CN102558136A - Synthetic method of amino-substituted cyclohexyl crown ether - Google Patents
Synthetic method of amino-substituted cyclohexyl crown ether Download PDFInfo
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- CN102558136A CN102558136A CN2011104249240A CN201110424924A CN102558136A CN 102558136 A CN102558136 A CN 102558136A CN 2011104249240 A CN2011104249240 A CN 2011104249240A CN 201110424924 A CN201110424924 A CN 201110424924A CN 102558136 A CN102558136 A CN 102558136A
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- crown ether
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Abstract
The invention discloses a synthetic method of amino-substituted cyclohexyl crown ether, which belongs to the technical field of synthetic technique of organic compound. The synthetic method uses nitro-substituted benzo crown ether as a substrate, uses high-activity Pichler ruthenium as a catalytic agent, uses high pressure hydrogen to achieve reduction of nitro and hydrogenation of phenyl group in substrate molecules simultaneously in one-step reaction, and accordingly obtains needed amino-substituted cyclohexyl crown ether products. The synthetic method enables the existing two-step reaction to be merged in a same system, and operation is greatly simplified. The temperature and the pressure of the needed reaction are relative mild, occurrence of side reaction is well avoided, and purity of obtained products is guaranteed. The ruthenium catalytic agent is high in catalytic activity, while cost is relatively lower than that of rhodium, platinum and the like, and the synthetic method has the cost advantage. Simultaneously, after reaction ends, the catalytic agent can be well separated and recycled.
Description
Technical field
The invention belongs to the organic cpds synthesis technical field, be specifically related to the compound method of a kind of amido substituted cyclohexyl and crown ether.
Background technology
In recent years, crown compound enjoys the concern of research fields such as coordination chemistry, extraction chemistry, water treatment because of it belongs to the ionic selective extraction capacity to GOLD FROM PLATING SOLUTION.In crown ether family, alicyclic crown ether often has better extraction complex ability relatively for metals ion, and in organic solvent, has better solvability and stability, so its purposes is also more extensive.Such as, Pb in dicyclohexyl--6 pairs of solution of 18-hat
2+High complexing coefficient just makes it to have application potential (Wu Chengtai etc., " crown ether chemistry ", Science Press, 1992) in the lead waste water process field.Simultaneously, aspect the extracting and separating of high heat release radioelement, alicyclic crown ether has also represented its value well in the nuclear fuel reprocessing flow process.As extraction agent, from high activity liquid waste, extract radioactivity 90Sr based on dicyclohexyl-18-crown-6
2+The existing report of ionic extraction, and passed through hot experiment checking (Wang Jianchen, etc. atomic energy science technology, 1998,32,57-62).In the solvent extraction process, the oil soluble that this alicyclic crown ether is fabulous also greatly facilitates the organic phase choice of Solvent.
Yet, in the solvent extraction process, unavoidably can run off as the alicyclic crown ether molecule of extraction agent, cause processing cost to increase.Especially solvent-extracted environment contains stronger acidity often, numerous free protons through with crown ether cycle on Sauerstoffatom form hydrogen bond, more can increase the tendency that crown compound is transferred to water, thereby increase loss amount.Therefore; People hope alicyclic crown ether is carried out chemically modified, make it to be with active reactive group, and the better verivate of processability thus; The perhaps chemical reaction through reactive group; It is bonded on the inertia solid phase carrier,, realizes respective metal ionic in the solution is separated through the extraction-chromatography technology.This wherein, substituted cyclohexyl of amido and crown ether because the high reaction activity of amido, are to enjoy one of selection scheme that everybody favors naturally.
Synthesizing of alicyclic crown ether, under certain temperature and catalyst action, utilize high pressure hydrogen that phenyl ring is carried out hydro-reduction normally based on corresponding benzo-crown ether or dibenzo dilating ether.Say from the organic synthesis design point of view; If will prepare substituted cyclohexyl of amido and crown ether; On the basis that obtains alicyclic crown ether, carrying out aminated is to be difficult to realize; The general characteristics that all need utilize electronic cloud enrichment on the corresponding aroma family crown ether aromatic ring obtain the substituted benzo-crown ether of amido through the nitration reaction and the nitro that reduces earlier, and then the product that obtains expecting through catalytic hydrogenation reduction phenyl ring.In this process, because the introducing of nitro, amido on the aromatic ring makes its catalytic hydrogenation process become complicated before comparing, so the substituted alicyclic crown ether of amido is synthetic comparatively difficult comparatively speaking, and correlative study all the time is also fewer.L.R.Sasykova once reported the synthetic of two amido dicyclohexyls and crown ether, and its way promptly is based on the dinitrobenzene dibenzo dilating ether, and the reduction nitro obtains two amido dibenzo dilating ethers earlier; And then obtain corresponding product (Sasykova, L.R, Izvestiya Ministerstva Nauki--Akademii Nauk Respubliki Kazakhstan through the catalytic hydrogenating reduction phenyl ring; Seriya Khimicheskaya; 1996, (6), 50-52).Its building-up process is carried out comparatively loaded down with trivial details in two steps, and selects catalyzer such as expensive Rh, Pt, and cost is higher.N.A.Tsarenko has reported the synthetic of two amido dicyclohexyl-18-crown-6s in patent SU 981318A119821215; But its experiment condition is very harsh; Highly active catalyzer Raney Ni consumption is big (10-100wt.%) very, and the temperature (130-150 ℃) and the pressure (150-250atm) that react required are all very high.
Metal Ru catalyst belongs to one type of platinum group catalyst that output is more, and is cheap with respect to precious metals such as rhodium, platinum.Pichler has reported ruthenium, Pottasium Hydroxide and saltpetre mixed melting the earliest, has processed water miscible potassium ruthenate, can obtain Pichler catalyzer (Pichler, H.et al., Advances in Catalysis, 1952,4,291) through the ethanol reduction again.Pichler ruthenium catalyst catalytic performance is excellent, and is with low cost, especially extremely insensitive to catalyzer poison, therefore, is widely used in the synthetic field of catalytic hydrogenation always.
Summary of the invention
The object of the present invention is to provide the compound method of a kind of amido substituted cyclohexyl and crown ether, solve existing amido substituted cyclohexyl and crown ether synthesis technique complex steps, severe reaction conditions, and the high problem of catalyzer cost.
The compound method of a kind of amido substituted cyclohexyl and crown ether, carry out according to following steps:
(1) nitro is replaced benzo-crown ether and be dissolved in the solvent, stir, obtain solvent system;
(2) with after the activated processing of Pichler ruthenium catalyst, be scattered in the solvent, join again in the solvent system that step (1) makes;
(3) the control temperature of reaction system is 60-135 ℃, and hydrogen pressure 5-15MPa keeps stirring, and reacts 4-24 hour; Temperature of reaction is preferably 75-110 ℃, and hydrogen pressure is preferably 6-8MPa, and the reaction times is preferably 6-12 hour;
(4) after reaction finished, filtering Pichler ruthenium catalyst and steaming desolventized and is lower than 90 ℃ material with boiling point, obtains amido substituted cyclohexyl and crown ether product.
It is the different isomerization body that single nitro replaces benzo-12-crown-4 that said nitro replaces benzo-crown ether; Single nitro replaces the different isomerization body of benzo-15-hat-5; Single nitro replaces the different isomerization body of benzo-18-hat-6; The different isomerization body of single nitro benzo-21-hat-7; The dinitrobenzene substituted diphenylamine also-the different isomerization body of 12-crown-4; The dinitrobenzene substituted diphenylamine also-the different isomerization body of 15-hat-5; The dinitrobenzene substituted diphenylamine also-the different isomerization body of 18-hat-6 or dinitrobenzene substituted diphenylamine also-the different isomerization body of 21-hat-7.
Said solvent is alcohol, glycol dimethyl ether, isopropyl benzene, the YLENE of carbonatoms 1-8, preferred alcohol, propyl carbinol, glycol dimethyl ether.
The mass ratio that step (1) solvent for use and nitro replace benzo-crown ether is (10-300): 1, preferred (50-150): 1.
Used Pichler ruthenium catalyst accounts for the 2-30% that nitro replaces the benzo-crown ether quality, preferred 5-10%.
Beneficial effect of the present invention: reaction of the present invention is an one-step synthesis, and to become amido and phenyl shortening to generate cyclohexyl be in same reaction process, to realize that technology is easy to nitroreduction in the substrate molecule; Select the Pichler ruthenium catalyst with higher catalytic activity for use, catalyst levels is little, and precious metals such as the relative rhodium of metal Ru price, platinum are not high in addition, and therefore, the whole cost of building-up reactions is relatively low; Temperature of reaction and pressure condition are gentle relatively, can greatly reduce side reaction such as crown ether cycle generation fracture in the high pressure catalytic reaction process, guarantee to estimate product higher purity and yield; It is easy that reaction finishes the after product separation, and directly filtration catalizer also steams and desolventizes and low-boiling point material, can obtain amido substituted cyclohexyl and crown ether product.And isolating ruthenium catalyst can reuse.
Embodiment
Below in conjunction with specific embodiment the present invention is further specified.
Synthesizing of 1: two amido dicyclohexyl-18-crown-6 of embodiment
With dinitrobenzene dibenzo-18-hat-6 is substrate, under the effect of Pichler ruthenium catalyst, utilizes the reaction equation of high pressure hydrogen one-step synthesis two amido dicyclohexyl-18-crown-6s following:
5.0g dinitrobenzene dibenzo-18-hat-6 is dissolved in 450mL ethanol, and adding volume is the autoclave of 3L.Take by weighing the new activatory Pichler of 1g ruthenium catalyst, be scattered in the 50mL ethanol, add in the still again.Close and lock reaction kettle, logical nitrogen displaces air in the still for three times, and nitrogen is fallen in three displacements of logical again hydrogen, and then feeding pressure is the hydrogen of 6MPa.Keep stirring, the control temperature in the kettle is 100 ℃, reacts stopped reaction after 8 hours, treats total system cooling back pressure release discharging.Filter, separate and recovery Pichler ruthenium, 60 ℃ of underspins steam solvent and the low-boiling point material removed in the filtrating and promptly obtain two amido dicyclohexyl-18-crown-6 products.The gc test result shows that raw material transforms fully, and product is the isomer mixture of isomorphism type not, and purity is 92%.Mass spectroscopy: 402.90 (calculated value is 402.53).Proton nmr spectra (chemical shift δ/ppm, solvent are DMSO-d6): 3.78-3.36 (CH
2, 16H, m), 2.68 (CH, 6H, m), 2.01 (CH
2, 2H, m), 1.87 (CH
2, 2H, m), 1.60-1.51 (C
H2,4H, m), 1.28 (CH
2, 2H, s), 1.15 (CH
2, 2H, m).Experimental data shows and meets the title product structure.
Embodiment 2: the amido substituted cyclohexyl also-12-crown-4 synthetic
Single nitro replaces benzo-12-crown-4 under the effect of Pichler ruthenium catalyst, utilize the high pressure hydrogen single step reaction generate the amido substituted cyclohexyl also-reaction equation of 12-crown-4 is following:
Taking by weighing the 10.0g nitro replaces benzo-12-crown-4 and in volume is the autoclave of 3L, is dissolved in the 700mL propyl carbinol.Take by weighing the new activatory Pichler of 0.8g ruthenium catalyst again, be scattered in the 100mL propyl carbinol, add in the still.Close and lock reaction kettle, logical nitrogen displaces air in the still for three times, and nitrogen is fallen in three displacements of logical again hydrogen, and then feeding pressure is the hydrogen of 7MPa.Keep stirring, the control temperature in the kettle is 85 ℃, reacts stopped reaction after 10 hours, treats total system cooling back pressure release discharging.Filter, separate and also reclaim the Pichler ruthenium, 70 ℃ of underspins steam remove in the filtrating solvent and low-boiling point material promptly obtain the amido substituted cyclohexyl also-the 12-crown-4 product.The gc test result shows that reaction substrate 100% transforms, and product purity is 94%.Purification of samples is through mass spectroscopy, and molecular weight is 245.74 (calculated value is 245.32).
3: two amido dicyclohexyls of embodiment also-15-hat-5 synthetic
Under the effect of Pichler ruthenium catalyst, utilize high pressure hydrogen one step reduction dinitrobenzene dibenzo-15-hat-5, generate two amido dicyclohexyls also-reaction equation of 15-hat-5 is following:
Be dissolved in 5.0g dinitrobenzene dibenzo-15-hat-5 the 300mL glycol dimethyl ether, join the autoclave that volume is 1L.Take by weighing the new activatory Pichler of 0.3g ruthenium catalyst, be scattered in the 50mL glycol dimethyl ether, add in the still again.Close and lock reaction kettle, logical nitrogen displaces air in the still for three times, and nitrogen is fallen in three displacements of logical again hydrogen, and then feeding pressure is the hydrogen of 9MPa.Keep stirring, the control temperature in the kettle is 110 ℃, and stopped reaction after 5 hours is treated total system cooling back pressure release discharging.Filter, separate and also reclaim the Pichler ruthenium, filtrating is removed solvent ethylene glycol dme and other low-boiling point materials at 60 ℃ of following rotary evaporations, promptly get two amido dicyclohexyls also-15-is preced with-5 products.The gc test shows that feed stock conversion reaches 100%, and product is the mixture of different configurational isomers, and product purity reaches 91%.Show that through mass spectroscopy the molecular weight of products therefrom is 358.23 (calculated value is 358.47).
Embodiment 4: the amido substituted cyclohexyl also-18-hat-6 synthetic
Select the substituted phendioxin 8-of single nitro hat-6 as reaction substrate, under the effect of Pichler ruthenium catalyst, utilize high pressure hydrogen one step reduction generate the amido substituted cyclohexyl also-reaction equation of 18-hat-6 is following:
The substituted phendioxin 8-hat-6 of the single nitro of 10.0g is dissolved in the 800mL Virahol, and adding volume is the autoclave of 3L.Take by weighing the new activatory Pichler of 0.75g ruthenium catalyst, be scattered in the 100mL Virahol, add in the still again.Close and lock reaction kettle, logical nitrogen displaces air in the still for three times, and nitrogen is fallen in three displacements of logical again hydrogen, and then feeding pressure is the hydrogen of 10MPa.Keep stirring, the control temperature in the kettle is 105 ℃, reacts stopped reaction after 7 hours, treats total system cooling back pressure release discharging.Filter, separate and also reclaim the Pichler ruthenium, 65 ℃ of underspins steam the solvent removed in the filtrating and low-boiling point material can obtain the substituted cyclohexyl of amido also-18-is preced with-6 products.The gc test result shows that raw material transforms fully, and product purity can reach 95%.Show that through mass spectroscopy the molecular weight of products therefrom is 333.67 (calculated value is 333.42).
Synthesizing of 5: two amido dicyclohexyl-21-crown-7s of embodiment
Dinitrobenzene dibenzo-21-hat-7 under the effect of Pichler ruthenium catalyst, utilize the high pressure hydrogen single step reaction generate diamines basic ring hexyl also-reaction equation of 21-hat-7 is following:
Take by weighing 7.0g dinitrobenzene dibenzo-21-hat-7 and in volume is the autoclave of 3L, be dissolved in the 700mL n-Octanol.Take by weighing the new activatory Pichler of 0.7g ruthenium catalyst again, be scattered in the 100mL n-Octanol, add in the still.Close and lock reaction kettle, logical nitrogen displaces air in the still for three times, and nitrogen is fallen in three displacements of logical again hydrogen, and then feeding pressure is the hydrogen of 10MPa.Keep stirring, the control temperature in the kettle is 115 ℃, reacts stopped reaction after 9 hours, treats total system cooling back pressure release discharging.Filter, separate and also reclaim the Pichler ruthenium, steam at 85 ℃ of underspins and remove in the filtrating solvent and low-boiling point material promptly obtains two amido dicyclohexyl-21-crown-7 products.The gc test result shows that reaction substrate 100% transforms, and product is an isomer mixture, and overall purity is 90%.Purification of samples is through mass spectroscopy, and molecular weight is 446.94 (calculated value is 446.58).
Claims (5)
1. the compound method of amido substituted cyclohexyl and crown ether is characterized in that, carries out according to following steps:
(1) nitro is replaced benzo-crown ether and be dissolved in the solvent, stir, obtain solvent system;
(2) with after the activated processing of Pichler ruthenium catalyst, be scattered in the solvent, join again in the solvent system that step (1) makes;
(3) the control temperature of reaction system is 60-135 ℃, and hydrogen pressure 5-15MPa keeps stirring, and reacts 4-24 hour;
(4) after reaction finished, filtering Pichler ruthenium catalyst and steaming desolventized and is lower than 90 ℃ material with boiling point, obtains amido substituted cyclohexyl and crown ether product.
2. according to the compound method of said a kind of amido substituted cyclohexyl of claim 1 and crown ether; It is characterized in that, said nitro replace different isomerization body that benzo-crown ether is different isomerization body, single nitro that single nitro the replaces benzo-12-crown-4 different isomerization body that replaces the benzo-different isomerization body of 15-hat-5, single nitro and replace benzo-18-hat-6, single nitro benzo-21-hat-7, dinitrobenzene substituted diphenylamine also-the different isomerization body of 12-crown-4, dinitrobenzene substituted diphenylamine also-the different isomerization body of 15-hat-5, dinitrobenzene substituted diphenylamine also-the different isomerization body of 18-hat-6 or dinitrobenzene substituted diphenylamine also-the different isomerization body of 21-hat-7.
3. according to the compound method of said a kind of amido substituted cyclohexyl of claim 1 and crown ether, it is characterized in that said solvent is alcohol, glycol dimethyl ether, isopropyl benzene, the YLENE of carbonatoms 1-8.
4. according to the compound method of said a kind of amido substituted cyclohexyl of claim 1 and crown ether, it is characterized in that the mass ratio that step (1) solvent for use and nitro replace benzo-crown ether is (10-300): 1.
5. according to the compound method of said a kind of amido substituted cyclohexyl of claim 1 and crown ether, it is characterized in that used Pichler ruthenium catalyst accounts for the 2-30% that nitro replaces the benzo-crown ether quality.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109206398A (en) * | 2018-08-08 | 2019-01-15 | 西北大学 | A kind of the anion self-assembling function material and preparation method of potassium ion sensitivity |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1709888A (en) * | 2005-07-15 | 2005-12-21 | 清华大学 | Improved systhesizing process for dicyclohexyl-18-crown-6 |
| CN102040584A (en) * | 2010-12-16 | 2011-05-04 | 清华大学 | Synthesis method of dicyclohexyl-18-crown-6 |
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2011
- 2011-12-16 CN CN2011104249240A patent/CN102558136A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1709888A (en) * | 2005-07-15 | 2005-12-21 | 清华大学 | Improved systhesizing process for dicyclohexyl-18-crown-6 |
| CN102040584A (en) * | 2010-12-16 | 2011-05-04 | 清华大学 | Synthesis method of dicyclohexyl-18-crown-6 |
Non-Patent Citations (2)
| Title |
|---|
| YAKSHIN, V. V., ET AL: "Method for immobilization of cycloaliphatic crown ethers on a polymeric matrix", 《DOKLADY AKADEMII NAUK》 * |
| 黄宪 等: "《新编有机合成化学》", 31 January 2003 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109206398A (en) * | 2018-08-08 | 2019-01-15 | 西北大学 | A kind of the anion self-assembling function material and preparation method of potassium ion sensitivity |
| CN109206398B (en) * | 2018-08-08 | 2019-05-14 | 西北大学 | A kind of the anion self-assembling function material and preparation method of potassium ion sensitivity |
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Application publication date: 20120711 |