CN105777547A - Synthesis method of m-nitrobenzaldehyde - Google Patents
Synthesis method of m-nitrobenzaldehyde Download PDFInfo
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- CN105777547A CN105777547A CN201610210433.9A CN201610210433A CN105777547A CN 105777547 A CN105777547 A CN 105777547A CN 201610210433 A CN201610210433 A CN 201610210433A CN 105777547 A CN105777547 A CN 105777547A
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- benzaldehyde
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- ZETIVVHRRQLWFW-UHFFFAOYSA-N 3-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC(C=O)=C1 ZETIVVHRRQLWFW-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000001308 synthesis method Methods 0.000 title abstract 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 46
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 27
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000012043 crude product Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001868 water Inorganic materials 0.000 claims abstract description 16
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 13
- 239000011541 reaction mixture Substances 0.000 claims abstract description 11
- 239000003021 water soluble solvent Substances 0.000 claims abstract description 11
- CMWKITSNTDAEDT-UHFFFAOYSA-N 2-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC=C1C=O CMWKITSNTDAEDT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 7
- 238000004064 recycling Methods 0.000 claims description 20
- 239000010413 mother solution Substances 0.000 claims description 15
- 238000010189 synthetic method Methods 0.000 claims description 12
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 238000013461 design Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- -1 wherein Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 15
- 238000001914 filtration Methods 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 2
- 239000012452 mother liquor Substances 0.000 abstract 2
- 238000001816 cooling Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 239000002994 raw material Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PVHUJELLJLJGLN-INIZCTEOSA-N (S)-nitrendipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OC)[C@@H]1C1=CC=CC([N+]([O-])=O)=C1 PVHUJELLJLJGLN-INIZCTEOSA-N 0.000 description 1
- UIAGMCDKSXEBJQ-IBGZPJMESA-N 3-o-(2-methoxyethyl) 5-o-propan-2-yl (4s)-2,6-dimethyl-4-(3-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylate Chemical compound COCCOC(=O)C1=C(C)NC(C)=C(C(=O)OC(C)C)[C@H]1C1=CC=CC([N+]([O-])=O)=C1 UIAGMCDKSXEBJQ-IBGZPJMESA-N 0.000 description 1
- QOVTVIYTBRHADL-UHFFFAOYSA-N 4-amino-6-(1,2,2-trichloroethenyl)benzene-1,3-disulfonamide Chemical compound NC1=CC(C(Cl)=C(Cl)Cl)=C(S(N)(=O)=O)C=C1S(N)(=O)=O QOVTVIYTBRHADL-UHFFFAOYSA-N 0.000 description 1
- KJEBULYHNRNJTE-DHZHZOJOSA-N Cinalong Chemical compound COCCOC(=O)C1=C(C)NC(C)=C(C(=O)OC\C=C\C=2C=CC=CC=2)C1C1=CC=CC([N+]([O-])=O)=C1 KJEBULYHNRNJTE-DHZHZOJOSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229960003020 cilnidipine Drugs 0.000 description 1
- 229960000275 clorsulon Drugs 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000003987 high-resolution gas chromatography Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229960000715 nimodipine Drugs 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 229960005425 nitrendipine Drugs 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a synthesis method of m-nitrobenzaldehyde. The method comprises the following steps: firstly, reacting, concretely carrying out reaction on copper nitrate, water, silver nitrate and benzaldehyde in a molar ratio of (1.03-1.1):(20-40):(0.001-0.0012):1.0, so that reaction mixture is obtained; secondly, preparing an m-nitrobenzaldehyde crude product, concretely, filtering while the reaction mixture is hot, so as to obtain mother liquor, and then cooling the mother liquor, filtering, and taking solid, so that the m-nitrobenzaldehyde crude product is obtained; and thirdly, preparing high-purity m-nitrobenzaldehyde, concretely, adding a water soluble solvent into the m-nitrobenzaldehyde crude product, filtering, and drying, so that high-purity m-nitrobenzaldehyde is obtained. By adopting the method provided by the invention, molar yield of the obtained m-nitrobenzaldehyde is more than 90%, chromatographic purity is more than 99.8%, and content of o-nitrobenzaldehyde is less than 0.1%; and fewer three wastes are produced in a production process, so that the method provided by the invention is environmentally friendly.
Description
Technical field
The present invention relates to organic compound synthesis technical field, be specifically related to the synthetic method of a kind of m-nitrobenzaldehyde.
Background technology
M-nitrobenzaldehyde is a kind of very important medicine intermediate, is widely used in the synthesis of multiple medicine, as clorsulon,
Cilnidipine, nitrendipine, nimodipine etc..At present, domestic production producer is considerably less, and its reason is existing production work
Skill is complicated, adjacency pair position poor selectivity, needs repeatedly recrystallization just to can get qualified products, and high purity product is the highest and quantity of three wastes
Very big, the biggest to environmental disruption.
At present, the method preparing m-nitrobenzaldehyde is as follows:
Ding Chengrong et al. was published in " Zhejiang Polytechnical University's journal " in 2005 and entitled " m-nitrobenzaldehyde synthesis is new
The research of technique " article, particular content is: with benzaldehyde as raw material, with isopropylamine react generation intermediate benzaldehyde
Contracting imines, then with mixed acid nitrification, then hydrolyze, obtain target product m-nitrobenzaldehyde.The emphasis raw material to nitration reaction
Proportioning, reaction temperature, response time and hydrolysis time are investigated, and the proportioning raw materials obtaining nitration reaction is: benzaldehyde
Contracting imines: sulphuric acid (mol ratio)=1:7, benzaldehyde contracting imines: nitric acid (mol ratio)=1:1.2, reaction temperature be 10～
15 DEG C, the response time is 2h, and hydrolysis time is 2.5h, and the yield of m-nitrobenzaldehyde is 88.4%, and its mass fraction is
99.1%.
Huang Yinhua et al. was published in " petrochemical industry " and entitled " synthesis technique of m-nitrobenzaldehyde " in 2008
Article, particular content is: benzaldehyde generates three benzaldehydes contracting diamidogen (TBDA) with ammonia condensation, through mixed acid nitrification, then water
Solve synthesis m-nitrobenzaldehyde.Have studied the influence factor of condensation, nitration reaction, optimize reaction condition, experimental result table
Bright: the preferable condition of condensation reaction is: n (benzaldehyde): n (ammonia)=1: 2.4, and reaction temperature 40 DEG C, during reaction
Between 12h, the yield of TBDA reaches 98.7% with this understanding；The preferable condition of nitration reaction is: n (TBDA): n is (dense
Sulphuric acid)=1: 16, n (TBDA): n (concentrated nitric acid)=1: 8, nitration reaction temperature is 10～15 DEG C, nitration reaction
Time is 2h, and the yield of the thick product of m-nitrobenzaldehyde reaches 86.3%；Thick product is through petroleum ether-toluene Mixed Solvent (volume ratio
It being 1.5: 1) purity reaches 99.8% after recrystallization, and the total recovery of m-nitrobenzaldehyde is 76.4%.
Institutes Of Technology Of Nanjing's Chemical Engineering was published in " fine-chemical intermediate " and entitled " m-nitro first in 2007
The synthesising process research of aldehyde " article, specifically: with meta-nitrotoluene as raw material, with AIBN (azodiisobutyronitrile) for urging
Agent synthesis m-nitrobenzaldehyde.At n (meta-nitrotoluene): n (chlorine bromic acid): n (hydrogen peroxide)=1: 3: 3, bromine
Changing temperature is 65～75 DEG C, and bromination time is 8～9h, and the oxydrolysis time is 8h, and the yield of m-nitrobenzaldehyde is 30.4%,
The purity of m-nitrobenzaldehyde is 99.2%.
The Master's thesis " synthesis of m-nitrobenzaldehyde " that the Diao Chunli of Institutes Of Technology Of Nanjing delivered in 2008 discloses two
The synthetic method of kind of m-nitrobenzaldehyde, Details as Follows: (1) with meta-nitrotoluene for raw material through bromo, hydrolyze, aoxidize
Prepare m-nitrobenzaldehyde, specifically three-step reaction condition is optimized, specifically: as n (meta-nitrotoluene): n
(Potassium bromate .): n (sodium bisulfate)=1:2.5:2.5, bromination time is 4h, and bromo temperature is 70 DEG C, and (bromo produces n
Thing): n (sodium carbonate) is 1:2, and hydrolysis time is 7h, and hydrolysis temperature is 100 DEG C, and oxidizing temperature is 100 DEG C, a nitre
The yield of benzaldehyde is 48.2%；(2) with meta-nitrotoluene as raw material, manganese sesquioxide managnic oxide is oxidant, and sulphuric acid is reaction
The selective oxidation of the meta-nitrotoluene of medium, when n (meta-nitrotoluene): n (manganese sesquioxide managnic oxide)=1:1.5, reaction
Temperature is 90 DEG C, and the response time is 7h, and the yield of m-nitrobenzaldehyde is 65.6%.
Above several method has that the yield of m-nitrobenzaldehyde is low, production cost is high, technological process of production length, pollute big etc.
Defect, is not easy to large-scale industrial production.
Along with the continuous renewal of technology, the patent of invention of Application No. 201110173084.5 discloses a kind of m-nitrobenzaldehyde
Production technology, specifically: with benzaldehyde as raw material, prepare through nitrification, addition, alkali analysis and the step such as refined.The present invention
Technique, by adjusting nitration condition, makes ortho isomer control below 15%, utilizes m-nitrobenzaldehyde and ortho isomer
The larger difference of addition product dissolubility under certain condition make overwhelming majority analysis ortho isomer be separated, the chromatograph of crude product
Purity reaches 99.2%, and refined rear chromatographic purity is up to more than 99.9%, and ortho isomer can be controlled in less than 0.06%.This
Though method has the highest yield, but also has the disadvantages that processing step length, production cost are the highest, and produce useless
The water yield is very big, and goes back the substantial amounts of nitrate of content and sulphite in waste water, and environmental pollution is the biggest.
In sum, it is badly in need of that a kind of production technology is simplified, the yield of m-nitrobenzaldehyde is high, pollute little production work in industry
Skill is to solve the deficiencies in the prior art.
Summary of the invention
Present invention aim at providing a kind of production technology to simplify, the yield of m-nitrobenzaldehyde is high, pollute little m-nitro
The synthetic method of formaldehyde, concrete technical scheme is as follows:
The synthetic method of a kind of m-nitrobenzaldehyde, comprises the following steps:
Step one: reaction, specifically: in reaction unit, add copper nitrate, water and silver nitrate, be warming up to 70 DEG C-80 DEG C；
Dropping benzaldehyde, time for adding is 1.8-2.5 hour；It is warming up to 85 DEG C-95 DEG C, is incubated and obtains reaction mixture in 2-3 hour；
From reaction mixture sampling carry out chromatograph detection, the content of benzaldehyde be less than 0.5%, wherein copper nitrate, water, silver nitrate with
And the mol ratio of benzaldehyde is 1.03-1.1:20-40:0.001-0.0012:1.0；
Step 2: m-nitrobenzaldehyde crude product processed, specifically: reaction mixture is filtered to remove hydroxide at 85 DEG C-95 DEG C
Copper precipitation obtains mother solution；Mother solution is cooled to 10 DEG C-20 DEG C；Cross leaching solid and i.e. obtain m-nitrobenzaldehyde crude product, described between
In nitrobenzaldehyde crude product, the content of 1-Formyl-2-nitrobenzene is less than 0.5%；
Step 3: the m-nitrobenzaldehyde of preparing high-purity, specifically: m-nitrobenzaldehyde crude product is loaded reaction unit, adds
The water-soluble solvent of m-nitrobenzaldehyde crude product volume 3.0-3.5 times, is warming up to 50 DEG C-55 DEG C；Cross after filtering to remove insoluble impurity
Add the water of water-soluble solvent same volume；Filter and dry after taking out the solid separated out, obtain high-purity m-nitrobenzaldehyde.
In above technical scheme preferably, in described step one, copper nitrate, silver nitrate, the quality standard of benzaldehyde are unskilled labor
Industry grade standard.
In above technical scheme preferably, described reaction unit is provided with mixing component, described step one and step 3 stir
The stir speed (S.S.) of parts is 120-160 rev/min.
In above technical scheme preferably, the temperature dried in described step 3 is 40 DEG C-50 DEG C, and the time is 8-12 hour.
In above technical scheme preferably, described water-soluble solvent be methanol, ethanol, isopropanol, dimethylformamide and
Any one of oxolane.
In order to reach superior technique effect, also include that recycling step, described recycling step include recycling step A and recovery
Step B, described recycling step A specifically: the Copper hydrate precipitation nitric acid obtained by second step is neutralized, and will obtain
Copper nitrate solution reaction in the first step；Described recycling step B is specifically: will filter mother liquid obtained warp in the 3rd step
Crossing process and be used as water-soluble solvent, wherein, in the mother solution after process, water content is less than 10%.
In above technical scheme preferably, in described recycling step B, the process step of mother solution is specifically: mother solution suction reclaimed
Solvent rectifying column, controls temperature and is less than 60 DEG C, by regulation reflux ratio, by moisture Control below 10%, in collection
Between fraction.
Application technical scheme, has the advantages that employing benzaldehyde, copper nitrate and silver nitrate are main
Raw material, raw material obtains easily, and cost of material is low；Utilize benzaldehyde and copper nitrate for primary raw material, in the catalysis of copper nitrate
Lower synthesis m-nitrobenzaldehyde crude product, m-nitrobenzaldehyde crude product obtains high-purity m-nitrobenzaldehyde after simple refining
Product, whole process steps is simplified, with short production cycle, and technological parameter is easily controlled, it is simple to large-scale production；The present invention
Use copper nitrate as nitrating agent, (live to increase the reaction of copper nitrate because its internal copper ion has big steric effect
Property, add silver nitrate as catalytic reagent), can at utmost avoid the generation of benzaldehyde ortho-nitration thing so that the present invention
The molar yield of gained m-nitrobenzaldehyde is more than 90%, and chromatographic purity is more than 99.8%, and 1-Formyl-2-nitrobenzene is less than 0.1%；
Copper hydrate of the present invention precipitation and the equal recoverable of mother solution of subtractive process, be substantially reduced the discharge of the three wastes, environmental protection.
In addition to objects, features and advantages described above, the present invention also has other objects, features and advantages.Under
Face will be with reference to specific embodiment, and the present invention is further detailed explanation.
Detailed description of the invention
It is described in detail below in conjunction with embodiments of the invention, but what the present invention can limit according to claim and cover
Multitude of different ways is implemented.
Embodiment 1:
The synthetic method of a kind of m-nitrobenzaldehyde, its raw material used and instrument refer to table 1.
Table 1 raw material and instrument statistical table
| Raw material parameter | Producer | Specification | Content |
| Copper nitrate | Do not limit | Seconds | >=99.5% |
| Silver nitrate | Do not limit | Seconds | >=99.0% |
| Benzaldehyde | Do not limit | Certified products | >=99.0% |
| Reaction unit | Do not limit | There-necked flask | - |
The synthesis of the present embodiment m-nitrobenzaldehyde specifically includes following steps:
Step one: reaction, specifically: in reaction unit, add the copper nitrate of 19.70 grams (0.105mol), under room temperature
It is slowly added into the water of 50 grams (2.78mol) copper nitrate to be completely dissolved obtain the copper nitrate solution (speed herein, added water
Adjustable, it is therefore an objective to realizing copper nitrate can be completely dissolved)；0.017 gram (0.000101mol) is added in copper nitrate solution
Silver nitrate obtain mixed liquor；The benzene first of 10.60 grams (0.10ml) is slowly dripped after mixed liquor is warming up to 70 DEG C (T1)
Aldehyde, time for adding is 2.0 hours (t1), obtains reaction solution after being added dropwise to complete；Reaction solution is warming up to 85 DEG C (T2)
Rear insulation 2.0 hours (t2) obtains reaction mixture；From reaction mixture, sampling carries out chromatograph detection, containing of benzaldehyde
Amount is less than 0.5%；
Step 2: m-nitrobenzaldehyde crude product processed, specifically: reaction mixture is filtered to remove hydrogen-oxygen when temperature is T2
Change copper precipitation and obtain mother solution；Mother solution is cooled to 10 DEG C (T3)；Cross leaching solid and i.e. obtain m-nitrobenzaldehyde crude product, a nitre
The weight of benzaldehyde crude product is 20 grams, and in described m-nitrobenzaldehyde crude product, the content of 1-Formyl-2-nitrobenzene is less than 0.5%；
Step 3: the m-nitrobenzaldehyde of preparing high-purity, specifically: m-nitrobenzaldehyde crude product is loaded reaction unit, adds
The methanol (water-soluble solvent) of 60 milliliters, is warming up to 50 DEG C (T4)；Cross the water adding 60 milliliters after filtering to remove insoluble impurity；
Filter and carry out drying (temperature herein dried is 40 DEG C-50 DEG C, and the time is 8-12 hour) after taking out the solid separated out, to obtain final product
High-purity m-nitrobenzaldehyde, now the weight of high-purity m-nitrobenzaldehyde is 14.0 grams.
Also including recycling step in said process, described recycling step includes recycling step A and recycling step B, described time
Receive step A specifically: the Copper hydrate precipitation nitric acid obtained by second step is neutralized, the copper nitrate solution obtained is used
Course of reaction in the first step；Described recycling step B is specifically: mother liquid obtained be used as filtering in the 3rd step through process
Water-soluble solvent, wherein, the process step of mother solution specifically: by mother solution suction recycling design rectifying column, control temperature and do not surpass
Crossing 60 DEG C, by regulation reflux ratio, (design of reflux ratio specifically can be carried out according to prior art and practical situation accordingly
Regulation, core be realize by moisture Control below 10%), by moisture Control below 10%, collect midbarrel.
Being provided with mixing component in described reaction unit, in described step one and step 3, the stir speed (S.S.) of mixing component is
120-160 rpm (both stir speed (S.S.) ratios are 11 speed ratios).
In said process, the control of temperature can use water bath, it is achieved the rising of temperature, reduction and constant；Copper nitrate
Molecular weight be 187.56, the molecular weight of water is 18, and the molecular weight of silver nitrate is 169.8731, and the molecular weight of benzaldehyde is
106.12。
The chemical equation related in said method mainly has two:
1, copper nitrate and benzaldehyde synthesize m-nitrobenzaldehyde and Copper hydrate precipitation under silver nitrate and certain reaction temperature.
2, Copper hydrate neutralizes through pernitric acid and obtains copper nitrate and water.
Chromatograph is used to detect, the results detailed in Table 4 the high-purity m-nitrobenzaldehyde of the present embodiment.
Chromatographic test strip part:
Chromatograph: good fortune founds 9790-II high resolution gas chromatography instrument；
Chromatographic column: HP-50 equivalence gas chromatographic column；
Detection temperature: 1-5min, 80 DEG C, 6-30min, 5 DEG C/min, 30-40min, 200 DEG C.
Embodiment 2-embodiment 6:
Embodiment 2-embodiment 6 difference from Example 1 is table 2.
The parametric statistics table of table 2 embodiment 2-embodiment 6
Embodiment 2-embodiment 6 gained high-purity m-nitrobenzaldehyde uses chromatographic detection method same as in Example 1, knot
Fruit refers to table 4.
Comparative example 1-comparative example 4:
Comparative example's 1-comparative example 4 difference from Example 1 is table 3:
The parametric statistics table of table 3 comparative example 1-comparative example 4
Comparative example 1-comparative example 4 uses detection method same as in Example 1, the results are shown in Table 4.
Table 4 comparative example 1-comparative example 4 and the chromatograph testing result statistical table of embodiment 1-embodiment 6
| Embodiment result | M-nitrobenzaldehyde yield/% | Chromatographic purity/% | 1-Formyl-2-nitrobenzene content/% | Three wastes situation |
| Embodiment 1 | 92.71 | 99.9 | ＜ 0.1 | <1.0g |
| Embodiment 2 | 90.73 | 99.8 | ＜ 0.1 | <1.0g |
| Embodiment 3 | 90.73 | 99.9 | ＜ 0.1 | <1.0g |
| Embodiment 4 | 91.39 | 99.9 | ＜ 0.1 | <1.0g |
| Embodiment 5 | 92.05 | 99.8 | ＜ 0.1 | <1.0g |
| Embodiment 6 | 90.73 | 99.8 | ＜ 0.1 | <1.0g |
| Comparative example 1 | 86.66 | 99.2 | ＜ 0.1 | <1.0g |
| Comparative example 2 | 88.00 | 99.5 | ＜ 0.1 | <1.0g |
| Comparative example 3 | 89.33 | 99.4 | ＜ 0.1 | <1.0g |
| Comparative example 4 | 87.33 | 99.1 | ＜ 0.1 | <1.0g |
By comparative example 1-comparative example 3 compared with embodiment 1-embodiment 6, the present invention prepares m-nitro first
During aldehyde, if the ratio of copper nitrate and benzaldehyde the least (such as comparative example 1-2), benzaldehyde reaction is incomplete,
The yield of nitrobenzaldehyde is on the low side；If the ratio of copper nitrate and benzaldehyde is too big (such as comparative example 3-4), benzaldehyde can fill
Divide reaction, but the yield of m-nitrobenzaldehyde does not the most have more preferably raising, but also some side reactions can be produced, cause
Yield and the decline of quality, it can be seen that, the mol ratio of copper nitrate and benzaldehyde elects 1.03-1.1:1.0 as.
In conjunction with prior art (content of background technology), comparative example 1-comparative example 3 and embodiment 1-embodiment 6
Understanding, the present invention has following technical effect that
1, raw material is readily available, and production cost is low.
2, processing step is simplified, and technological parameter is easily controlled, with short production cycle, it is simple to industrialized production.
3, the yield of m-nitrobenzaldehyde is high (higher than 90%), and chromatographic purity is more than 99.8%, the content of 1-Formyl-2-nitrobenzene
＜ 0.1%.
4, the Copper hydrate precipitation produced in production technology and the 3rd step filter mother liquid obtained all can realization recycle,
And the three wastes are few, pollute few, environmental protection.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for those skilled in the art
For Yuan, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, any amendment of being made,
Equivalent, improvement etc., should be included within the scope of the present invention.
Claims (7)
1. the synthetic method of a m-nitrobenzaldehyde, it is characterised in that comprise the following steps:
Step one: reaction, specifically: in reaction unit, add copper nitrate, water and silver nitrate, be warming up to 70 DEG C-80 DEG C；
Dropping benzaldehyde, time for adding is 1.8-2.5 hour；It is warming up to 85 DEG C-95 DEG C, is incubated and obtains reaction mixture in 2-3 hour；
From reaction mixture sampling carry out chromatograph detection, the content of benzaldehyde be less than 0.5%, wherein copper nitrate, water, silver nitrate with
And the mol ratio of benzaldehyde is 1.03-1.1:20-40:0.001-0.0012:1.0；
Step 2: m-nitrobenzaldehyde crude product processed, specifically: reaction mixture is filtered to remove hydroxide at 85 DEG C-95 DEG C
Copper precipitation obtains mother solution；Mother solution is cooled to 10 DEG C-20 DEG C；Cross leaching solid and i.e. obtain m-nitrobenzaldehyde crude product, described between
In nitrobenzaldehyde crude product, the content of 1-Formyl-2-nitrobenzene is less than 0.5%；
Step 3: the m-nitrobenzaldehyde of preparing high-purity, specifically: m-nitrobenzaldehyde crude product is loaded reaction unit, adds
Enter the water-soluble solvent of m-nitrobenzaldehyde crude product volume 3.0-3.5 times, be warming up to 50 DEG C-55 DEG C；Cross and filter to remove insoluble impurity
The water of rear addition water-soluble solvent same volume；Filter and dry after taking out the solid separated out, obtain high-purity m-nitro first
Aldehyde.
The synthetic method of m-nitrobenzaldehyde the most according to claim 1, it is characterised in that in described step one
Copper nitrate, silver nitrate, the quality standard of benzaldehyde are general industry grade standard.
The synthetic method of m-nitrobenzaldehyde the most according to claim 1, it is characterised in that in described reaction unit
Being provided with mixing component, in described step one and step 3, the stir speed (S.S.) of mixing component is 120-160 rev/min.
The synthetic method of m-nitrobenzaldehyde the most according to claim 1, it is characterised in that dry in described step 3
Dry temperature is 40 DEG C-50 DEG C, and the time is 8-12 hour.
5. according to the synthetic method of the m-nitrobenzaldehyde described in claim 1-4 any one, it is characterised in that described water
Soluble solvent is any one of methanol, ethanol, isopropanol, dimethylformamide and oxolane.
The synthetic method of m-nitrobenzaldehyde the most according to claim 5, it is characterised in that also include recycling step,
Described recycling step includes recycling step A and recycling step B, described recycling step A specifically: obtained by second step
Copper hydrate precipitation nitric acid is neutralized, the reaction being used in the first step by the copper nitrate solution obtained；Described recycling step
B is specifically: will filter in the 3rd step and mother liquid obtained be used as water-soluble solvent, wherein, water in the mother solution after process through processing
Content is less than 10%.
The synthetic method of m-nitrobenzaldehyde the most according to claim 6, it is characterised in that described recycling step B
The process step of middle mother solution is specifically: by mother solution suction recycling design rectifying column, controls temperature less than 60 DEG C, by adjusting
Joint reflux ratio, by moisture Control below 10%, collects midbarrel.
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| CN114478260A (en) * | 2021-12-30 | 2022-05-13 | 廊坊市北辰创业树脂材料股份有限公司 | Method for preparing m-nitrobenzaldehyde by using microchannel reactor |
| CN114478260B (en) * | 2021-12-30 | 2023-12-22 | 廊坊市北辰创业树脂材料股份有限公司 | Method for preparing m-nitrobenzaldehyde by utilizing microchannel reactor |
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