CN1329371C - Solvent for separating and purifying 1, 5-naphthalene diamino formic ether and its use - Google Patents
Solvent for separating and purifying 1, 5-naphthalene diamino formic ether and its use Download PDFInfo
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- CN1329371C CN1329371C CNB2005100481479A CN200510048147A CN1329371C CN 1329371 C CN1329371 C CN 1329371C CN B2005100481479 A CNB2005100481479 A CN B2005100481479A CN 200510048147 A CN200510048147 A CN 200510048147A CN 1329371 C CN1329371 C CN 1329371C
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Abstract
一种用于1，5-萘二氨基甲酸酯分离提纯的溶剂组成为沸程范围为60～90℃的石油醚与乙酸乙酯体积比为60～100∶1。用于1，5-萘二氨基甲酸酯分离提纯方法是将1，5-萘二胺与碳酸二甲酯反应制备1，5-萘二氨基甲酸甲酯的反应液除去催化剂，再将过量的未参与反应的碳酸二甲酯蒸去得到固体混合物；按固体混合物与溶剂重量比为1∶20-100的比例加入溶剂中，室温下缓慢搅拌1～10小时，过滤，滤饼为1，5-萘二氨基甲酸甲酯产品。本发明具有简便易行，高收率，高纯度的优点。A solvent used for the separation and purification of 1,5-naphthalene dicarbamate is composed of petroleum ether with a boiling range of 60-90° C. and ethyl acetate in a volume ratio of 60-100:1. The separation and purification method for 1,5-naphthalene dicarbamate is to prepare 1,5-naphthalene dicarbamate by reacting 1,5-naphthalene diamine with dimethyl carbonate. Dimethyl carbonate that did not participate in the reaction was distilled off to obtain a solid mixture; the weight ratio of the solid mixture to the solvent was 1: 20-100, added to the solvent, stirred slowly at room temperature for 1 to 10 hours, filtered, and the filter cake was 1, Methyl 5-naphthalene dicarbamate product. The invention has the advantages of simple operation, high yield and high purity.
Description
Technical field
The invention belongs to 1, the 5-5-naphthalene diamino formic ether separates purifies with solvent and application method thereof, relates in particular to 1 5-naphthylene diamine and methylcarbonate preparation 1, the purified reaction product is used in the 5-5-naphthalene diamino formic ether process solvent and application method thereof.
Background technology
With 1, the 5-naphthalene diisocyanate is that raw material synthetic urethane has advantages such as hardness height, good, the hot damping and amortization of wear resistance be good, is used for the inefficient workplace of other urethane more.1,5-naphthalene diamino methyl-formiate is preparation 1, the important intermediate of 5-naphthalene diisocyanate, and it is synthetic to carry out the methoxycarbonyl reaction with methylcarbonate and 1.5-naphthylene diamine without phosgene at present.Because normal generation intermediate product 5-amino-naphthyl-1-Urethylane that boiling point is higher and polarity is close and by product 5-N-(methyl)-naphthyl-1 Urethylane generate in this reaction process, make 1, the separation of 5-naphthalene diamino methyl-formiate is purified and is become difficult.
Summary of the invention
The purpose of this invention is to provide a kind of solvent and application of being made up of sherwood oil and ethyl acetate miscellany thereof, this solvent is used for separating and purifying 1,1 of 5-naphthylene diamine and dimethyl carbonate preparation, 5-naphthalene diamino methyl-formiate.
The principle of foundation of the present invention is to utilize intermediate 5-amino-naphthyl-1-Urethylane, product 1, the polarity difference of 5-naphthalene diamino methyl-formiate and by product 5-N-(methyl)-naphthyl-1 Urethylane, selection has suitable polar solvent with 1,5-naphthylene diamine, intermediate 5-amino-naphthyl-1-Urethylane, by product 5-N-(methyl)-naphthyl-1 Urethylane are extracted in the solvent solvent, and then reach and separate to purify 1, the purpose of 5-naphthalene diamino methyl-formiate.
Solvent composition of the present invention is: the boiling range scope is that 60～90 ℃ sherwood oil and ethyl acetate volume ratio is 60～100: 1.
The preparation method of solvent of the present invention is that to get the boiling range scope be 60～90 ℃ sherwood oil and ethyl acetate, is 60～100: 1 with the volume ratio of sherwood oil and ethyl acetate, and is at room temperature evenly mixed, promptly is prepared into solvent required for the present invention.
The application method of solvent of the present invention is:
(1) with 1,5-naphthylene diamine and dimethyl carbonate preparation 1, the reaction solution of 5-naphthalene diamino methyl-formiate is removed catalyzer, again the excessive methylcarbonate that has neither part nor lot in reaction is boiled off obtain a kind of by intermediate 5-amino-naphthyl-1-Urethylane, by product 5-N-(methyl)-naphthyl-1 Urethylane and product 1, the solid mixture that 5-naphthalene diamino methyl-formiate is formed;
(2) be 1 in solid mixture with the weight of solvent ratio with this solid mixture: the ratio of 20-100 adds in the solvent, slowly stirs 1～10 hour under the room temperature, filters, and filter cake is 1,5-naphthalene diamino formic ether product.
Advantage of the present invention is as follows:
1) use solvent of the present invention, adopt extraction and separation technology to purify 1,1 of 5-naphthylene diamine and dimethyl carbonate preparation, 5-naphthalene diamino methyl-formiate makes the separation purification process simple and easy to do.
2) use this solvent, the employing extraction and separation technology can be with reaction product 1, intermediate and by product and unreacted raw material 1 that 5-naphthalene diamino methyl-formiate generates from it and reaction process, separate in the mixture that the 5-naphthylene diamine is formed, and high yield high purity obtain 1,5-naphthalene diamino methyl-formiate.
Embodiment
Embodiment 1:
1g1,5-naphthylene diamine (NDA) and 30ml methylcarbonate after abundant reaction, prepare 1, the reaction solution of 5-naphthalene diamino methyl-formiate (NDC), after removing catalyzer, the excessive methylcarbonate that has neither part nor lot in reaction is boiled off, obtain 5-amino-naphthalene-1-Urethylane (ANC), N-(methyl)-5-amino-naphthalene-1-Urethylane (MANC) and 1, the solid mixture 1.61g of 5-naphthalene diamino methyl-formiate.Adopt U.S. Waters company 510 type high performance liquid chromatographs (HPLC), 996 type diodes shake and split detector analysis (chromatographic column: BAX Bonus-RP C-18 (_ 4.6 * 250mm, 5 μ m); Moving phase: methanol=45/55 (V/V); Flow velocity: 0.8ml/min; Ultraviolet detection wavelength 239.6nm), each component concentration: ANC, 16%, MANC, 0.6%; NDC, 83.4%.
Adding the boiling range scope in this solid miscellany is that 60～90 ℃ of sherwood oils and ethyl acetate volume ratio are 60/1 solvent 32.2g, stirred 1 hour down in room temperature condition, filter, obtain filter cake 1.27g, the filter cake that takes a morsel is dissolved in N, be that 3.96min and 11.44min place obtain DMF and 1 respectively only with efficient liquid phase chromatographic analysis in dinethylformamide (DMF) solvent in retention time, the ultraviolet absorption peak of 5-naphthalene diamino methyl-formiate.The filter cake that takes a morsel is done ultimate analysis, and the result is: C, and 61.38%, H, 5.22%, N, 10.23%, for NDC (C
14H
14N
2O
4), the calculated value of these elements is: C, and 61.31%, H, 5.11%, N, 10.22%, illustrate that the NDC purity of purifying out is higher, and 1, the yield of 5-naphthalene diamino methyl-formiate is 94.77%.
Embodiment 2:
The solid miscellany of the reaction product that will prepare by embodiment 1 method, joining 96.6g is that 60～90 ℃ of sherwood oils and ethyl acetate are by volume in 80/1 solvent that is made into by the boiling range scope, stirred 5 hours down in room temperature condition, filter, obtain filter cake 1.30g, adopt under the condition of high performance liquid chromatography in embodiment 1 and analyze, getting retention time is two absorption peaks of 3.96min (DMF) and 11.44min (1,5-naphthalene diamino methyl-formiate).The filter cake that takes a morsel is done ultimate analysis, and the result is: C, and 61.38%, H, 5.22%, N, 10.23%, for NDC (C
14H
14N
2O
4), the calculated value of these elements is: C, and 61.31%, H, 5.11%, N, 10.22%, illustrate that the NDC purity of purifying out is higher, and 1, the yield of 5-naphthalene diamino methyl-formiate is 97.01%.
Embodiment 3:
The solid miscellany of the reaction product that will prepare by embodiment 1 method, joining 161g is that 60～90 ℃ of sherwood oils and ethyl acetate are by volume in 100/1 solvent that is made into by the boiling range scope, stirred 10 hours down in room temperature condition, filter, obtain filter cake 1.33g, the filter cake that takes a morsel is dissolved in N, is that 3.96min and 11.44min place obtain DMF and 1 respectively in retention time only with efficient liquid phase chromatographic analysis in dinethylformamide (DMF) solvent, the ultraviolet absorption peak of 5-naphthalene diamino methyl-formiate.The filter cake that takes a morsel is done ultimate analysis, and the result is: C, and 61.38%, H, 5.22%, N, 10.23%, for NDC (C
14H
14N
2O
4), the calculated value of these elements is: C, and 61.31%, H, 5.11%, N, 10.22%, illustrate that the NDC purity of purifying out is higher, and the yield of 1.5-naphthalene diamino methyl-formiate is 99.25%.
Embodiment 4:
With 1g1,5-naphthylene diamine (NDA) and 30ml methylcarbonate are without 1 of abundant reaction, the reaction solution of 5-naphthalene diamino methyl-formiate (NDC), after removing catalyzer, the excessive methylcarbonate that has neither part nor lot in reaction is boiled off, obtain 1.58g by 1,5-naphthylene diamine, 5-amino-naphthalene-1-Urethylane (ANC), N-(methyl)-5-amino-naphthalene-1-Urethylane (MANC) and 1, the solid mixture that 5-naphthalene diamino methyl-formiate is formed.Adopt U.S. Waters company 510 type high performance liquid chromatographs (HPLC), 996 type diodes shake and split detector analysis (chromatographic column: BAXBonus-RP C-18 (_ 4.6 * 250mm, 5 μ m); Moving phase: methanol=45/55 (V/V); Flow velocity: 0.8ml/min; Ultraviolet detection wavelength 239.6nm), each component concentration: NDA:8%; ANC:16%; MANC, 0.4%; NDC, 75.6%.
With this solid miscellany, joining 79g is that 60～90 ℃ sherwood oil and ethyl acetate are by volume in 60/1 solvent that is made into by the boiling range scope, stirred 3 hours down in room temperature condition, filter, obtain filter cake 1.13g, the filter cake that takes a morsel is dissolved in N, is that 3.96min and 11.44min place obtain DMF and 1 respectively in retention time only with efficient liquid phase chromatographic analysis in dinethylformamide (DMF) solvent, the ultraviolet absorption peak of 5-naphthalene diamino methyl-formiate.The filter cake that takes a morsel is done ultimate analysis, and the result is: C, and 61.38%, H, 5.22%, N, 10.23%, for NDC (C
14H
14N
2O
4), the calculated value of these elements is: C, and 61.31%, H, 5.11%, N, 10.22%, illustrate that the NDC purity of purifying out is higher, and the yield of 1.5-naphthalene diamino methyl-formiate is 94.96%.
Embodiment 5
The solid miscellany of the reaction product that will prepare by embodiment 4 methods, joining 47.4g is that 60～90 ℃ sherwood oil and ethyl acetate are by volume in 90/1 solvent that is made into by the boiling range scope, stirred 7 hours down in room temperature condition, filter, obtain filter cake 1.15g, the filter cake that takes a morsel is dissolved in N, is that 3.96min and 11.44min place obtain DMF and 1 respectively in retention time only with efficient liquid phase chromatographic analysis in dinethylformamide (DMF) solvent, the ultraviolet absorption peak of 5-naphthalene diamino methyl-formiate.The filter cake that takes a morsel is done ultimate analysis, and the result is: C, and 61.38%, H, 5.22%, N, 10.23%, for NDC (C
14H
14N
2O
4), the calculated value of these elements is: C, and 61.31%, H, 5.11%, N, 10.22%, illustrate that the NDC purity of purifying out is higher, and the yield of 1.5-naphthalene diamino methyl-formiate is 96.64%.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100481479A CN1329371C (en) | 2005-12-01 | 2005-12-01 | Solvent for separating and purifying 1, 5-naphthalene diamino formic ether and its use |
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| CNB2005100481479A CN1329371C (en) | 2005-12-01 | 2005-12-01 | Solvent for separating and purifying 1, 5-naphthalene diamino formic ether and its use |
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| CN1329371C true CN1329371C (en) | 2007-08-01 |
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| CN110256296A (en) * | 2019-05-20 | 2019-09-20 | 江苏蓝丰生物化工股份有限公司 | The synthetic method of 1,5- naphthalene diisocyanate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1426988A (en) * | 2001-12-21 | 2003-07-02 | 沈阳协合集团有限公司 | Method of extracting beta endesmol from mangnolia officinalis |
| CN1429813A (en) * | 2003-01-26 | 2003-07-16 | 河北工业大学 | Synthetic method of 1,5-methyl naphtualene diamino formate |
| CN1528765A (en) * | 2003-09-29 | 2004-09-15 | 南开大学 | Preparation method of insecticide dianon |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1426988A (en) * | 2001-12-21 | 2003-07-02 | 沈阳协合集团有限公司 | Method of extracting beta endesmol from mangnolia officinalis |
| CN1429813A (en) * | 2003-01-26 | 2003-07-16 | 河北工业大学 | Synthetic method of 1,5-methyl naphtualene diamino formate |
| CN1528765A (en) * | 2003-09-29 | 2004-09-15 | 南开大学 | Preparation method of insecticide dianon |
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