CN103787847B - A kind of take ionic liquid as the technique of solvent continuous production trimethyl orthoacetate - Google Patents
A kind of take ionic liquid as the technique of solvent continuous production trimethyl orthoacetate Download PDFInfo
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- CN103787847B CN103787847B CN201410047965.6A CN201410047965A CN103787847B CN 103787847 B CN103787847 B CN 103787847B CN 201410047965 A CN201410047965 A CN 201410047965A CN 103787847 B CN103787847 B CN 103787847B
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- C07—ORGANIC CHEMISTRY
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/60—Preparation of compounds having groups or groups
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- C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
- C07C257/04—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines without replacement of the other oxygen atom of the carboxyl group, e.g. imino-ethers
- C07C257/06—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines without replacement of the other oxygen atom of the carboxyl group, e.g. imino-ethers having carbon atoms of imino-carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms, or to carbon atoms of rings other than six-membered aromatic rings
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Abstract
One class hydrophobic ionic liquid prepares the method for trimethyl orthoacetate as solvent, it anhydrous acetonitrile, anhydrous methanol and solvent is sent in reactor to carry out low temperature cold to-5 DEG C, dry hydrogen chloride gas is passed in still, stirring reaction 6h afterwards, described solvent is a class hydrophobic ionic liquid, is conveyed into by mixed solution in the second reactor, adds pre-cold methanol at 5 DEG C and stir 0.5h, reaction system pH is regulated to be 5-6, at 40 DEG C of alcoholysis mixed solution 12h with ammonia; Alcoholysis liquid is cooled to 0 DEG C, by ammonia adjust ph to 8.0, afterwards alcoholysis liquid is conveyed into atmospheric distillation tower, collect 107 ~ 109 DEG C of cuts, obtain product trimethyl orthoacetate; Still liquid at the bottom of rectifying tower is sent in washing kettle and is washed, and lower floor's liquid is sent in drying kettle and dried, and the solvent after oven dry carries out recycle.Method of the present invention provides cost savings and reduces energy consumption, achieves the green production of trimethyl orthoacetate.
Description
Technical field
The present invention relates to a class hydrophobic ionic liquid prepares trimethyl orthoacetate method as solvent.
Background technology
Trimethyl orthoacetate (CAS:11445-45-0) is a kind of colourless transparent liquid, is soluble in the organic solvent such as alcohol, ether, except for except the synthesis of New Sweetening Agent Trichlocromethyl Sucrose, is widely used in the chemical such as medicine, agricultural chemicals, spices.Trimethyl orthoacetate synthetic method bibliographical information both domestic and external is few, mainly contains sodium Metal 99.5 method and acetonitrile method, and wherein with acetonitrile method report at most, this method raw material is easy to get, is widely used.
According to relevant report, generally low boiling point solvent is used in industrial production, as anhydrous diethyl ether, sherwood oil, chloroform, tetracol phenixin, benzene, toluene, (the PeterP.T.Sah such as ethanol, J.Am.Chem.Soc., 1928, 50:516, S.M.McElvain, J.Am.Chem.Soc., 1942, 64:1825, analogy reason moral, In Jiangxi Science, 2005, 23 (6): 744, Yu Mingxing, agricultural chemicals, 1991, 30 (5): 19, sand is gone away for some great undertakings, Anhui chemical industry, 1992, (2): 11, Lin Yuehua, Guangdong chemical industry, 1999, (5): 26, Lu Xueliang, application chemical industry, 2003, 32 (2): 21, Li Jing, Guangzhou chemistry, 1992, (2): 61).Ethyliminum methyl ether hydrochloride, chloride solid precipitation can be produced in producing, need the low boiling point solvent adding 5-6 times of volume to disperse.Aftertreatment is cumbersome, needs first to steam solvent, then steams product.Not only energy consumption is high for this method, solvent loss large, and product heated time is long, easily occurs decomposing, and causes yield not high.
In recent years, bibliographical information is had to adopt high boiling solvent, as (Chen Kun, agricultural chemicals such as kerosene, chlorobenzene, dibutyl phthalate, trimethylbenzenes, 2004,43 (11): 507, Zhou Xueyong, Yunnan chemical, 2000,27 (5): 4), product is when being separated, and solvent can be used as thermal conductor, only needs to steam trimethyl orthoacetate.Although this method simplifies technique, before distillation, byproduct ammonium chloride still needs suction filtration to be separated, and solvent needs again to purify after repeatedly recycling, and its wastage rate also can up to 27%.
Summary of the invention
The object of the invention is employing one class hydrophobic ionic liquid as solvent to prepare trimethyl orthoacetate, for the building-up process of trimethyl orthoacetate, this kind of ionic liquid has following feature: can dissolve intermediate ethyliminum methyl ether hydrochloride and by-product ammonium chloride, thus make technological process be easy to realize the operation of complete canalization, ionic liquid can be recycled by washing, can recycled for multiple times and substantially do not have loss, thus realize the simplification of technique and improve product yield.
One class hydrophobic ionic liquid prepares the method for trimethyl orthoacetate as solvent, its flow process is shown in accompanying drawing 1, and it comprises the following steps:
Step 1. is by anhydrous acetonitrile, anhydrous methanol and solvent are sent in the first reactor (E-1) and are carried out subcooling, the consumption of solvent is 1-2 times of anhydrous acetonitrile and anhydrous methanol total mass, the consumption of anhydrous methanol and anhydrous acetonitrile equimolar amount, be cooled to temperature and be about-5 DEG C, the dry hydrogen chloride gas with anhydrous acetonitrile equimolar amount is passed in still, abundant stirring reaction about 6h afterwards, described solvent is a class hydrophobic ionic liquid, its positively charged ion is N, N-dialkylimidazolium cation or N-alkyl pyridine cationoid, negatively charged ion is phosphofluoric acid negatively charged ion or two trifluoromethanesulfonimide ion, concrete chemical structural formula is:
In formula: R
1be selected from the straight chained alkyl of C4 ~ C8;
The mixed solution that step 1 obtains is conveyed in the second reactor (E-2) by step 2., temperature in the kettle is 5 DEG C, add the pre-cold methanol of two times of anhydrous acetonitrile molar weights and stir 0.5h, the pH value of reaction system is regulated to be 5-6 to pH, then at about 40 DEG C alcoholysis mixed solution 12h with the ammonia in liquid ammonia storage tank (E-3);
The step 3. alcoholysis liquid to 0 DEG C that cooling step 2 obtains in the second reactor (E-2), by ammonia adjust ph to 8.0, afterwards alcoholysis liquid is conveyed into atmospheric distillation tower (E-4), collects 107 ~ 109 DEG C of cuts, obtain product trimethyl orthoacetate;
Still liquid at the bottom of step 4. rectifying tower (E-4) tower is sent in washing kettle (E-5) and is washed, and lower floor's liquid is sent in drying kettle (E-6) and dried, and the solvent after oven dry is sent in the first reactor (E-1), carries out recycle.
Invention before the present invention is better than: the method is by using hydrophobic ionic liquid as solvent, solubilized intermediate ethyliminum methyl ether hydrochloride and solid by-product ammonium chloride, thus make technological process be easy to realize the operation of complete canalization, be conducive to the serialization realizing technique, without the need to suction filtration operation before distillation.Meanwhile, the still liquid after distillation terminates, can remove through simple washing the ammonium chloride by-product be dissolved in ionic liquid, ionic liquid can recycle after drying, and provides cost savings and reduces energy consumption, achieving the green production of trimethyl orthoacetate.
Accompanying drawing explanation
Fig. 1 is that the present invention uses hydrophobic ionic liquid to prepare the process flow diagram of trimethyl orthoacetate for solvent, wherein: E-1 is the first reactor; E-2 is the second reactor; E-3 is liquid ammonia storage tank; E-4 is rectifying tower; E-5 is washing kettle; E-6 is drying kettle.
Embodiment
Embodiment 1: adopt butyl methyl limidazolium hexafluorophosphate as solvent
In reactor, drop into anhydrous acetonitrile 41.0g(1mol), anhydrous methanol 32.0g(1mol) and butyl methyl limidazolium hexafluorophosphate 73.0g, reaction solution is stirred and is cooled to-5 DEG C, dry hydrogen chloride gas 36.5g(1mol is slowly passed into) by distribution pipe, logical finish after slow temperature is risen to 5 DEG C, abundant stirring reaction 6h, obtains ethyliminum methyl ether hydrochloride solution simultaneously.Solution is cooled to 0 DEG C, and adds precooling anhydrous methanol 64.0g(2mol wherein), with ammonia regulation system pH=5.5, temperature is risen to 40 DEG C and stirring reaction 12h.Cooling reaction solution to 0 DEG C, with ammonia regulation system pH to 8.0.107 DEG C ~ 109 DEG C cuts are collected in reaction solution air distillation, and obtain trimethyl orthoacetate 110.76g, yield is 92.3%.
Be similar to embodiment 1, operate at different conditions, acquired results is as shown in the table:
| Embodiment | Solvent quality (g) | Alcoholysis pH value | Product yield % |
| 2 | 109.5 | 5.5 | 93.4 |
| 3 | 146.0 | 5.5 | 93.8 |
| 4 | 73.0 | 5.0 | 90.2 |
| 5 | 73.0 | 6.0 | 85.0 |
Note: solvent is butyl methyl limidazolium hexafluorophosphate
Embodiment 6:
In reactor, drop into anhydrous acetonitrile 41.0g(1mol), anhydrous methanol 32.0g(1mol) and hexyl methyl limidazolium hexafluorophosphate 73.0g, reaction solution is stirred and is cooled to-5 DEG C, dry hydrogen chloride gas 36.5g(1mol is slowly passed into) by distribution pipe, logical finish after slow temperature is risen to 5 DEG C, abundant stirring reaction 6h, obtains ethyliminum methyl ether hydrochloride solution simultaneously.Solution is cooled to 0 DEG C, and adds precooling anhydrous methanol 64.0g(2mol wherein), with ammonia regulation system pH=5.5, temperature is risen to 40 DEG C and stirring reaction 12h.Cooling reaction solution to 0 DEG C, with ammonia regulation system pH to 8.0.107 DEG C ~ 109 DEG C fractions are collected in reaction solution air distillation, and obtain trimethyl orthoacetate 113.52g, yield is 94.6%.
Be similar to embodiment 6, adopt different ionic liquids to operate, acquired results is as shown in the table:
| Embodiment | Solvent | Product yield % |
| 7 | Octyl methyl limidazolium hexafluorophosphate | 95.8 |
| 8 | Butyl-pyridinium hexafluorophosphate | 92.6 |
Embodiment 9:
In reactor, drop into anhydrous acetonitrile 41.0g(1mol), anhydrous methanol 32.0g(1mol) and embodiment 7 reclaim octyl methyl limidazolium hexafluorophosphate 73.0g, reaction solution is stirred and is cooled to-5 DEG C, dry hydrogen chloride gas 36.5g(1mol is slowly passed into) by distribution pipe, logical finish after slow temperature is risen to 5 DEG C, abundant stirring reaction 6h, obtains ethyliminum methyl ether hydrochloride solution simultaneously.Solution is cooled to 0 DEG C, and adds precooling anhydrous methanol 64.0g(2mol wherein), with ammonia regulation system pH=5.5, temperature is risen to 40 DEG C and stirring reaction 12h.Cooling reaction solution to 0 DEG C, with ammonia regulation system pH to 8.0.107 DEG C ~ 109 DEG C cuts are collected in reaction solution air distillation, and obtain trimethyl orthoacetate 114.12g, yield is 95.5%.
Be similar to embodiment 9, the octyl methyl limidazolium hexafluorophosphate that Reusability reclaims, acquired results is as shown in the table:
| Embodiment | Recycle number of times | Product yield % |
| 10 | 5 | 94.8 |
| 11 | 10 | 93.6 |
| 12 | 15 | 92.7 |
| 13 | 20 | 91.6 |
Claims (1)
1. a class hydrophobic ionic liquid prepares the method for trimethyl orthoacetate as solvent, it is characterized in that comprising the following steps:
Step 1. is by anhydrous acetonitrile, anhydrous methanol and solvent are sent in the first reactor (E-1) and are carried out subcooling, the consumption of solvent is 1-2 times of anhydrous acetonitrile and anhydrous methanol total mass, the consumption of anhydrous methanol and anhydrous acetonitrile equimolar amount, be cooled to temperature and be about-5 DEG C, the dry hydrogen chloride gas with anhydrous acetonitrile equimolar amount is passed in still, abundant stirring reaction about 6h afterwards, described solvent is a class hydrophobic ionic liquid, its positively charged ion is N, N-dialkylimidazolium cation or N-alkyl pyridine cationoid, negatively charged ion is phosphofluoric acid negatively charged ion, concrete chemical structural formula is:
In formula: R
1be selected from the straight chained alkyl of C4 ~ C8;
The mixed solution that step 1 obtains is conveyed in the second reactor (E-2) by step 2., temperature in the kettle is 5 DEG C, add the pre-cold methanol of two times of anhydrous acetonitrile molar weights and stir 0.5h, the pH value of reaction system is regulated to be 5-6 to pH, then at about 40 DEG C alcoholysis mixed solution 12h with the ammonia in liquid ammonia storage tank (E-3);
The step 3. alcoholysis liquid to 0 DEG C that cooling step 2 obtains in the second reactor (E-2), by ammonia adjust ph to 8.0, afterwards alcoholysis liquid is conveyed into atmospheric distillation tower (E-4), collects 107 ~ 109 DEG C of cuts, obtain product trimethyl orthoacetate;
Still liquid at the bottom of step 4. rectifying tower (E-4) tower is sent in washing kettle (E-5) and is washed, lower floor's liquid is sent in drying kettle (E-6) and is dried, solvent after oven dry is sent in the first reactor (E-1), carries out recycle.
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| CN104072346A (en) * | 2014-06-19 | 2014-10-01 | 常州吉恩化工有限公司 | Method for preparing orthoester compound |
| CN111675607A (en) * | 2020-06-09 | 2020-09-18 | 杭州众立化工科技有限公司 | Method for producing trimethyl orthoacetate through differential circulation and continuous production |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102060678A (en) * | 2010-12-27 | 2011-05-18 | 江苏优士化学有限公司 | Synthesis process of trimethyl orthoacetate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102060678A (en) * | 2010-12-27 | 2011-05-18 | 江苏优士化学有限公司 | Synthesis process of trimethyl orthoacetate |
Non-Patent Citations (2)
| Title |
|---|
| Ionic Liquid [bmim]PF6-Mediated Synthesis of 1,2-Orthoesters;Saithalavi Anas et al.,;《Bull. Chem. Soc. Jpn.》;20071231;第80卷(第3期);553-560 * |
| Synthesis of 2-R-2,2-dinitroethanol orthoesters in ionic liquids;Aleksei B. Sheremetev et al.,;《mendeleev communications》;20051231;第15卷(第5期);204-205 * |
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