CN1429813A - Synthetic method of 1,5-methyl naphtualene diamino formate - Google Patents
Synthetic method of 1,5-methyl naphtualene diamino formate Download PDFInfo
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- CN1429813A CN1429813A CN 03102864 CN03102864A CN1429813A CN 1429813 A CN1429813 A CN 1429813A CN 03102864 CN03102864 CN 03102864 CN 03102864 A CN03102864 A CN 03102864A CN 1429813 A CN1429813 A CN 1429813A
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Abstract
A process for synthesizing 1,5-methyl naphthalenediamino formate includes such steps as reaction between 1.5-diaminonaphthalene and dimethyl carbonate in solvent for catalytic synthesising of said product, cooling the resultant, and separating to obtain 1,5-methyl naphthalene-diaminoformate. Its advantages are high output rate up 95%, low cost of catalyst, and no environmental pollution.
Description
The technology of the present invention field
The invention belongs to a kind of chemical synthesis process, particularly a kind of usefulness 1,5-diaminonaphthalene (claim 1 again, the 5-naphthylene diamine is called for short NDA) synthesizes 1, the method for 5-naphthalene diamino methyl-formiate (being called for short NDC) with methylcarbonate (being called for short DMC) catalytic reaction.
Background technology of the present invention
1,5-naphthalene diamino methyl-formiate (NDC) is to synthesize 1, the intermediate of 5-naphthalene diisocyanate (being called for short NDI).NDI is the raw material of synthetic senior urethane, its goods fusing point height, intensity height, rebound resilience is good, dynamic property is excellent, heat-resisting, wear-resisting, oil resistant, life-span are long, can be used for the workplace of unappeasable requirement of conventional polyurethanes or early failure, have a extensive future.
At present, 1, phosgenation is adopted in the production of 5-naphthalene diisocyanate (NDI).Phosgenation need use the phosgene and the liquid phosgene of severe toxicity to make raw material, severe operational environment, and severe reaction conditions, seriously polluted, technical process is long, technical sophistication; The a large amount of hydrochloric acid of by-product in synthetic, etching apparatus; Residual chlorine is difficult to remove in the product, refining difficulty.
US4330479, EP396976, JP344730, Chem Commun, 1998, (23): disclose a kind of 1 in the 2575-2576 document, 5-5-naphthalene diamino formic ether cracking synthetic 1, the method of 5-naphthalene diisocyanate (NDI) is a Future Development 1, the only way of 5-naphthalene diisocyanate (NDI), and 1, the synthetic of 5-5-naphthalene diamino formic ether is the key of this route.
Disclose a kind ofly with 1 in the US4278805 document, 5-diaminonaphthalene (NDA), urethanum, ethanol are that catalytic material is synthetic 1, the method for 5-naphthalene diamino ethyl formate.In 180 ℃ of reactions 12 hours, 1,5-diaminonaphthalene (NDA) transformation efficiency 71%, selectivity 82.8%.This method long reaction time, transformation efficiency is not high.
Disclose a kind ofly with 1 in the US4593117 document, 5-diaminonaphthalene (NDA) and N-phenyl-O-dodecyl carbamate and dodecanol catalysis are synthetic 1,5-naphthalene diamino dodecyl ester.220 ℃, 500mbar reaction 5 hours, yield was 87%.This method temperature of reaction height can cause poly-and causes selectivity to descend, and complicated operation.
At document J.Am.Chem.Soc., 1993, (115): report among the 3778-3779 with 1,5-dinitronaphthalene and CO, methyl alcohol are raw material, with Pd-clay, Ru
3(CO)
12, 2,2 '-two pyridines are catalyzer, reaction is 12 hours under 180 ℃, 70atm, synthetic NDC yield 72%.This method not only uses precious metal to be catalyzer, and the reaction pressure height, and the time is long.
Technology contents of the present invention
The present invention mainly solves problems such as the complex process, severe reaction conditions, the yield that exist in the prior art are low, production cost height, thereby provide that a kind of technology is simple and safe, reaction conditions is gentle, yield is high, production cost is low, non-environmental-pollution 1, the synthetic method of 5-naphthalene diamino methyl-formiate.
Technical solution of the present invention is as follows:
1, the synthetic method of 5-naphthalene diamino methyl-formiate is 1, and 5-diaminonaphthalene and methylcarbonate react in solvent, and catalysis synthesizes 1,5-naphthalene diamino methyl-formiate, and its processing step is as follows:
(1) with 1,5-diaminonaphthalene and methylcarbonate, catalyzer, solvent are put into reactor;
(2) be heated to temperature when being 175～200 ℃, reacted 1～4.5 hour;
(3) after reaction finishes, be cooled to room temperature, take out reaction mixture, separate, promptly make 1,5-naphthalene diamino methyl-formiate.
Employed 1 in the above-mentioned synthetic method, the 5-diaminonaphthalene is 1: 10～1: 25 with the ratio of the amount of substance of methylcarbonate.
Employed catalyzer and 1 in the above-mentioned synthetic method, the ratio of the amount of substance of 5-diaminonaphthalene is 0.45: 1～0.9: 1.
Employed catalyzer is in the above-mentioned synthetic method: the zinc carbonate in the mineral acid zinc, zinc sulfate, zinc nitrate; Zinc formate in the organic acid zinc, trimethylacetic acid zinc, trichoroacetic acid(TCA) zinc, zinc oxalate, zinc propionate, zinc butyrate, isopropylformic acid zinc, zinc valerate, Zincum val, caproic acid zinc, Zinc Heptylate, isoamyl acetic acid zinc, zinc octoate, isocaprylic acid zinc, zinc pelargonate, capric acid zinc, dodecylic acid zinc, tetradecanoic acid zinc, hexadecanoic acid zinc, octadecanoic acid zinc, docosoic acid zinc, Zinc dibenzoate, toluylic acid zinc, zinc salicylate; Barium acetate in the acetate, magnesium acetate, manganous acetate, cadmium acetate, lead acetate, venus crystals, nickelous acetate.
Employed solvent is isopropylcarbinol, Virahol, methyl alcohol, ethanol, acetone, dioxane, tetrahydrofuran (THF), methylcarbonate, acetonitrile, pyridine, N in the above-mentioned synthetic method, dinethylformamide, tetramethylene sulfone, dimethyl sulfoxide (DMSO).
Employed 1 in the above-mentioned synthetic method, the concentration of 5-diaminonaphthalene is 19～57g/100ml solvent.
Separation method in the above-mentioned synthetic method is: will react the slurries filtration under diminished pressure that obtains after finishing, filter cake is handled after drying with dilute sulphuric acid, obtains solid phase prod 1,5-naphthalene diamino methyl-formiate; Also obtain solid phase prod 1,5-naphthalene diamino methyl-formiate after the filtrate decompression distillation; Utilize again after the distillate solvent recuperation.
Through IR, MS, NMR
1H, NMR
13Means such as C and meta analysis characterize, and are 1,5-naphthalene diamino methyl-formiate.
The present invention compared with prior art has following beneficial effect:
(1) synthetic method of the present invention uses " green chemical " methylcarbonate (DMC) to be raw material, can realize handy and safe, free of contamination cleaner production.
(2) synthetic method of the present invention by-product methyl alcohol only, and methyl alcohol is the raw material of Synthesis of dimethyl carbonate (DMC) is in conjunction with methyl alcohol and CO, O
2The technology of oxidative carbonylation Synthesis of dimethyl carbonate (DMC) can be accomplished " zero release " of chemical process like this, realizes atom economy.
(3) synthesising method reacting condition gentleness of the present invention, easy handling, catalyst system therefor is cheap, and the product yield height can reach 95%.
The specific embodiment of the present invention is as follows
Embodiment 1
(1) with 5g1,5-diaminonaphthalene (NDA), 67ml methylcarbonate (DMC) (NDA: DMC=1: 25, the ratio of amount of substance), 3.2g trimethylacetic acid zinc (trimethylacetic acid zinc: NDA=0.5: 1, the ratio of amount of substance), drop in the reactor;
(2) be heated under 180 ℃ of temperature, reacted 4.5 hours;
(3) after reaction finishes, be cooled to room temperature, take out reaction mixture and separate;
(4) isolating method is the slurries filtration under diminished pressure that obtains after reaction is finished.The filtrate decompression distillation obtains solid phase prod 1,5-naphthalene diamino methyl-formiate (NDC); Filter cake is handled with dilute sulphuric acid simultaneously, also obtains solid phase prod 1,5-naphthalene diamino methyl-formiate (NDC).After reclaiming, distillate utilizes again.
Product is through IR, MS, NMR
1H, NMR
13C and meta analysis are 1,5-naphthalene diamino methyl-formiate (NDC), and the result is as follows:
IR(cm
-1)：3291，2962，1702，1601，1502，1335，1261，1099，791；
MS：274，242，210，183，169，156，128，115，102，59；
NMR
1H(ppm)：9.54786，7.58014，7.52888，7.90431，7.86363，7.48920，3.69039；
NMR
13C(ppm)：155.460，133.987，128.691，125.465，121.553，119.505，51.893；
Meta analysis: measured value: C:61.46%, H:4.85%, N:10.05%;
Actual value: C:61.31%, H:5.11%, N:10.22%;
Product is measured through high performance liquid chromatography (HPLC), and 1,5-diaminonaphthalene (NDA) transformation efficiency 100%, 1,5-naphthalene diamino methyl-formiate (NDC) yield 95.0%, catalyzer specific activity 154.9gNDC/ (mol-cat) .h.
Embodiment 2
(1) with 5g1,5-diaminonaphthalene (NDA), 67ml methylcarbonate (DMC) (NDA: DMC=1: 25, the ratio of amount of substance), the ring fourth alum of 60ml, and the 3.0g zinc propionate (zinc propionate: NDA=0.45: 1, the ratio of amount of substance), drop in the reactor;
(2) be heated under 185 ℃ of temperature, reacted 4 hours;
(3) after reaction finishes, be cooled to room temperature, take out reaction mixture and separate, just obtain the solid 1 of white, 5-naphthalene diamino methyl-formiate (NDC).Separation method is with embodiment 1.
Measure through HPLC, 1,5-diaminonaphthalene (NDA) transformation efficiency 100%, 1,5-naphthalene diamino methyl-formiate (NDC) yield 92.2%, catalyzer specific activity 87.1gNDC/ (mol-cat) .h.
Embodiment 3
(1) with 5g1,5-diaminonaphthalene (NDA), 27ml methylcarbonate (DMC) (NDA: DMC=1: 10, the ratio of amount of substance), the dimethyl alum of 67ml, and the 4.7g zinc valerate (zinc valerate: NDA=0.75: 1, the ratio of amount of substance), drop in the reactor;
(2) be heated under 190 ℃ of temperature, reacted 3 hours;
(3) after reaction finishes, be cooled to room temperature, take out reaction mixture and separate; Just obtain the solid 1 of white, 5-naphthalene diamino methyl-formiate (NDC).Separation method is with embodiment 1.
Measure through HPLC, 1,5-naphthalene diamino methyl-formiate (NDC) yield 78.7%.
Embodiment 4
(1) with 5g1,5-diaminonaphthalene (NDA), 54ml methylcarbonate (DMC) (NDA: DMC=1: 20, the ratio of amount of substance), the ring fourth alum of 50ml, 3.2g trimethylacetic acid zinc (trimethylacetic acid zinc: NDA=0.5: 1, the ratio of amount of substance), drop in the reactor;
(2) be heated under 175 ℃ of temperature, reacted 2.5 hours;
(3) after reaction finishes, be cooled to room temperature, take out reaction mixture and separate; Just obtain the solid 1 of white, 5-naphthalene diamino methyl-formiate (NDC).Separation method is with embodiment 1.
Measure through HPLC, 1,5-naphthalene diamino methyl-formiate (NDC) yield 81.4%.
Embodiment 5
(1) with 5g1,5-diaminonaphthalene (NDA), 67ml methylcarbonate (DMC) (NDA: DMC=1: 25, the ratio of amount of substance), the acetonitrile of 55ml, and 4.4g dodecylic acid zinc (dodecylic acid zinc: NDA=0.8: 1, the ratio of amount of substance), drop in the reactor;
(2) be heated under 190 ℃ of temperature, reacted 4.5 hours;
(3) after reaction finishes, be cooled to room temperature, take out reaction mixture and separate; Just obtain the solid 1 of white, 5-naphthalene diamino methyl-formiate (NDC).Separation method is with embodiment 1.
Measure through HPLC, 1,5-naphthalene diamino methyl-formiate (NDC) yield 89.7%.
Embodiment 6
(1) with 5g1,5-diaminonaphthalene (NDA), 27ml methylcarbonate (DMC) (NDA: DMC=1: 10, the ratio of amount of substance), the N of 50ml, dinethylformamide, 3.9g zinc valerate (zinc valerate: NDA=0.45: 1, the ratio of amount of substance), drop in the reactor;
(2) be heated under 200 ℃ of temperature, reacted 1 hour;
(3) after reaction finishes, be cooled to room temperature, take out reaction mixture and separate; Just obtain the solid 1 of white, 5-naphthalene diamino methyl-formiate (NDC).Separation method is with embodiment 1.
Measure through HPLC, 1,5-naphthalene diamino methyl-formiate (NDC) yield 21.5%.
Embodiment 7
(1) with 5g1,5-diaminonaphthalene (NDA), 67ml methylcarbonate (DMC) (NDA: DMC=1: 25, the ratio of amount of substance), 6.0g octadecanoic acid zinc (octadecanoic acid zinc: NDA=0.45: 1, the ratio of amount of substance), drop in the reactor;
(2) be heated under 175 ℃ of temperature, reacted 4.5 hours;
(3) after reaction finishes, be cooled to room temperature, take out reaction mixture and separate; Just obtain the solid 1 of white, 5-naphthalene diamino methyl-formiate (NDC).Separation method is with embodiment 1.
Measure through HPLC, 1,5-naphthalene diamino methyl-formiate (NDC) yield 93.2%.
Claims (7)
1. one kind 1, the synthetic method of 5-naphthalene diamino methyl-formiate is characterized in that: its processing step is as follows:
(1) with 1,5-diaminonaphthalene and methylcarbonate, catalyzer, solvent are put into reactor;
(2) be heated to temperature when being 175 ℃～200 ℃, reacted 1～4.5 hour;
(3) after reaction finishes, be cooled to room temperature, take out reaction mixture, separate, promptly make 1,5-naphthalene diamino methyl-formiate.
2. said 1 according to claim 1, the synthetic method of 5-naphthalene diamino methyl-formiate is characterized in that: 1 of use, the 5-diaminonaphthalene is 1: 10～1: 25 with the ratio of the amount of substance of methylcarbonate.
3. said 1 according to claim 1, the synthetic method of 5-naphthalene diamino methyl-formiate is characterized in that: the catalyzer of use and 1, the ratio of the amount of substance of 5-diaminonaphthalene is 0.45: 1～0.9: 1.
4. said 1 according to claim 1, the synthetic method of 5-naphthalene diamino methyl-formiate is characterized in that: employed catalyzer is: the zinc carbonate in the mineral acid zinc, zinc sulfate, zinc nitrate; Zinc formate in the organic acid zinc, trimethylacetic acid zinc, trichoroacetic acid(TCA) zinc, zinc oxalate, zinc propionate, zinc butyrate, isopropylformic acid zinc, zinc valerate, Zincum val, caproic acid zinc, Zinc Heptylate, isoamyl acetic acid zinc, zinc octoate, isocaprylic acid zinc, zinc pelargonate, capric acid zinc, dodecylic acid zinc, tetradecanoic acid zinc, hexadecanoic acid zinc, octadecanoic acid zinc, docosoic acid zinc, Zinc dibenzoate, toluylic acid zinc, zinc salicylate; Barium acetate in the acetate, magnesium acetate, manganous acetate, cadmium acetate, lead acetate, venus crystals, nickelous acetate.
5. according to claim 1 said 1, the synthetic method of 5-naphthalene diamino methyl-formiate, it is characterized in that: employed solvent is isopropylcarbinol, Virahol, methyl alcohol, ethanol, acetone, dioxane, tetrahydrofuran (THF), methylcarbonate, acetonitrile, pyridine, N, dinethylformamide, tetramethylene sulfone, dimethyl sulfoxide (DMSO).
6. said 1 according to claim 1, the synthetic method of 5-naphthalene diamino methyl-formiate is characterized in that: employed 1, the concentration of 5-diaminonaphthalene is 19～57g/100ml solvent.
7. according to claim 1 said 1, the synthetic method of 5-naphthalene diamino methyl-formiate is characterized in that: the product separation method is: will react the slurries filtration under diminished pressure that obtains after finishing, filter cake is handled after drying with dilute sulphuric acid, obtain solid phase prod 1,5-naphthalene diamino methyl-formiate; Also obtain solid phase prod 1,5-naphthalene diamino methyl-formiate after the filtrate decompression distillation; Utilize again after the distillate solvent recuperation.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329371C (en) * | 2005-12-01 | 2007-08-01 | 中国科学院山西煤炭化学研究所 | Solvent for separating and purifying 1, 5-naphthalene diamino formic ether and its use |
| CN100369671C (en) * | 2005-12-01 | 2008-02-20 | 中国科学院山西煤炭化学研究所 | Method for preparing N-substituted carbamate using cyclohexane zine butyrate |
| CN100408557C (en) * | 2003-08-26 | 2008-08-06 | 河北工业大学 | Method for preparing 2,4-toluene diamino menthyl formate |
| CN110066228A (en) * | 2019-05-31 | 2019-07-30 | 上海应用技术大学 | A kind of preparation method of 1,5- naphthalene diisocyanate |
| 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 |
| CN110981753A (en) * | 2019-12-19 | 2020-04-10 | 山东华阳农药化工集团有限公司 | Preparation of diphenyl ethane diisocyanate by dimethyl carbonate method and application thereof |
| CN112479931A (en) * | 2020-12-09 | 2021-03-12 | 安徽广信农化股份有限公司 | Synthesis process of cyclohexyl |
-
2003
- 2003-01-26 CN CNB031028640A patent/CN1176065C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100408557C (en) * | 2003-08-26 | 2008-08-06 | 河北工业大学 | Method for preparing 2,4-toluene diamino menthyl formate |
| CN1329371C (en) * | 2005-12-01 | 2007-08-01 | 中国科学院山西煤炭化学研究所 | Solvent for separating and purifying 1, 5-naphthalene diamino formic ether and its use |
| CN100369671C (en) * | 2005-12-01 | 2008-02-20 | 中国科学院山西煤炭化学研究所 | Method for preparing N-substituted carbamate using cyclohexane zine butyrate |
| 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 |
| CN110066228A (en) * | 2019-05-31 | 2019-07-30 | 上海应用技术大学 | A kind of preparation method of 1,5- naphthalene diisocyanate |
| CN110066228B (en) * | 2019-05-31 | 2021-07-20 | 上海应用技术大学 | Preparation method of 1, 5-naphthalene diisocyanate |
| CN110981753A (en) * | 2019-12-19 | 2020-04-10 | 山东华阳农药化工集团有限公司 | Preparation of diphenyl ethane diisocyanate by dimethyl carbonate method and application thereof |
| CN112479931A (en) * | 2020-12-09 | 2021-03-12 | 安徽广信农化股份有限公司 | Synthesis process of cyclohexyl |
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