the slow aqueous solution that drips phosphofluoric acid 0.1mol under 20 ℃ of stirrings, dripped off in 30 minutes, and continued stirring reaction 2 hours at 60 ℃, heating, vacuum is except anhydrating, namely 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), the slow solution that drips phosphoric acid 0.1mol under 60 ℃ of stirrings, dripped off in 30 minutes, and continued stirring reaction 2 hours at 80 ℃, heating, vacuum is except anhydrating, namely 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), slowly drip 36% hydrochloric acid 0.1mol under 20 ℃ of stirrings, dripped off in 30 minutes, continued stirring reaction 2 hours at 100 ℃, heating, vacuum is except anhydrating, namely 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), slowly drip the toluene solution 30mL that trifluoromethanesulfonic acid 15.0 restrains (0.1mol) under 40 ℃ of stirrings, dripped off in 30 minutes, continued stirring reaction 2 hours at 60 ℃, heating, vacuum is removed toluene, namely 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), the slow solution that drips lactic acid 0.1mol under 20 ℃ of stirrings, dripped off in 30 minutes, continued stirring reaction 2 hours at 50 ℃, heating, vacuum namely obtains N, N-diethyl butyramide nitrate solid product except anhydrating, 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 NEM 12.5 grams (0.1mol), slowly drip the cyclohexane solution 30mL that phenylformic acid 12.2 restrains (0.1mol) under 60 ℃ of stirrings, dripped off in 30 minutes, continued stirring reaction 2 hours at 100 ℃, heating, vacuum is removed hexanaphthene, namely obtain NEM 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), slowly drip the cyclohexane solution 30mL that trifluoroacetic acid 11.4 restrains (0.1mol) under 60 ℃ of stirrings, dripped off in 30 minutes, continued stirring reaction 2 hours at 60 ℃, heating, vacuum is removed hexanaphthene, namely 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), slowly drip the benzole soln 30mL that toluylic acid 13.61 restrains (0.1mol) under 60 ℃ of stirrings, dripped off in 30 minutes, and continued stirring reaction 4 hours at 80 ℃, heating, vacuum is removed benzene, namely 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, the control 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, the control 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, the control 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, the control 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, the control 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, the control 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 β-crotonic acids and 7.9 gram methyl alcohol with 5 and insert in the reaction flask, stir, the control 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 β-crotonic acids and 26 gram n-Octanols with 20 inserts in the reaction flask, stir, heating, the control temperature is 100 ℃, reacts 8 hours, reaction solution leaves standstill, gravity settling is told esterification products β-crotonic acid 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, the control 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, the control 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, the control 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, the control 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, the control 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, the control 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, the control 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, the control 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, the control 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, the control 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, the control 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, the control 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 NEM benzoates and 12.29 gram phenylformic acid and 18.63 gram lauryl alcohols with 27 and put into reaction flask, stir, heating, the control 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 (8)

1. phosphinylidyne-containing amine group
Figure FSB00000933845600011
Acidic cpd, its chemical structural formula is:
Figure FSB00000933845600012
R wherein 1Be selected from hydrogen, methyl, ethyl, propyl group, butyl, amyl group or hexyl; R 2Be selected from hydrogen, methyl or ethyl; X -Representative The anionic group of acid HX, described
Figure FSB00000933845600014
The anionic group X of acid HX -Be selected from BF 4 -, PF 6 -, HCOO -, ClCH 2COO -, CF 3COO -, CH 3CH 2COO -, Cl -, Br -, I -, CH 3SO 3 -, CF 3SO 3 -, HSO 4 -, H 2PO 4 -, CH 3CHOHCOO -, C 6H 5COO -, C 6H 4OHCOO -, C 6H 5CH 2COO -In a kind of.
2. claim 1 described phosphinylidyne-containing amine group
Figure FSB00000933845600015
The preparation method of acidic cpd is characterized in that: amide compound with
Figure FSB00000933845600016
Acid HX process neutralization reaction under 0~100 ℃ makes phosphinylidyne-containing amine group
Figure FSB00000933845600017
Acidic cpd, wherein amide compound is
Figure FSB00000933845600018
R in the formula 1Be selected from hydrogen, methyl, ethyl, propyl group, butyl, amyl group or hexyl; R 2Be selected from hydrogen, methyl or ethyl.
3. preparation method as claimed in claim 2 is characterized in that: amide compound with
Figure FSB00000933845600019
The mol ratio of acid HX is between 3: 1 and 1: 3.
4. preparation method as claimed in claim 2 or claim 3, 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.
5. claim 1 or 2 described phosphinylidyne-containing amine groups
Figure FSB000009338456000110
Acidic cpd is as the application of catalyzer in esterification of esterification.
6. according to claim 5 described application is characterized in that: claim 1 or 2 described phosphinylidyne-containing amine groups
Figure FSB000009338456000111
Acidic cpd is as 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, react complete leaving standstill, gravity settling is told catalyst layer and product ester layer, obtains esterification products; Described lipid acid is acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, β-crotonic acid, 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.
7. application as claimed in claim 6 is characterized in that: phosphinylidyne-containing amine group
Figure FSB00000933845600021
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.
8. application as claimed in claim 6 is characterized in that: catalyst layer is reused by dehydration.
CN 200810236684 2008-12-05 2008-12-05 Br<Phi>nsted acid compound containing amide group, preparation and uses thereof Expired - Fee Related CN101429135B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 200810236684 CN101429135B (en) 2008-12-05 2008-12-05 Br<Phi>nsted acid compound containing amide group, preparation and uses thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 200810236684 CN101429135B (en) 2008-12-05 2008-12-05 Br<Phi>nsted acid compound containing amide group, preparation and uses thereof

Related Child Applications (1)

Application Number Title Priority Date Filing Date
CN201210344602XA Division CN102898344A (en) 2008-12-05 2008-12-05 Br[phi]nsted acidic compound containing amide groups, and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN101429135A CN101429135A (en) 2009-05-13
CN101429135B true CN101429135B (en) 2013-03-20

Family

ID=40644804

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 200810236684 Expired - Fee Related CN101429135B (en) 2008-12-05 2008-12-05 Br<Phi>nsted acid compound containing amide group, preparation and uses thereof

Country Status (1)

Country Link
CN (1) CN101429135B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1880303A (en) * 2005-06-17 2006-12-20 广东工业大学 substituted pyrrolidone synthesized ion liquid and its synthesis method

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1880303A (en) * 2005-06-17 2006-12-20 广东工业大学 substituted pyrrolidone synthesized ion liquid and its synthesis method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JINFANG HUANG ET AL..BRONSTED ACIDIC ROOM TEMPERATURE IONIC LIGUIDS DERIVED FROM N,N-DIMETHYLFORMAMIDE AND SIMILAR PROTOPHILIC AMIDES.《GREEN CHEMISTRY》.2006,(第8期), *
JINFANGHUANGETAL..BRONSTEDACIDICROOMTEMPERATUREIONICLIGUIDSDERIVEDFROMN N-DIMETHYLFORMAMIDE AND SIMILAR PROTOPHILIC AMIDES.《GREEN CHEMISTRY》.2006

Also Published As

Publication number Publication date
CN101429135A (en) 2009-05-13

Similar Documents

Publication Publication Date Title
CN100503043C (en) Ion liquid catalyst of esterification reaction, preparation method and usage
Zhang et al. Task-specific ionic liquids as absorbents and catalysts for efficient capture and conversion of H2S into value-added mercaptan acids
CN101863855B (en) Preparation of temperature sensitive acidic ionic liquid and method of using the same in catalyzing alcoholic acid esterification
TWI385150B (en) Branched carboxylic acid diesters
CN101429135B (en) Br&lt;Phi&gt;nsted acid compound containing amide group, preparation and uses thereof
CN105461654B (en) A kind of benzothiazole ionic liquid and its preparation method and application
Zieba et al. Transesterification of triglycerides with methanol catalyzed by heterogeneous zinc hydroxy nitrate catalyst. Evaluation of variables affecting the activity and stability of catalyst.
Mohammadbagheri et al. KCC-1/Pr-SO3H as an efficient heterogeneous catalyst for production of n-butyl levulinate from furfuryl alcohol
Zięba et al. Activity and stability of polyaniline-sulfate-based solid acid catalysts for the transesterification of triglycerides and esterification of fatty acids with methanol
CN106674005A (en) Method for preparing advanced fatty acid ester by using catalysis of solid-supported ionic liquid catalyst
CN102824929B (en) Preparation method of dioctyl terephthalate and used catalyst
CN113603580B (en) Method for synthesizing methacrylic acid by decarboxylation of itaconic acid
CN101024612B (en) Method for catalyzing alcohol acid esterization by acidic ion liquid
CN102898344A (en) Br[phi]nsted acidic compound containing amide groups, and preparation method and application thereof
CN105732694B (en) A kind of method that absorption purifies 1,1,1,3,5,5,5- heptamethyltrisiloxane
CN103387495A (en) Method for the continuous production of carboxylic acid esters
CN109402640B (en) Corrosion inhibitor and preparation method thereof
CN103910656B (en) Functionalized acidic ionic liquid and preparation thereof and the application in ethyl lactate synthesizes
CN104326989A (en) Preparation method of 2-methyl-4-amino-5-(aminomethyl) pyrimidine
CN104284880A (en) Hydroxyalkyl (meth)acrylate and method for producing same
NL2009377C2 (en) Ester formation.
CN103214423B (en) A kind of preparation method of acrylic ester compound
CN103435487A (en) Preparation method of phthalic acid esters
CN104311482B (en) Preparation method of 8-hydroxyquinoline temperature sensitive ionic liquid, and method for catalyzing long-chain fatty acid esterification by using ionic liquid
CN112239405B (en) Synthesis method of 2, 6-dimethyl naphthalene dicarboxylate

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20130320

Termination date: 20161205

CF01 Termination of patent right due to non-payment of annual fee