CN102786423A - Micro-reaction method for synthesizing 2,6-dinitroaniline herbicide by one-step nitration - Google Patents
Micro-reaction method for synthesizing 2,6-dinitroaniline herbicide by one-step nitration Download PDFInfo
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- CN102786423A CN102786423A CN201110131815XA CN201110131815A CN102786423A CN 102786423 A CN102786423 A CN 102786423A CN 201110131815X A CN201110131815X A CN 201110131815XA CN 201110131815 A CN201110131815 A CN 201110131815A CN 102786423 A CN102786423 A CN 102786423A
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Abstract
The invention relates to one-step synthesis of 2,6-dinitroaniline herbicides in a micro-reactor. Substituted phenyl amine substances and concentrated nitric acid are used as initial reaction materials; a solution containing substituted phenyl amines and concentrated nitric acid are pumped into a micro-reactor through a constant pump parallelly, and the dinitration reaction is completed in micron channels of the micro-reactor. The concentration of the substituted phenyl amines is 30%-90%; the mass concentration of the nitric acid is 65-98%; the amount of substance ratio of the nitric acid and the substituted phenyl amines is 2.0-3.0; the retention time of the reaction materials is 0.1-10 seconds; the reaction temperature is from normal temperature to a boiling point of the reactants. The micro-reaction method of the invention is used for synthesizing pendimethalin; the reaction conversion rate can reach 100% under an optimized condition; the ratio of the main product of pendimethalin to the by product of N-nitroso pendimethalin is increased to 8:2, while in an original double-kettle serial connection technology, the ratio is 3:7.
Description
Technical field
The present invention relates to nitrated Synthetic 2 of a step, little reaction method of 6-dinitroaniline herbicide, particularly little reaction technology of nitrated synthetic herbicide pendimethalin of a step.
Background technology
The seventies, American Cyanamid Co. developed a series of 2; 6-dinitroaniline herbicide (US 4025538), pendimethalin wherein, chemical name N-(1-ethyl propyl)-3; 4-dimethyl--2; The 6-dinitraniline has broad-spectrum high efficacy, low toxicity, highly selective, becomes maximum in the world selective herbicide.
Existing synthesis technique is taked the reductive alkylation nitrofication process; It is raw material 3; 4-dimethyl nitrobenzene elder generation hydrogenating reduction is produced for aniline, and with the last nitrated former medicine of pendimethalin that gets of propione alkylation, wherein nitrifying process is that nitrating acid carries out in the two-stage tank reactor with nitric acid again.Patent US 4621157 has reported the caldron process of preparation dinitraniline and compound thereof, with rare nitric acid and the nitrated in two steps preparation pendimethalin of concentrated nitric acid, intermediate N in the first step (1-ethyl propyl)-3; 4-xylidine and nitric acid mol ratio 1: 1, concentration of nitric acid 35.1%, midbody mass concentration 37%; 60 ℃ of temperature of reaction; Form a kind of aniline salt midbody (on the imino-combine a part nitric acid), in second step, 70% concentrated nitric acid of aniline salt midbody that the first step generates and 2.2 times of amounts is mixed under 60 ℃; And under this temperature, stirred 1 hour, obtain the pendimethalin bullion.
As everyone knows; Substituted benzene amine material is meeting by-product N-nitroso compound in nitrifying process; It has carinogenicity to most of Mammalss; Must control elimination, the method for the reduction nitro thing of leading of having appeared in the newspapers has two: one, and in nitrifying process, add suppressor factor and reduce by product and generate, the 2nd, use the method for reductive agent to handle by product after the nitration reaction and make it to be converted into title product; Relate to like US 5196585 and in nitrifying process, to add sulphite, CN200710055752 is reported in and adds four water iron protochloride reductive agents in the former medicine of generation to transform nitroso compound be title product.By-product N-nitroso compound can be thought nitrated product, and in kettle type nitration technology, long residence time of material made nitrated aggravation.
The microreactor technology is applied to the existing patent report of aromatic nitration process; US 6861527, US 7032607 etc. have reported mono-nitration reaction in the microreactor; CN200810010790, CN200810010797 take the lead in adopting the microreactor technology to carry out two nitrated reactions of toluene and chlorobenzene; Continuous conversion reaction thing in the residence time of material of tens of Milliseconds, transformation efficiency and two nitrated selectivity of product all reach more than 98%, become the technological guide in this field.At present, 2, little reactive synthesis technique of 6-dinitroaniline material also is not reported.
Summary of the invention
The purpose of this invention is to provide a kind of little reaction technology that utilizes, in tens of millisecond to several seconds stage material the residence time, safety, continuously, efficient, the high nitrated conversion substituted benzene amine material of selecting of a step, little reaction technology of pendimethalin preparation is provided especially.
Be to realize above-mentioned purpose, adopt little nitrated Synthetic 2 of one step of reaction method, the 6-dinitroaniline herbicide, nitration reaction is carried out in a hydraulic diameter is the microreactor of 100-1000 micron order passage, is I (R with structural formula
1, R
2Be Wasserstoffatoms, C
1-C
6Alkyl, C
2-C
6Alkylene, naphthenic base, alkylhalide group etc., R
3Be C
1-C
4Alkyl, halogen, C
2-C
4Alkylene etc., R
4Be C
1-C
4Alkyl, C
2-C
4Alkylene, alkoxyl group etc.) midbody---substituted benzene amine solution and mass concentration are that the concentrated nitric acid of 65-98% is squeezed in the microreactor through pump of constant delivery type is parallel; Nitric acid and intermediate materials amount than the condition of 2.0-4.0, the 0.1-10 second reaction mass residence time and midbody mass concentration 30-90% under continuous nitrification composite structure formula be 2 of II, the 6-dinitroaniline herbicide.
Said one-step synthesis 2, in the method for 6-dinitroaniline herbicide, nitric acid is at least 2.0 with intermediate materials amount ratio; The nitration reaction temperature is carried out at normal temperatures, or the boiling temperature of lower boiling reactant is interval in normal temperature to reaction mass, so that be liquid-liquid two phase reaction process in the microreactor.
In the method for the present invention, R among the intermediate structure formula I
1Be preferably hydrogen, R
3And R
4Be all methyl, work as R
2During for the 1-ethyl propyl, midbody is N-(1-ethyl propyl)-3, and the 4-xylidine is a raw material with it, is N-(1-ethyl propyl)-3 through a step two nitrated products therefroms, 4-dimethyl--2,6-dinitraniline, that is weedicide pendimethalin.When synthesizing pendimethalin, midbody dissolves with organic solvent such as ethylene dichloride, and concentration can be appointed fixed; Because of liquid holdup in the microreactor little; Therefore the reaction mass residence time, increases reacting material concentration in the hope of in shorter residence time of material, improving nitration reaction intrinsic speed generally between tens of milliseconds to several seconds; Thereby the raising yield reduces solvent load.Find that through experiment the concentration of 4-xylidine is brought up to 50-90%, particularly under 80% condition, uses concentration can make the reactant per pass conversion reach 100% as the nitric acid of 65-68% with N-(1-ethyl propyl)-3.
In synthetic pendimethalin process, the reaction mass residence time is selected 0.1-5.0 second, and different with kettle type nitration, the long residence time (being low-speed) is unfavorable for the mass transfer of nitration reaction process in the microreactor.As everyone knows; Two nitrated reactions are strong exothermal reaction, when adopting two stills two to go on foot nitration processes, require gentle relatively nitration condition to reduce intrinsic speed; The rate of heat transfer of itself and reaction kettle is complementary; This gentle relatively nitration condition comprises: lower intermediate concentration or lower nitrating acid concentration or lower reaction control temperature, this gentle relatively processing condition require the residence time of reaction mass in stirring tank longer, transform with abundant completion reaction mass.
Except that above-mentioned condition; The optimal conditions of nitrated synthetic pendimethalin method also comprises: temperature of reaction is chosen as 50-80 ℃, and this temperature is lower than the boiling temperature of midbody or nitric acid or solvent, under this temperature; Microreactor outlet product can guarantee not solidify blocking pipe, the process safe and continuous.And under this reactor drum controlled temperature, vaporization phenomenon is not seen in the microreactor outlet of being adopted, and two of substituted aniline nitrated reactions are liquid-liquid two phase reaction in the microreactor.
Adopt method of the present invention to synthesize pendimethalin; Under optimal conditions, intermediate N (1-ethyl propyl)-3,4-xylidine at least 95% is converted into product; The selectivity at least 60% of title product pendimethalin in the product, by-product N-nitroso-group pendimethalin at the most 40%.
Microreactor of the present invention is made up of wall scroll or many parallel micron order passages of longshore current body flow direction; And include two fluid intakes and a fluid outlet; Described micron order passage equivalent diameter is 100-1000 μ m; Preferred 300-500 μ m is with chemical etching method or the preparation of precision sizing method.The initial action material and the nitrating acid that contain substituted aniline get into reactor drum by two on microreactor inlets; Before two fluid streams are mixed, begin by access road, per share fluid warp is bifurcated repeatedly; Form equate with the passage equivalent diameter, the uniform fine branch fluid of multiply; Little hybrid channel (or claiming little reaction channel) is preceding getting into, and with bubbling style or T-shape or the contact of " Y " type hybrid mode, and in little reaction channel, accomplishes nitration reaction.The temperature control method of little reaction can adopt known electrical heating method, also can be in microreactor integrated little heat exchanger channels, the fluid that will have certain temperature imports heat exchanger channels and then realizes the effective regulation and control to the reactor drum interior reaction temperature.
The invention property ground is applied to little reaction technology two nitrated reactions of substituted benzene amine material; Reactant concn significantly improves; Reactant per pass conversion 100%; And cross nitration product nitroso-group selectivity and obviously reduce,, also will be applicable to the nitrated conversion of o-Xylol class material for synthetic herbicide provides little reaction technology of safe and continuous.The parallel amplification characteristics of microreactor can realize the industrialization production of this process.
Description of drawings
Fig. 1 is for can be used for the inner micron order channel architecture synoptic diagram (the Y type is hybrid) of microreactor of the present invention.1,1 ' is the fluidic branched bottom among the figure, and 2 for equivalent diameter equals the micron order reaction channel (parallel 16) of 400 μ m, 3 thin chambeies of product affluxs for flowing out parallel micron order reaction channel, and 4 is the public outlet of microreactor product.A, B represent profit two phase reaction thing.
Fig. 2 is the reaction temperatures affect graphic representation of the synthetic pendimethalin of little reaction technology.Hollow identification point is represented reaction conversion ratio on the diagram curve, and solid identification point is represented by-product NSC 223080 selectivity.
Embodiment
Below advance one through non-limiting enforcement and explain the present invention, and be that example details the inventive method with synthetic pendimethalin especially.
In the inventive method, except that the microreactor of indispensability, also need continuous measurement to carry former medicine and nitration acid equipment,, accurately two strands of reaction masses of said concentration are squeezed in the microreactor in the ratio of being put down in writing is parallel like volume pump; Microreactor carries out temperature control by specified temperature of reaction in advance, and temperature control uses the temperature controller instruments and meters, also can use the temperature of the inner micron order reaction channel of method controlling reactor of heat exchange or oil bath; Adjust the flow of two fluid pumps by the reaction mass residence time that the present invention put down in writing, one step of substituted aniline nitratedly is converted into 2, the 6-dinitraniline.
Present method does not relate to the by product NSC 223080 and removes or conversion processing, and therefore, in force, the pendimethalin that microreactor outlet obtains and the mix products of N nitroso-group pendimethalin be directly with dilution in acetonitrile, the feed liquor analysis of hplc.Chromatographic instrument is a UV230+ ultraviolet-visible variable-wavelenght detector, joins Agilent XDB-C18 separator column, is moving phase with acetonitrile and water, flow velocity 0.7ml/min, and wavelength 220nm adopts area normalization method to confirm the product composition.
Microreactor involved in the present invention is known to those skilled in the art; Be primary structure promptly with micron to millimeter order reaction passage; Two feed(raw material)inlets and a products export of being aided with the ligation passage, and with the little heat exchanger channels of reaction channel coupled.The microreactor technology is applied to when of the present invention, and the micron order passage in the microreactor requires in 100-1000 μ m interval, to select, and along with the maturation of microchannel process technology, the passage that is lower than 100 μ m will be applicable to that equally substituted benzene amine material two is nitrated.
In the specific embodiment below; Be etched with parallel 16 isometrical micron order reaction channels (2) in the microreactor (accompanying drawing 1); Equivalent diameter 400 μ m; The substituted aniline (A) of participating in reaction reacts with identical concentration, ratio and flow velocity in parallel microchannel (2) with nitric acid (B), by a public outlet (4) outflow reactor.
Embodiment 1
Use two Series II type digital pump (Chrom Tech, Inc.) with intermediate N (1-ethyl propyl)-3, the dichloroethane solution of 4-xylidine is parallel with concentrated nitric acid to be squeezed in the microreactor shown in Figure 1; The microreactor effective volume is 200 μ l, midbody mass concentration 80%, concentration of nitric acid 68%; Microreactor is with 60 ℃ of water-bath temperature controls; Regulate the flow output of two digital pump, nitric acid and midbody are got in the micron order reaction channel in the microreactor with 3: 1 proportioning of mol ratio continuously, the apparent residence time of reaction mass is 1.76 seconds; Be that the midbody solution volumetric flow rate is 3.8ml/min, 68% nitrating acid flow 3.0ml/min.Get product 1-2 and drip, with 100 times of anhydrous acetonitrile dilutions, the feed liquor facies analysis, reactant substituted aniline transformation efficiency 100%, nitration product diformazan penta is 97.6% with by product N-nitroso-group diformazan penta overall selectivity, the mole selectivity of N-nitroso-group diformazan penta is 21.3%.
Embodiment 2
Process is with reference to embodiment 1, and 50 ℃ of control bath temperatures are adjusted two strands of mass flows, changes the apparent residence time value of reaction mass.Reactant per pass conversion, product overall selectivity and by-product N-NSC 223080 selectivity are listed in the table below:
Embodiment 3
Process is with reference to embodiment 1.
Condition one: midbody mass concentration 30%, concentration of nitric acid 98%, microreactor is with 80 ℃ of water-bath temperature controls; Midbody solution and 98% nitrating acid volumetric flow rate are respectively 1.0ml/min and 0.5ml/min, i.e. 8 seconds apparent residence time, get product 1-2 and drip; With 100 times of anhydrous acetonitrile dilutions, feed liquor facies analysis, reactant substituted aniline transformation efficiency 84.7%; Nitration product diformazan penta is 64.0% with by product N-nitroso-group diformazan penta overall selectivity, and the mole selectivity of N-nitroso-group diformazan penta is 36.7%.
Condition two: midbody mass concentration 30%, concentration of nitric acid 65%, nitric acid and midbody ratio are any, and the apparent residence time is any, and no product generates, reaction mass N-(1-ethyl propyl)-3, the 4-xylidine does not have conversion.
Condition three: midbody mass concentration 50%, concentration of nitric acid 65%, 1 second apparent residence time; Getting product 1-2 drips; With 100 times of anhydrous acetonitrile dilutions, feed liquor facies analysis, reactant substituted aniline transformation efficiency 80.0%; Nitration product diformazan penta is 94.0% with by product N-nitroso-group diformazan penta overall selectivity, and the mole selectivity of N-nitroso-group diformazan penta is 15.5%.
Condition four: midbody mass concentration 50%, concentration of nitric acid 98%, 1 second apparent residence time; Getting product 1-2 drips; With 100 times of anhydrous acetonitrile dilutions, feed liquor facies analysis, reactant substituted aniline transformation efficiency 90.5%; Nitration product diformazan penta is 94.0% with by product N-nitroso-group diformazan penta overall selectivity, and the mole selectivity of N-nitroso-group diformazan penta is 18.5%.
This result of implementation shows, initial action material N-(1-ethyl propyl)-3, and 4-xylidine concentration should be higher than 30% at least.
Embodiment 4
Process is identical with embodiment 1, and (ChromTech is Inc.) with intermediate N (1-ethyl propyl)-3 to use two Series II type digital pump; The dichloroethane solution of 4-xylidine is parallel with concentrated nitric acid to be squeezed in the microreactor shown in Figure 1; The microreactor effective volume is 200 μ l, midbody mass concentration 80%, concentration of nitric acid 68%; Microreactor is with 80 ℃ of water-bath temperature controls; Regulate the flow output of two digital pump, nitric acid and midbody are got in the micron order reaction channel in the microreactor with 2.1: 1 proportioning of mol ratio continuously, the apparent residence time of reaction mass is 1.1 seconds; Be that the midbody solution volumetric flow rate is 7.2ml/min, 68% nitrating acid flow 4.0ml/min.Get product 1-2 and drip, with 100 times of anhydrous acetonitrile dilutions, the feed liquor facies analysis, reactant substituted aniline transformation efficiency 69.9%, nitration product diformazan penta is 89.3% with by product N-nitroso-group diformazan penta overall selectivity, the mole selectivity of N-nitroso-group diformazan penta is 27.2%.
Embodiment 5
With reference to embodiment 2.Investigate the reactor drum controlled temperature to reaction-ure conversion-age and by-product N-nitroso-group-N-(1-ethyl propyl)-3,4-dimethyl--2, the 6-dinitraniline optionally influences.Form with chart (accompanying drawing 2) provides influence curve; Visible by graphic representation, in selected 50-80 ℃ interval, the nitrated transformation efficiency of reactant one way can reach more than 98%; But the by product after nitrated also rises with temperature and increases, and the optimum operating temperature of reactor drum should be lower than 60 ℃.
Above instance is to the synthetic the inventive method of having described of weedicide pendimethalin; Be pointed out that; Every structure is that the dinitro of the substituted benzene amine midbody pointed out of right item 1 is combined to 2; The 6-dinitroaniline all can adopt the inventive method in the limited number of time test, to obtain optimum operation condition, and it also should be covered by within the protection domain of the present invention.
The present invention is used for synthetic pendimethalin, and reaction conversion ratio can reach 100% under the optimal conditions, and the ratio of principal product pendimethalin and by-product N-nitroso-group pendimethalin is brought up to 8: 2 by 3: 7 of former pair of still tandem process.
Claims (7)
1. one go on foot nitrated Synthetic 2; Little reaction method of 6-dinitroaniline herbicide;, hydraulic diameter carries out in being the microreactor of 100-1000 μ m level passage; It is characterized in that: the midbody solution that will contain structural formula and be I and mass concentration are that the concentrated nitric acid of 65-98% is squeezed in the microreactor through pump of constant delivery type is parallel; Nitric acid and intermediate materials amount than the condition of 2.0-4.0, the 0.1-10 second reaction mass residence time and midbody mass concentration 30-90% under continuous nitrification composite structure formula be 2 of II, the 6-dinitroaniline herbicide;
R
1, R
2Be Wasserstoffatoms, C
1-C
6Alkyl, C
2-C
6A kind of in alkylene, naphthenic base, the alkylhalide group, R
3Be C
1-C
4Alkyl, halogen, C
2-C
4A kind of in the alkylene, R
4Be C
1-C
4Alkyl, C
2-C
4A kind of in alkylene, the alkoxyl group.
2. the method for claim 1, it is characterized in that: the nitration reaction temperature is a normal temperature, or the boiling temperature of lower boiling reactant is interval in normal temperature to reaction mass.
3. the method for claim 1 is characterized in that: R among the intermediate structure formula I
1Be hydrogen, R
3And R
4Be all methyl.
4. method as claimed in claim 3 is characterized in that: midbody is N-(1-ethyl propyl)-3, the 4-xylidine, and be dissolved in the organic solvent, weedicide is a pendimethalin.
5. method as claimed in claim 4 is characterized in that: intermediate N (1-ethyl propyl)-3, and 4-xylidine concentration is selected 50-90%; The reaction mass residence time is selected 0.1-5.0 second, temperature of reaction 50-80 ℃.
6. method as claimed in claim 4; It is characterized in that: intermediate N (1-ethyl propyl)-3; 4-xylidine at least 95% is converted into product, the selectivity at least 60% of title product pendimethalin in the product, by-product N-nitroso-group pendimethalin at the most 40%.
7. the method for claim 1, it is characterized in that: wherein micron order passage hydraulic diameter is 300-500 μ m in the microreactor.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106748795A (en) * | 2016-11-18 | 2017-05-31 | 天津市安凯特科技发展有限公司 | A kind of Safe production method of ketone musk |
| CN109320424A (en) * | 2017-07-31 | 2019-02-12 | 江苏永安化工有限公司 | A kind of purification process of pendimethalin |
| CN111960947A (en) * | 2020-08-24 | 2020-11-20 | 百合花集团股份有限公司 | Method for synthesizing 4-chloro-2, 5-dimethoxy nitrobenzene by using microreactor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544567A (en) * | 2008-03-28 | 2009-09-30 | 中国科学院大连化学物理研究所 | Nitration method for synthesizing dinitrotoluene in one step, and microchannel reactor |
| CN101891631A (en) * | 2010-07-08 | 2010-11-24 | 上海海事大学 | Method for preparing pendimethalin |
-
2011
- 2011-05-20 CN CN201110131815XA patent/CN102786423A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544567A (en) * | 2008-03-28 | 2009-09-30 | 中国科学院大连化学物理研究所 | Nitration method for synthesizing dinitrotoluene in one step, and microchannel reactor |
| CN101891631A (en) * | 2010-07-08 | 2010-11-24 | 上海海事大学 | Method for preparing pendimethalin |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106748795A (en) * | 2016-11-18 | 2017-05-31 | 天津市安凯特科技发展有限公司 | A kind of Safe production method of ketone musk |
| CN109320424A (en) * | 2017-07-31 | 2019-02-12 | 江苏永安化工有限公司 | A kind of purification process of pendimethalin |
| CN109320424B (en) * | 2017-07-31 | 2021-12-21 | 江苏永安化工有限公司 | Method for purifying pendimethalin |
| CN111960947A (en) * | 2020-08-24 | 2020-11-20 | 百合花集团股份有限公司 | Method for synthesizing 4-chloro-2, 5-dimethoxy nitrobenzene by using microreactor |
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Application publication date: 20121121 |