CN103450002A - Synthesis method of symmetrical anhydride - Google Patents
Synthesis method of symmetrical anhydride Download PDFInfo
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- CN103450002A CN103450002A CN2013103200039A CN201310320003A CN103450002A CN 103450002 A CN103450002 A CN 103450002A CN 2013103200039 A CN2013103200039 A CN 2013103200039A CN 201310320003 A CN201310320003 A CN 201310320003A CN 103450002 A CN103450002 A CN 103450002A
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- anhydride
- symmetric anhydride
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- symmetrical anhydride
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Abstract
The invention relates to a synthesis method of symmetrical anhydride, belonging to the field of organic synthesis. The method comprises the following steps of: based on an aldehyde RCHO corresponding to the symmetrical anhydride as a raw material, under the catalytic action of Bu4NI and ferric salt, oxidizing the raw material by TBHP (tert-butyl hydroperoxide), and reacting at 50-80 DEG C for 20-35 hours in organic solvent to obtain the product. The method has mild reaction conditions, is easy to operate and has high yield. In comparison with the other existing synthesis approaches, the method is novel, catalyst dosage is low, the product is easy to purify, and waste gas discharge is avoided, so that the method is more environment-friendly, and is a synthesis method of symmetrical anhydride with better popularization and application foreground.
Description
Technical field
The present invention relates to a kind of synthetic method of symmetric anhydride, specifically adopt aldehyde to prepare the production method of symmetric anhydride as starting raw material, belong to the organic synthesis field.
Background technology
Acid anhydrides is applied very extensive in organic synthesis, pharmaceutically being used for the carboxylic acid derivative of synthetic high value, comprises and prepares acid amides, ester etc., and be applied in the middle of protein and peptide synthetic.The industrial chemical intermediates such as cellulose acetate, fuel, spices of also manufacturing with diacetyl oxide.Phthalic anhydride also is used to synthetic softening agent, vibrin, dyestuff etc.
Before the present invention provides, the synthetic method of existing acid anhydrides also has more report, normally uses acyl halide and carboxylic metallic salt (or under the condition of alkali existence with carboxylic acid) to react and obtains; Another kind of method be by carboxylic acid with the dehydration coupling agent as isocyanic ester, Ph
3the reactions such as P/ Trichloroacetonitrile, Tosyl chloride, thionyl chloride, phosgene, 1,3,5-triazines make.Yet these coupling reagents are too active, and great majority have severe toxicity, and it is produced, transportation and use and all have larger potential safety hazard.In addition, in use often also can produce and be difficult to the waste gas of administering, as chlorine, sulfurous gas etc., three-waste pollution is serious.In addition, also there is in recent years the researchist to do further research to acid anhydrides synthetic, such as the achievement in research of Stephenson, suc as formula 1, with carboxylic acid, made the synthetic symmetrical acid anhydrides of raw material.This route main drawback is to have used as metal Ru as catalyzer, expensive, the application of this reaction is restricted, CBr
4, 2, the 6-lutidine has very high toxicity, and reaction needed carries out under blue light illumination, the operability more complicated is also high to the requirement of equipment, is not suitable for suitability for industrialized production.
The research of Xiao, suc as formula 2, be take iodo aromatic hydrocarbons as the synthetic symmetrical aryl acid anhydrides of raw material.The method has also been used the reagent such as precious metal palladium, DPPP, expensive, has limited the widespread use of this method, and in addition, reactive applications is to CO gas, and temperature of reaction is higher, and substrate also only limits to iodo aromatic hydrocarbons, is not suitable for large-scale industrial production.
The achievement in research of Alejandro, suc as formula 3, is made the synthetic acid anhydrides of raw material with acyl chlorides.The method need to consume the Metal Zn of equivalent, and discharges a large amount of inorganic villaumites, also is not suitable for being applied to industrialization.Therefore it is necessary developing a kind of method easy, that be easy to realize.
All the time, the scientific research personnel is devoted to develop new, more advanced, the preparation method of environmental protection more.
Summary of the invention
The synthetic method that the purpose of this invention is to provide more advanced, milder, safety and reliability, more environmental protection, reaction yield is high, cost is low, the three wastes are little a kind of symmetric anhydride.
The technical solution used in the present invention is as follows:
A kind of synthetic method of the symmetric anhydride be shown below, described method is: the aldehyde corresponding with symmetric anhydride (RCHO) of take is raw material, at Bu
4under the common katalysis of NI and molysite, by tertbutanol peroxide (TBHP) oxidation, in organic solvent, in 50-80 ℃ of reaction 20-35h.After reaction finishes, mixture can obtain the target molecule symmetric anhydride through later simple processing.Described raw material aldehyde: catalyst B u
4nI: catalyzer molysite: the amount of substance ratio that feeds intake of oxygenant tertbutanol peroxide is: 1:0.1:0.1:2.0.Reaction equation is as follows:
Direct-connected or the branched paraffin that wherein R is 2-10 carbon atom or be furans, phenyl ring, monosubstituted phenyl ring, the substituting group on phenyl ring can be for one of following: alkyl, alkoxyl group, ester group.
Organic solvent of the present invention can be selected from following any one: acetonitrile, chlorobenzene, ethyl acetate etc.
The consumption of described organic solvent is recommended as 3-6mL/g in the carboxylic acid quality.
Aftertreatment of the present invention can adopt following method: if symmetric anhydride is liquid under standard state, reaction mixture first under reduced pressure boils off solvent, then obtains symmetric anhydride with molecular distillation; If described symmetric anhydride is solid under standard state, reaction mixture first boils off solvent under normal pressure, and resistates obtains symmetric anhydride through recrystallization again, and recrystallization solvent commonly used is hexanaphthene.
The present invention is a kind of preparation method of synthetic symmetric anhydride, and its innovative technology is that employing TBHP is oxygenant, molysite and Bu
4nI is catalyzer, the reaction conditions gentleness, and easy to operate, yield is high.With existing other route of synthesis, compare, the method novelty, catalyst levels is few, and product is easy to purify, non-exhaust emission, more environmental protection, be a kind of preparation method with symmetric anhydride of better popularizing application prospect.
Specific implementation method
Below with specific examples, technical scheme of the present invention is described, but protection scope of the present invention is not limited to this:
Embodiment 1: propionic anhydride synthetic
Feed intake amount of substance than propionic aldehyde: Bu
4nI: molysite: oxygenant is: 1:0.1:0.1:2.0, catalyzer is Bu
4nI and molysite, oxygenant is tertbutanol peroxide, and organic solvent is ethyl acetate, and its consumption is 6 times of propionic aldehyde quality.
In thermometer, reflux condensing tube and churned mechanically 100mL there-necked flask are housed, add successively Bu under room temperature
4nI3.7g (0.01mol), molysite 1.3g (0.01mol), propionic aldehyde 5.8g (0.1mol), ethyl acetate 35mL and tertbutanol peroxide 18.0g (0.20mol).Finish, be warming up to 50 ℃, insulation reaction 25h, after reaction finishes, the pressure reducing and steaming solvent, then obtain propionic anhydride 5.7g in molecular distillation, product yield 88%, colorless oil.
IR(KBr,cm
-1)1786,1725;
1H?NMR(400MHz，CDCl
3)δ(ppm):1.18(t,J=3.6Hz,6H),2.50(q,J=6.8Hz,4H);
13C(100MHz,CDCl
3)δ(ppm):170.2,28.0,8.41;HRMS(ESI)calc.for(M+Na
+)153.14;found153.14.
Embodiment 2: benzoyl oxide synthetic
Feed intake amount of substance than propionic aldehyde: Bu
4nI: molysite: oxygenant is: 1:0.1:0.1:2.0, catalyzer is Bu
4nI and molysite, oxygenant is tertbutanol peroxide, and organic solvent is acetonitrile, and its consumption is 5 times of phenyl aldehyde quality.
In thermometer, reflux condensing tube and churned mechanically 100mL there-necked flask are housed, add successively Bu under room temperature
4nI3.7g (0.01mol), molysite 1.3g (0.01mol), phenyl aldehyde 10.6g (0.1mol), acetonitrile 53mL and tertbutanol peroxide 18.0g (0.20mol).Finish, be warming up to 80 ℃, insulation reaction 28h, after reaction finishes, the pressure reducing and steaming solvent, residue can obtain benzoyl oxide 10.3g with the hexanaphthene recrystallization, product yield 91%, solid.Fusing point: 42-44 ℃.
IR(KBr,cm
-1)3064,1788,1713,1609,1212,1167,1000;
1H?NMR(300MHz，CDCl
3)δ(ppm):8.16(d,J=8.5Hz,4H),7.68(t,7.5Hz,2H),7.49-7.44(m,4H);
13C(75MHz,CDCl
3)δ(ppm):162.4,134.5,128.8;HRMS(ESI)calc.for(M+Na
+)249.0522;found249.0520.
Embodiment 3: p-methylbenzoic acid acid anhydride synthetic
Feed intake amount of substance than propionic aldehyde: Bu
4nI: molysite: oxygenant is: 1:0.1:0.1:2.0, catalyzer is Bu
4nI and molysite, oxygenant is tertbutanol peroxide, and organic solvent is acetonitrile, and its consumption is 6 times of p-tolyl aldehyde quality.
In thermometer, reflux condensing tube and churned mechanically 100mL there-necked flask are housed, add successively Bu under room temperature
4nI3.7g (0.01mol), molysite 1.3g (0.01mol), p-tolyl aldehyde 12g (0.1mol), acetonitrile 72mL and tertbutanol peroxide 18.0g (0.20mol).Finish, be warming up to 80 ℃, insulation reaction 28h, after reaction finishes, the pressure reducing and steaming solvent, residue can obtain p-methylbenzoic acid acid anhydride 11.8g, product yield 93%, solid with the hexanaphthene recrystallization.Fusing point: 78-80 ℃.
IR(KBr,cm
-1)3010,1775,1717,1616,1229,1175,1943,1000;
1H?NMR(300MHz,CDCl
3)δ(ppm):8.04(d,J=7.8Hz,4H),7.32(d,J=7.8Hz,4H),2.46(s,6H);
13C?NMR(75MHz,CDCl
3)δ(ppm):162.6,145.5,130.6,129.6,126.3,21.8;HRMS(ESI)calc.for(M+Na
+)227.0835;found227.0836.
Embodiment 4: anisic acid acid anhydride synthetic
Feed intake amount of substance than propionic aldehyde: Bu
4nI: molysite: oxygenant is: 1:0.1:0.1:2.0, catalyzer is Bu
4nI and molysite, oxygenant is tertbutanol peroxide, and organic solvent is tetrahydrofuran (THF), and its consumption is 3.5 times of aubepine quality.
In thermometer, reflux condensing tube and churned mechanically 100mL there-necked flask are housed, add successively Bu under room temperature
4nI3.7g (0.01mol), molysite 1.3g (0.01mol), aubepine 13.6g (0.1mol), acetonitrile 48mL and tertbutanol peroxide 18.0g (0.20mol).Finish, be warming up to 50 ℃, insulation reaction 20h, after reaction finishes, the pressure reducing and steaming solvent, residue can obtain methoxyl group benzoic anhydride 13.2g, product yield 92%, off-white color solid with the hexanaphthene recrystallization.Fusing point: 88-93 ℃.
IR(KBr,cm
-1)3010,1790,2937,1720,1620,1300，1220,1180cm
-1;
1H?NMR(300MHz,CDCl
3)δ(ppm):8.10(d,J=7.4Hz,4H),6.98(d,J=7.4Hz,4H),3.90(s,6H);
13C(75MHz,CDCl
3)δ(ppm):164.9,162.3,132.8,121.3,114.2,55.6;HRMS(ESI)calc.for(M+Na
+)309.0739;found309.0733.
Embodiment 5: furans-2-carboxylic acid anhydride synthetic
Feed intake amount of substance than propionic aldehyde: Bu
4nI: molysite: oxygenant is: 1:0.1:0.1:2.0, catalyzer is Bu
4nI and molysite, oxygenant is tertbutanol peroxide, and organic solvent is DCM, and its consumption is 5 times of furfural quality.
In thermometer, reflux condensing tube and churned mechanically 100mL there-necked flask are housed, add successively Bu under room temperature
4nI3.7g (0.01mol), molysite 1.3g (0.01mol), furfural 9.6g (0.1mol), acetonitrile 48mL and tertbutanol peroxide 18.0g (0.20mol).Finish, be warming up to 50 ℃, insulation reaction 30h, after reaction finishes, the pressure reducing and steaming solvent, residue can obtain furans-2-carboxylic acid anhydride 8.8g, product yield 85%, solid with the hexanaphthene recrystallization.Fusing point: 71-72 ℃.
IR(KBr,cm
-1)3139,1776,1722,1563,1464,1388,1230,1158;
1H?NMR(300MHz，CDCl
3)δ(ppm):7.69(bs,2H),7.40(d,J=4Hz,2H),6.60(bs,2H);
13C(75MHz,CDCl
3)δ(ppm):153.1,148.9,143.1,122.1,112.9;HRMS(ESI)calc.for(M+Na
+)229.0107;found232.0108.
Synthesizing of embodiment 6:1-naphthalene acid anhydride
Feed intake amount of substance than propionic aldehyde: Bu4NI: molysite: oxygenant is: 1:0.1:0.1:2.0, catalyzer is Bu
4nI and molysite, oxygenant is tertbutanol peroxide, and organic solvent is acetonitrile, and its consumption is 5 times of 1-naphthaldehyde quality.
In thermometer, reflux condensing tube and churned mechanically 100mL there-necked flask are housed, add successively Bu under room temperature
4nI3.7g (0.01mol), molysite 1.3g (0.01mol), 1-naphthaldehyde 15.6g (0.1mol), acetonitrile 48mL and tertbutanol peroxide 18.0g (0.20mol).Finish, be warming up to 80 ℃, insulation reaction 35h, after reaction finishes, the pressure reducing and steaming solvent, residue can obtain 1-naphthalene acid anhydride 10.2g, product yield 91%, solid with the hexanaphthene recrystallization.Fusing point: 142-144 ℃.
IR(KBr,cm
-1):3054,1771,1705,1593,1225,1171,1054,958cm
-1;
1H?NMR(400MHz,CDCl
3)δ(ppm):9.1(d,J=8.6Hz,2H),8.4(d,J=4.5Hz,2H),8.1(d,J=8.1Hz,2H),7.9(d,J=7.9Hz,2H),7.5–7.7(m,6H);
13C?NMR(100MHz,CDCl
3)δ(ppm):162.9,135.5,134.0,132.1,128.8,129.3,127.2,126.8,126.2,125.2,124.9;HRMS(ESI)calc.for(M+Na
+)349.0841;found349.0838。
Claims (3)
1. the synthetic method of a symmetric anhydride, is characterized in that, the aldehyde RCHO corresponding with symmetric anhydride of take is raw material, at Bu
4under the common katalysis of NI and molysite, by the TBHP oxidation, in organic solvent, in 50-80 ℃ of reaction 20-35h, reaction equation is as follows:
Direct-connected or the branched paraffin that wherein R is 2-10 carbon atom or be furans, phenyl ring, monosubstituted phenyl ring, the substituting group on phenyl ring can be for one of following: alkyl, alkoxyl group, ester group.
2. the synthetic method of symmetric anhydride according to claim 1, is characterized in that its Raw aldehyde: catalyst B u
4nI: catalyzer molysite: the amount of substance ratio that feeds intake of oxygenant tertbutanol peroxide is: 1:0.1:0.1:2.0.
3. according to the synthetic method of claim 1 or 2 described symmetric anhydride, it is characterized in that, described organic solvent is acetonitrile, chlorobenzene or ethyl acetate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018189077A1 (en) | 2017-04-12 | 2018-10-18 | Bayer Aktiengesellschaft | Mesoionic imidazopyridines for use as insecticides |
| EP3636644A1 (en) | 2018-10-11 | 2020-04-15 | Bayer Aktiengesellschaft | Mesoionic imidazopyridines as insecticides |
| CN115322166A (en) * | 2021-05-10 | 2022-11-11 | 中国科学院大连化学物理研究所 | Method for synthesizing difurfuryl ether |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB545971A (en) * | 1939-12-27 | 1942-06-22 | British Celanese | Manufacture of aliphatic anhydrides |
| US4962206A (en) * | 1989-11-20 | 1990-10-09 | Occidental Chemical Corporation | Process for the preparation of 4-bromophthalic anhydride |
| CN1113655A (en) * | 1993-08-18 | 1995-12-20 | 大世吕化学工业株式会社 | Process for producing acetic anhydride alone or both of acetic anhydride and acetic acid |
| CN1517330A (en) * | 2003-01-16 | 2004-08-04 | 三菱瓦斯化学株式会社 | Method for preparing 1,2,4,5-benzene tetra-acid and 1,2,4,5-benzene tetra-anhydride |
-
2013
- 2013-07-26 CN CN2013103200039A patent/CN103450002A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB545971A (en) * | 1939-12-27 | 1942-06-22 | British Celanese | Manufacture of aliphatic anhydrides |
| US4962206A (en) * | 1989-11-20 | 1990-10-09 | Occidental Chemical Corporation | Process for the preparation of 4-bromophthalic anhydride |
| CN1113655A (en) * | 1993-08-18 | 1995-12-20 | 大世吕化学工业株式会社 | Process for producing acetic anhydride alone or both of acetic anhydride and acetic acid |
| CN1517330A (en) * | 2003-01-16 | 2004-08-04 | 三菱瓦斯化学株式会社 | Method for preparing 1,2,4,5-benzene tetra-acid and 1,2,4,5-benzene tetra-anhydride |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018189077A1 (en) | 2017-04-12 | 2018-10-18 | Bayer Aktiengesellschaft | Mesoionic imidazopyridines for use as insecticides |
| EP3636644A1 (en) | 2018-10-11 | 2020-04-15 | Bayer Aktiengesellschaft | Mesoionic imidazopyridines as insecticides |
| CN115322166A (en) * | 2021-05-10 | 2022-11-11 | 中国科学院大连化学物理研究所 | Method for synthesizing difurfuryl ether |
| CN115322166B (en) * | 2021-05-10 | 2024-01-30 | 中国科学院大连化学物理研究所 | Method for synthesizing difurfuryl ether |
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