CN101357884B - Method for preparing symmetrical acid anhydride - Google Patents
Method for preparing symmetrical acid anhydride Download PDFInfo
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- CN101357884B CN101357884B CN2008101209019A CN200810120901A CN101357884B CN 101357884 B CN101357884 B CN 101357884B CN 2008101209019 A CN2008101209019 A CN 2008101209019A CN 200810120901 A CN200810120901 A CN 200810120901A CN 101357884 B CN101357884 B CN 101357884B
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- symmetric anhydride
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Abstract
The invention discloses a preparation method for symmetric anhydride, which comprises the following steps: raw materials are corresponding carboxylic acid RCOOH and bis(trichloromethyl) carbonic ester, which react in organic solvent under the action of catalyst for 1 to 10h under the temperature of 40 to 100 DEG C. The reacted mixture is post-processed, and the symmetric anhydride indicated in formula (II) is obtained. The catalyst is tertiary amine with N-formyl group, and the molar ratio of the carboxylic acid, bis (trichloromethyl) carbonic ester and the catalyst is 1:0.17-0.19:0.005-0.1. The preparation method has the advantages of advanced technical route, mild reaction condition, high reaction yield, low three-waste, low catalyst consumption, and the like, and is the preparation method for symmetric anhydride with good popularization and application prospect.
Description
(1) technical field
The present invention relates to a kind of preparation method of symmetric anhydride.
(2) background technology
Acid anhydrides is a kind of important acylating reagent, uses very extensively in organic synthesis, common can be used for making chemical intermediates such as cellulose acetate, fuel and spices as the acetyl acid anhydride industrial.Phthalic anhydride then is widely used for synthetic dyestuff, vibrin, Synolac, softening agent, terylene etc.
Symmetric anhydride also is used for preparing asymmetric acid anhydrides usually.In addition, also in medication preparation the person of having use comparatively widely.
Before the present invention provides, existing acid anhydrides synthetic method mainly be corresponding carboxylic acid and dehydrated reagent such as P
2O
5, DCC, Ph
3P/COCl
2, effect such as sulfur oxychloride makes.More or less there is following shortcoming in aforesaid method: expensive raw material price, and reaction yield is low, and condition is relatively more violent, catalyzer is unstable, reaction reagent is severe toxicity and high malicious reagent is unfriendly to environment.Be the chemical weapons that United Nations stipulates as reagent such as sulfur oxychloride, five phosphorus oxide, phosgene, its production, transportation and use all exist bigger safety and environmental protection hidden danger, use also to be strictly controlled.Often produce waste gas such as the sulfurous gas that is difficult to administer in the use, three-waste pollution is serious.In addition, document prepares acid anhydrides with BTC also report, and adopting triethylamine in the document is acid-capture agent, mole such as required amount and reactant, and also reaction yield is low.Triethylamine forms triethylamine hydrochloride with the hydrogenchloride that reaction produces is difficult to separate the aftertreatment trouble with solid product.
(3) summary of the invention
It is simple that the technical problem to be solved in the present invention provides a kind of technology, the preparation method of a kind of symmetric anhydride that production safety is reliable, reaction yield is high, cost is low, the three wastes are little.
The technical solution used in the present invention is as follows:
A kind of preparation method suc as formula the symmetric anhydride shown in (II), described method is: is raw material with described symmetric anhydride corresponding carboxylic acid RCOOH with two (trichloromethyl) carbonic ethers, under catalyst action, in organic solvent, react 1～10h in 40～100 ℃, reaction mixture obtains described symmetric anhydride through aftertreatment, described catalyzer is the tertiary amine that contains N-formyl group, described carboxylic acid: two (trichloromethyl) carbonic ether: the amount of substance ratio that feeds intake of catalyzer is 1: 0.17～0.19: 0.005～0.1; Reaction equation is as follows:
Wherein R is the straight or branched alkane of 2-10 carbon atom or is phenyl ring, single-substituted ring, and it is one of following that the substituting group on the phenyl ring is selected from: halogen, nitro, alkyl, alkoxyl group.
Further, described catalyzer is preferred one of following: N-formyl-piperidines, N-formyl-morpholine, N, dinethylformamide, more preferably N, dinethylformamide.
Organic solvent of the present invention can be the mixture of following one or more arbitrary proportions: the halohydrocarbon of toluene, 2-methyltetrahydrofuran, ethyl acetate, C1～C4.The halohydrocarbon of described C1～C4 can be selected methylene dichloride, trichloromethane, ethylene dichloride etc.Described organic solvent is preferably the mixture of following one or both arbitrary proportions: toluene, ethyl acetate.
The consumption of described organic solvent is recommended as 0.5～5ml/g in the carboxylic acid quality, preferred 2～3ml/g.
Further, described carboxylic acid: two (trichloromethyl) carbonic ether: the amount of substance ratio that feeds intake of catalyzer is preferably 1:0.17-0.19:0.005～0.01.
Whether described reaction was preferably carried out under 60～90 ℃ 3～7 hours, specifically can according to also have hydrogenchloride to generate and judge reaction end.
Aftertreatment of the present invention can be adopted following method: if described symmetric anhydride is liquid under standard state, then reaction mixture elder generation normal pressure boils off solvent, and molecular distillation gets symmetric anhydride again; If described symmetric anhydride is solid under standard state, then reaction mixture elder generation normal pressure boils off solvent, and resistates gets symmetric anhydride through recrystallization, and recrystallization solvent commonly used has hexanaphthene.
The concrete preparation method of described symmetric anhydride that recommends carries out according to following steps: according to carboxylic acid RCOOH: two (trichloromethyl) carbonic ether: N, the amount of substance of dinethylformamide feeds intake than for 1:0.17-0.19:0.005～0.1, add organic solvent, consumption of organic solvent is 2～3 times of corresponding carboxylic acid quality, described organic solvent is toluene or ethyl acetate, being warming up to 60～90 ℃ reacted 3～7 hours down, after normal pressure boiled off solvent, resistates molecular distillation or resistates carried out recrystallization and get corresponding symmetric anhydride.
The present invention compared with prior art, its beneficial effect is embodied in:
(1) compares with original method, got rid of the use of materials such as hypertoxic high poison such as sulfur oxychloride, five phosphorus oxide, phosgene;
(2) avoided sulfur dioxide gas to atmospheric pollution or avoided phosphorus to pollute the oxygen enrichmentization of the environment that causes;
(3) the inventive method yield height not only, most of anhydride reaction yields 〉=90%, catalyst levels is few, only is that 0.5% of raw material carboxylic acid amount of substance gets final product;
To sum up, operational path advanced person of the present invention, the reaction conditions gentleness, the reaction yield height, advantage such as the three wastes are little, and catalyst levels is few is a kind of preparation method with symmetric anhydride of better popularizing application prospect.
(4) embodiment:
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Embodiment 1: the preparation of propionic anhydride
Feed intake amount of substance than carboxylic acid RCOOH: two (trichloromethyl) carbonic ether: catalyzer is 1:0.17:0.01, and RCOOH is a propionic acid, and catalyzer is N, and dinethylformamide, organic solvent are ethyl acetate, and its consumption is 3 times of carboxylic acid quality.
In thermometer, reflux condensing tube and churned mechanically 250mL there-necked flask are housed, add propionic acid 7.4g (100mmol), two (trichloromethyl) carbonic ether 5.0g (17mmol), ethyl acetate 22.2ml and N, dinethylformamide 0.07g (1mmol).Finish, be warming up to 60-65 ℃, insulation reaction 6h, after reaction finishes, the pressure reducing and steaming solvent, and then molecular distillation gets propionic anhydride 6.3g, product yield 97.0%, oily matter.
1H-NMR(400MHz，CDCl
3)：1.18(6H，t，J＝3.6Hz)，2.50(4H，q，J＝6.8Hz)；IR(KBr，cm
-1)：1786，1725；m/z(％)＝112(M+1，3)，73(8)，57(100)；
13C?NMR(100MHz，CDCl
3)：170.2，28.0，8.41.
Embodiment 2: the preparation of benzoyl oxide
Feed intake amount of substance than carboxylic acid RCOOH: two (trichloromethyl) carbonic ether: catalyzer is 1:0.17:0.005, and RCOOH is a phenylformic acid, and catalyzer is N, and dinethylformamide, organic solvent are toluene, and its consumption is 2 times of carboxylic acid quality.
In thermometer, reflux condensing tube and churned mechanically 250mL there-necked flask are housed, add phenylformic acid 12.2g (100mmol), two (trichloromethyl) carbonic ether 17g (17mmol), toluene 24.4ml and N, dinethylformamide 0.04g (0.5mmol).Finish, be warming up to 70-75 ℃, insulation reaction 5h, after reaction finishes, the pressure reducing and steaming solvent, resistates promptly obtains benzoyl oxide 11.0g with the hexanaphthene recrystallization, product yield 97.0%, solid.Fusing point: 43-44 ℃.
1H-NMR(400MHz，CDCl
3)：8.12(4H，d，J＝8.4Hz，ArH)，7.68-7.58(2H，m，ArH)，7.54-7.48(4H，m，ArH)IR(KBr，cm
-1)1785，1726。
Embodiment 3: the preparation of 0-chloro-benzoic acid acid anhydride
Replace phenylformic acid with 0-chloro-benzoic acid, reaction solvent is a methylene dichloride, and temperature of reaction is 40～45 ℃, and the reaction times is 10h, and operating process and embodiment 2 obtain the 0-chloro-benzoic acid acid anhydride, yield 94%, solid together.Fusing point: 79-81 ℃.
1H-NMR(400MHz，CDCl
3)：8.04(dd，2H，J＝2，16Hz)，7.54-7.48(4H，m)，7.42-7.26(2H，m)；IR(KBr，cm
-1)：1780，1718；MS(EI)：m/z(％)＝259(M+1，56)，141(39)，139(100)，113(17)，111(44)，75(18).
13C?NMR(100MHz，CDCl
3)：160.34，135.1，134.2，132.6，131.6，127.8，126.9.
Embodiment 4: the preparation of parabromobenzoic acid acid anhydride
Feed intake amount of substance than carboxylic acid RCOOH: two (trichloromethyl) carbonic ether: catalyzer is 1:0.17:0.1, and RCOOH is a parabromobenzoic acid, and catalyzer is N, and dinethylformamide, organic solvent are toluene, and its consumption is 3 times of carboxylic acid quality.
Temperature of reaction is 95～100 ℃, and the reaction times is 1h, and other is operated with embodiment 2, obtains the parabromobenzoic acid acid anhydride, product yield 95%, white solid.Fusing point: 222-224 ℃.
1H-NMR(400MHz，CDCl
3)：8.10(4H，d，J＝8.4Hz)，7.53(4H，d，J＝8.4Hz)；IR(KBr，cm
-1)：3098，1785，1721；m/z(％)＝384(M+，15)，386(M+2，6)，183(100)，155(22)，75(17)；
13C?NMR(100MHz，CDCl
3)：161.6，136.1，131.5，128.3，125.7.
Embodiment 5: the preparation of p-nitrobenzoic acid acid anhydride
Feed intake amount of substance than carboxylic acid RCOOH: two (trichloromethyl) carbonic ether: catalyzer is 1:0.17:0.05, RCOOH is a p-nitrobenzoic acid, charging capacity is 100mmol, catalyzer is N-formyl-morpholine, its consumption is 0.5g (5mmol), organic solvent is 1, and 2-ethylene dichloride, its consumption are 3 times of p-nitrobenzoic acid quality.
Temperature of reaction is 75～80 ℃, and other is operated with embodiment 3, obtains the p-nitrobenzoic acid acid anhydride, product yield 95.5%, yellow solid; Fusing point: 195-198 ℃.；
1H-NMR(400MHz，CDCl
3)：8.36(4H，d，J＝2.4Hz)，8.21(4H，d，J＝2.4Hz)；IR(KBr，cm
-1)：1684，1602；MS(EI)：m/z(％)＝316(M+1，3)，150(100)，104(29)，76(17).
13C?NMR(100MHz，CDCl
3)：165.7，150.0，136.3，130.6，123.8.
Embodiment 6: the preparation of anisic acid acid anhydride
Feed intake amount of substance than carboxylic acid RCOOH: two (trichloromethyl) carbonic ether: catalyzer is 1:0.17:0.08, RCOOH is 100mmol for the anisic acid charging capacity, catalyzer is N-formyl-piperidines, its consumption is 0.8g (8mmol), organic solvent is a chloroform, and its consumption is 2.5 times of p-nitrobenzoic acid quality.
Temperature of reaction is a reflux temperature, and other operation gets anisic acid acid anhydride, product yield 95%, off-white color solid point: 96-97 ℃ with embodiment 2.
1H-NMR(400MHz，CDCl
3)：8.11(4H，d，J＝8.0Hz，ArH)，7.82(4H，d，J＝8.0Hz，ArH)，3.84(6H，s，2×CH
3)IR(KBr，cm
-1)：1785，1711m/z(％)＝298(M+1，3)，105(94)，87(100)，77(20)；
13C?NMR(100MHz，CDCl
3)：187.4，124.5，125.2，120.3，105.4，56.2.
Embodiment 8: the preparation of lauric anhydride
Feed intake amount of substance than carboxylic acid RCOOH: two (trichloromethyl) carbonic ether: catalyzer is 1:0.17:0.1, and RCOOH is a lauric acid, and catalyzer is N, and dinethylformamide, organic solvent are ethyl acetate, and its consumption is 5 times of carboxylic acid quality.
Temperature of reaction is 60-65 ℃, and other is operated with embodiment 2, gets lauric anhydride, product yield 92.1%, off-white color solid fusing point: 41-41.5 ℃.
1H-NMR(400MHz，CDCl
3)：2.44(4H，t，CH
2，J＝1.4Hz)，1.70-1.62(4H，m，CH
2)，1.30-1.26(32H，m，CH
2)，0.88(6H，t，CH
3，J＝1.4Hz)；IR(KBr，cm
-1)：2924，1793，1711；MS(EI)：m/z(％)＝199(18)，183(100)，57(47).
13C?NMR(100MHz，CDCl
3)：169.6，35.4，32.1，29.7，29.5，29.3，28.9，24.4，22.8，14.1.
Embodiment 9: the preparation of trimethylacetic acid acid anhydride
Feed intake amount of substance than carboxylic acid RCOOH: two (trichloromethyl) carbonic ether: catalyzer is 1:0.17:0.1, and RCOOH is a trimethylacetic acid, and catalyzer is N, and dinethylformamide, organic solvent are the 2-methyltetrahydrofuran, and its consumption is 1 times of carboxylic acid quality.
Temperature of reaction is 40-45 ℃, and other is operated with embodiment 1, gets the trimethylacetic acid acid anhydride, product yield 90.1%, and oily matter,
1H-NMR (400MHz, CDCl
3): 1.266 (18H, S); IR (KBr, cm
-1): 1809,1741; MS (EI): m/z (%)=112 (11), 85 (79), and 57 (100);
13C NMR (100MHz, CDCl
3): 173.9,40.2,26.5.
Embodiment 10: the preparation of propionic anhydride
Feed intake amount of substance than carboxylic acid RCOOH: two (trichloromethyl) carbonic ether: catalyzer is 1:0.18:0.05, and RCOOH is a propionic acid, and catalyzer is N, and dinethylformamide, organic solvent are the 2-methyltetrahydrofuran, and its consumption is 1.5 times of carboxylic acid quality.
Temperature of reaction is a reflux temperature, and other is operated with embodiment 1, gets propionic anhydride, product yield 93.0%, oily matter.Physical data is with embodiment 1.
Embodiment 11: the preparation of propionic anhydride
Feed intake amount of substance than carboxylic acid RCOOH: two (trichloromethyl) carbonic ether: catalyzer is 1:0.17:0.1, and RCOOH is a propionic acid, and catalyzer is N, and dinethylformamide, organic solvent are toluene, and its consumption is 0.5 times of carboxylic acid quality.
Temperature of reaction is 85-90 ℃, and the reaction times is 3h, and other is operated with embodiment 1, gets propionic anhydride, product yield 91.0%, oily matter.Physical data is with embodiment 1.
Embodiment 12: the preparation of propionic anhydride
Feed intake amount of substance than carboxylic acid RCOOH: two (trichloromethyl) carbonic ether: catalyzer is 1:0.19:0.008, and RCOOH is a propionic acid, and catalyzer is N, and dinethylformamide, organic solvent are toluene, and its consumption is 1.5 times of carboxylic acid quality.
Temperature of reaction is 80-85 ℃, and the reaction times is 4h, and other is operated with embodiment 1, gets propionic anhydride, product yield 90.0%, oily matter.Physical data is with embodiment 1.
Claims (9)
1. preparation method suc as formula the symmetric anhydride shown in (II), it is characterized in that described method is: with described symmetric anhydride corresponding carboxylic acid RCOOH be raw material with two (trichloromethyl) carbonic ethers, under catalyst action, in organic solvent, react 1～10h in 40～100 ℃, reaction mixture obtains described symmetric anhydride through aftertreatment, described catalyzer is the tertiary amine that contains N-formyl group, described catalyzer is one of following: N-formyl-piperidines, N-formyl-morpholine, N, dinethylformamide, described carboxylic acid: two (trichloromethyl) carbonic ether: the amount of substance ratio that feeds intake of catalyzer is 1: 0.17～0.19: 0.005～0.1;
Wherein R is the straight or branched alkane of 2-10 carbon atom or is phenyl ring, single-substituted ring, and it is one of following that the substituting group on the phenyl ring is selected from: halogen, nitro, alkyl, alkoxyl group.
2. the preparation method of symmetric anhydride as claimed in claim 1 is characterized in that described organic solvent is the mixture of following one or more arbitrary proportions: the halohydrocarbon of toluene, 2-methyltetrahydrofuran, ethyl acetate, C1～C4.
3. the preparation method of symmetric anhydride as claimed in claim 2 is characterized in that the consumption of described organic solvent is counted 0.5～5ml/g with the carboxylic acid quality.
4. the preparation method of symmetric anhydride as claimed in claim 3, it is characterized in that described carboxylic acid: two (trichloromethyl) carbonic ether: the amount of substance ratio that feeds intake of catalyzer is 1: 0.17～0.19: 0.005～0.01.
5. the preparation method of symmetric anhydride as claimed in claim 1 is characterized in that described being reflected under 60～90 ℃ carry out, and the reaction times is 3～7 hours.
6. the preparation method of symmetric anhydride as claimed in claim 2 is characterized in that described organic solvent is the mixture of following one or both arbitrary proportions: toluene, ethyl acetate.
7. the preparation method of symmetric anhydride as claimed in claim 4 is characterized in that the consumption of described organic solvent is counted 2～3ml/g with the carboxylic acid quality.
8. the preparation method of symmetric anhydride as claimed in claim 1 is characterized in that described aftertreatment is: if described symmetric anhydride is liquid under standard state, then reaction mixture elder generation normal pressure boils off solvent, and residual solution molecular distillation again gets symmetric anhydride.
9. the preparation method of symmetric anhydride as claimed in claim 1 is characterized in that described aftertreatment is: if described symmetric anhydride is solid under standard state, then reaction mixture elder generation normal pressure boils off solvent, and resistates gets symmetric anhydride through recrystallization.
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| EP2447242A1 (en) | 2010-10-29 | 2012-05-02 | LANXESS Deutschland GmbH | Method for producing all-E sorbic acid anhydride |
| CN102070455B (en) * | 2010-12-25 | 2013-09-18 | 温州大学 | Chemical synthesis method for o-chlorobenzoic acid chloro butyl ester |
| EP2607346A1 (en) | 2011-12-21 | 2013-06-26 | Saltigo GmbH | Method for producing, stabilising and packing sorbic acid hydride |
| KR20200050946A (en) * | 2017-09-05 | 2020-05-12 | 가부시끼가이샤 도꾸야마 | Production method of protective L-carnosine derivative, L-carnosine, and crystalline L-carnosine zinc complex |
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| US5994545A (en) * | 1995-06-30 | 1999-11-30 | Ajinomoto Co., Inc. | Process for producing optically active amides |
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| US5994545A (en) * | 1995-06-30 | 1999-11-30 | Ajinomoto Co., Inc. | Process for producing optically active amides |
Non-Patent Citations (5)
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| Remigiusz Kocz et al.A Convenient Triphosgene-Mediated Synthesis of Symmetric Carboxylic Acid An hydrides.《J.Org.Chem.》.1994, * |
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