CN106854162A - A kind of nitroaniline of 2,3 dichloro 6 and preparation method thereof - Google Patents
A kind of nitroaniline of 2,3 dichloro 6 and preparation method thereof Download PDFInfo
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- CN106854162A CN106854162A CN201611145132.9A CN201611145132A CN106854162A CN 106854162 A CN106854162 A CN 106854162A CN 201611145132 A CN201611145132 A CN 201611145132A CN 106854162 A CN106854162 A CN 106854162A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 title abstract description 4
- 125000003963 dichloro group Chemical group Cl* 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 52
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 31
- BGKIECJVXXHLDP-UHFFFAOYSA-N 1,2,3-trichloro-4-nitrobenzene Chemical class [O-][N+](=O)C1=CC=C(Cl)C(Cl)=C1Cl BGKIECJVXXHLDP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006396 nitration reaction Methods 0.000 claims abstract description 21
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 15
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical class ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 52
- AWZRAQWGIUYTOH-UHFFFAOYSA-N n-chloro-2-nitroaniline Chemical class [O-][N+](=O)C1=CC=CC=C1NCl AWZRAQWGIUYTOH-UHFFFAOYSA-N 0.000 claims description 32
- 229910021529 ammonia Inorganic materials 0.000 claims description 26
- 239000010410 layer Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 16
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000009413 insulation Methods 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 11
- 238000011084 recovery Methods 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000013517 stratification Methods 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 239000012044 organic layer Substances 0.000 claims description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 claims description 2
- 229910017435 S2 In Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000005915 ammonolysis reaction Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 description 11
- 230000036632 reaction speed Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000004176 ammonification Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 150000008422 chlorobenzenes Chemical class 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CMVQZRLQEOAYSW-UHFFFAOYSA-N 1,2-dichloro-3-nitrobenzene Chemical class [O-][N+](=O)C1=CC=CC(Cl)=C1Cl CMVQZRLQEOAYSW-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- NTBYINQTYWZXLH-UHFFFAOYSA-N 1,2-dichloro-4-nitrobenzene Chemical class [O-][N+](=O)C1=CC=C(Cl)C(Cl)=C1 NTBYINQTYWZXLH-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 0 C[C@@](C*#C[I+])*CN Chemical compound C[C@@](C*#C[I+])*CN 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- HFZKOYWDLDYELC-UHFFFAOYSA-N Cc(c(C)c1)ccc1[N+]([O-])=O Chemical compound Cc(c(C)c1)ccc1[N+]([O-])=O HFZKOYWDLDYELC-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FSGTULQLEVAYRS-UHFFFAOYSA-N Nc(cc(c(Cl)c1)Cl)c1[N+]([O-])=O Chemical compound Nc(cc(c(Cl)c1)Cl)c1[N+]([O-])=O FSGTULQLEVAYRS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001555 benzenes Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- -1 nitre ion Chemical class 0.000 description 1
- 230000001546 nitrifying effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/52—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of nitroaniline of 2,3 dichloro 6 and preparation method thereof, belong to organic synthesis field.The present invention prepares the nitroaniline of 2,3 dichloro 6 by two-step method, and first with 1,2,3 trichloro-benzenes are raw material, in sulfuric acid system, nitration reaction is carried out with nitric acid, prepares 2,3,4 trichloronitrobenzenes；Then 2,3,4 trichloronitrobenzenes issue raw ammonolysis reaction with ammoniacal liquor at 120 150 DEG C in organic solvent, and DCONA is obtained.This preparation method is simple to operate, and reaction condition is gentle, and yield and purity are higher, and environmental protection, and the sulfuric acid that is used in preparation process, organic solvent, ammoniacal liquor can be reclaimed effectively.
Description
Technical field
The present invention relates to one kind chloro- 6- nitroanilines of 2,3- bis- and preparation method thereof, belong to organic synthesis field.
Background technology
Chloro- 6- nitroanilines (DCONA) molecular formula of 2,3- bis- are C6H4Cl2N2O2, it is a kind of important pesticide intermediate,
In the prior art, the preparation of DCONA is main with o-dichlorohenzene as raw material, through nitration reaction, isolate 2,3- dichloronitrobenzenes and
3,4- dichloronitrobenzenes, wherein 2,3- dichloronitrobenzenes are again through reduction, nitrification synthesis target product (route A)；3 for isolating,
4- dichloronitrobenzenes synthesize target product (route B) through ammonification.
The raw material of this process route is readily available, but product is not readily separated, in order to make full use of raw material, it is necessary to design
Two sets of production technologies, easily cause when feeding intake and alter material, to difficulty is brought in management, increased the potential safety hazard in production；Together
When, in A routes, amide nitration reaction terminates rear sulfuric acid and is unable to recovery, and environmental protection pressure is than larger.And in B routes also
The chloro- 6- nitroanilines of 3.4- bis- can be produced, it is as follows, there are problems that separating.
The content of the invention
The present invention overcomes the deficiencies in the prior art, there is provided a kind of high income, simple to operate, and reaction condition is gentle, green ring
The preparation method of chloro- 6 nitroanilines of 2,3- bis- of guarantor.
The purpose of the present invention can be realized by following technical proposal：2,3- bis- chloro- 6- nitroanilines, its hydrogen nuclear magnetic resonance
The chemical shift of spectrum is 8.02 (d, J=9.3Hz, 1H), 7.55 (s, 2H), 6.90 (d, J=9.3Hz, 1H).
The preparation method of the chloro- 6- nitroanilines of one kind 2,3- bis-, the preparation method is comprised the following steps：
The preparation of S1,2,3,4- trichloronitrobenzene：To sulfuric acid and 1 is pumped into nitration reaction kettle, 2,3- trichloro-benzenes are opened and stirred
Mix, temperature of reaction kettle is risen to 45-55 DEG C, after treating that 1,2,3- trichloro-benzenes all dissolve, pumped into toward head tank well mixed
Sulfuric acid and nitric acid, nitration mixture is added drop-wise in nitration reaction kettle, and time for adding is 20-35min, after completion of dropping, in certain temperature
The lower insulation reaction of degree, after reaction terminates, stratification, sulfuric acid layer goes recovery kettle distillation treatment rear enclosure to use, and the bed of material is washed with water, point
Water layer is removed, 2,3,4- trichloronitrobenzene crude products are obtained, lower step is directly used in and is fed intake；
The preparation of the chloro- 6- nitroanilines of S2,2,3- bis-：Organic solvent, ammoniacal liquor are pumped into toward autoclave and through S1 steps
2,3, the 4- trichloronitrobenzenes for preparing, open stirring, at a certain temperature insulation reaction, after reaction terminates, are cooled to room temperature, feed liquid
It is layered in press filtration to layering kettle, organic layer is used through Distillation recovery rear enclosure, the recovered treatment rear enclosure use of ammoniacal liquor layer, filter cake is through 40-60
DEG C hot wash obtains target product 2, the chloro- 6- nitroanilines of 3- bis- to neutrality, after drying.
Wherein the mass fraction of sulfuric acid is 98%, and the mass fraction of nitric acid is 95%.
In nitration reaction, using nitric acid and sulfuric acid as nitrating agent, the reaction between two kinds of acid can produce nitre ion
(NO2 +), NO2 +Attack 1,2,3- trichloro-benzenes phenyl ring, the H on substituted benzene ring+, the reaction mechanism mechanism of reaction is as follows：
From the foregoing, it will be observed that NO in course of reaction2 +Concentration have influence on reaction speed and conversion ratio, and NO2 +Concentration depend on again
In HNO3And H2SO4Concentration in the reactive mixture, NO2 +Concentration is general to be risen and decline with water concentration, therefore in high concentration
H2SO4In, HNO3Almost all ion turns to NO2 +, increase NO2 +Concentration, promotes reaction.
There is ammonolysis reaction in 2,3,4- trichloronitrobenzenes, DCONA is obtained under the high temperature conditions with ammoniacal liquor in organic solvent,
Its reaction equation is as follows：
Ammonolysis are substantially nucleophilic displacement reaction, due to the effect of the electron withdraw groups such as nitro and chlorine substituent, make its ortho position
Electron deficient and band δ+, so the amino molecule with unshared electron pair is to the carbon atom generation nucleophilic being connected with ortho position chlorine on phenyl ring
Attack, obtain middle the addition compound product with polarized, the rapid armaticity for converting and recovering phenyl ring of its addition compound product, then again with
The reaction of one molecules of ammonia obtains product.The reaction needs to be carried out in aprotic polar solvent, and solvent polarization makes ammonia
Molecule polarizes, and produces more NH2 -Ion attack δ+Position, promotes amino reaction to carry out.Simultaneously appropriate reaction temperature energy
NH is enough provided2 -Ion attack δ+The activation energy of position, accelerates reaction.
Preferably, the nitric acid in step S1 and 1, the mol ratio of 2,3- trichloro-benzenes is (1.05-1.15):1, sulfuric acid dehydration
Value (the weight ratio of sulfuric acid and its reclaimed water in spent acid) DVS is 3-5.From above-mentioned nitration reaction reaction equation, NO2 +Concentration
Have influence on reaction speed and final conversion ratio, and NO2 +Concentration depends on HNO again3And H2SO4Concentration in the reactive mixture.By
In the electrophilic inductive effect of chlorine substituent so that the velocity constant K values of second step reaction are very small, only as the NO for producing2 +
When concentration is sufficiently large, the reaction speed and final conversion ratio of nitrification are just shown, thus when nitric acid and 1,2,3- trichloro-benzenes rub
When that ratio and DVS reach certain numerical value, reaction speed and final conversion ratio can just be improved, when nitric acid and 1,2,3- trichlorines
The mol ratio of benzene is (1.05-1.15)：1, DVS be 3-5 when, conversion ratio substantially remains in more than 98%.
Preferably, the insulation reaction temperature in step S1 is 50-60 DEG C, the reaction time is 2-3h.With temperature and instead
Rising nitration product yield and reaction speed between seasonable are improved, reacted at 50-60 DEG C 2-3h yields substantially remain in 96% with
On, temperature is too high, the reaction time is long, there is side reaction, influences yield and increases energy consumption.
Preferably, the organic solvent in step S2 is one or more in benzene, chlorobenzene, dimethylbenzene, chloroform.The reaction
Needs are carried out in aprotic polar solvent, and solvent polarization makes amino molecule polarize, and produce more NH2 -Ion attack
δ+Position, promotes amino reaction to carry out.Further preferably, organic solvent is chlorobenzene.Chlorobenzene is repeatable by simple distillation treatment
Use, the DCONA for obtaining is easy to separate because being precipitated insoluble in chlorobenzene.
Preferably, 2,3,4- trichloronitrobenzenes and the weight ratio of ammoniacal liquor are 1 in step S2：(3-8).Excess of ammonia water can
The solubility of 2,3,4- trichloronitrobenzenes is improved, improves the mobility of reaction mass, reduce accessory substance NH4Corrosion of the Cl to equipment
Property, but consumption is excessive, can increase the recovery load of ammonia, reduces the generative capacity of equipment.
Preferably, the mass percent concentration of ammoniacal liquor is 25-50% in step S2.The concentration of ammoniacal liquor increases, and can improve
Solubility of 2,3, the 4- trichloronitrobenzenes in ammoniacal liquor, accelerates reaction speed, and improve feed stock conversion.But dissolved by ammonia
The limitation of degree, the ammoniacal liquor for configuring high concentration is relatively difficult, and at that same temperature, the concentration of vapour pressure and ammonia is directly proportional, and pair sets
Standby voltage endurance capability proposes requirement higher.Therefore present invention selection ammonia concn is 25-50%.
Preferably, the insulation reaction temperature in step S2 is 120-150 DEG C, the reaction time is 5-10h.Improving temperature can
To increase solubility of 2,3, the 4- trichloronitrobenzenes in ammoniacal liquor, there is provided NH higher2 -Ion attack δ+The activation energy of position, accelerates
Reaction speed, but with the rising of temperature, reaction pressure is also increased, and the requirement to equipment will be improved, and energy consumption also increases therewith
Greatly.Simultaneously as ammonolysis are exothermic reaction, if reaction is too fast, will shift reaction heat and difficulty occurs, so as to cause local mistake
Heat, causes vicious circle.
Preferably, the recovery ammoniacal liquor layer step described in step S2 is as follows：Alkaline matter is added by the ammonium in ammoniacal liquor layer
After ion conversion is free ammonia, then heating evaporation is carried out；Free ammonia in steam is returned after being absorbed with water and prepares the chloro- 6- of 2,3- bis-
The burden process of nitroaniline.In the preparation process of DCONA, the accessory substance NH of generation4Cl is dissolved in ammoniacal liquor layer, can be with alkalescence
Substance reaction generates free ammonia, and after heated evaporation and water absorb, the ammoniacal liquor of generation can be recycled, and reduce ammonia in production process
The usage amount of water.
Preferably, described alkaline matter is one or more in calcium oxide, calcium hydroxide, NaOH.Enter one
Step is preferred, and described alkaline matter is calcium oxide.Calcium oxide and NH4Cl reacts to form ammonia and calcium chloride solution, and calcium chloride is molten
Liquid recyclable calcium chloride powder after evaporation process.
The chemical equation of synthetic method of the invention is as follows：
Compared with prior art, the invention has the advantages that：
With 1,2,3- trichloro-benzenes are raw material to the present invention, by synthesizing DCONA after nitrification and ammonification, solvent in the technical process
Usage amount is less, and more based on water solvent, the sulfuric acid in nitrifying process can reach the purpose of recovery by simple process,
And the waste water containing ammonia and ammonium chloride in ammonifying process is processed through the absorption of pervaporation water, it is recycled and recycles free ammonia, reduces
The consumption of ammonia, greatly reduces environmental protection pressure.The technological reaction condition is relatively mild simultaneously, and process safety is higher, by-product
The few high income of thing, yield >=98%, product purity relatively up to more than 97% is not required to carry out purification processes to can be used or sell,
It is simple to operate, easily realize industrialized production.
Brief description of the drawings
Fig. 1 is DCONA liquid chromatograms prepared by embodiment 2.
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of DCONA of the present invention.
Specific embodiment
The following is specific embodiment of the invention, technical scheme is further described with reference to accompanying drawing, but
The present invention is not limited to these embodiments.
Embodiment 1
The preparation method of the chloro- 6- nitroanilines of 2,3- bis- is comprised the following steps：
The preparation of S1,2,3,4- trichloronitrobenzene：To pumping into the 1 of the sulfuric acid of 200g 98% and 1816g in nitration reaction kettle,
2,3- trichloro-benzenes, open stirring, and temperature of reaction kettle is risen into 45 DEG C, after treating that 1,2,3- trichloro-benzenes all dissolve, the pump toward head tank
Enter well mixed 551g98% sulfuric acid and the nitric acid of 696g 95%, nitric acid and 1, the mol ratio of 2,3- trichloro-benzenes is 1.05：1, sulphur
Sour dehydration value DVS is 3.2.Nitration mixture is added drop-wise in nitration reaction kettle, time for adding is 20min, after completion of dropping, reaction
Temperature is 50 DEG C, insulation reaction 3h；After reaction terminates, stratification, sulfuric acid layer is gone to reclaim kettle distillation treatment rear enclosure use, and the bed of material is used
Water washing, branch vibration layer obtains the trichloronitrobenzene crude products of 2239g 2,3,4-, is directly used in lower step and feeds intake；
The preparation of the chloro- 6- nitroanilines of S2,2,3- bis-：3000g chlorobenzenes, 11195g ammoniacal liquor and warp are pumped into toward autoclave
2,3,4- trichloronitrobenzenes prepared by S1 steps, the mass percent concentration of ammoniacal liquor is 30%, 2,3,4- trichloronitrobenzenes and ammonia
The weight ratio of water is 1：5.Stirring is opened, reaction temperature is 120 DEG C, insulation reaction 10h, and after reaction terminates, logical cooling water makes reaction
Liquid is cooled to room temperature, is layered in feed liquid press filtration to layering kettle, and chlorobenzene layer is used through Distillation recovery rear enclosure, is added in ammoniacal liquor layer and aoxidized
Calcium, after ammonium ion therein is converted into free ammonia, then carries out heating evaporation；Free ammonia in steam returns to system after being absorbed with water
The burden process of the chloro- 6- nitroanilines of standby 2,3- bis-；Filter cake obtains target product through 40-60 DEG C of hot wash to neutrality, after drying
The chloro- 6- nitroanilines of thing 2,3- bis-.
The DCONA product liquid chromatograies purity for obtaining is 97.2%, and yield is 98.2%.
Embodiment 2
The preparation method of the chloro- 6- nitroanilines of 2,3- bis- is comprised the following steps：
The preparation of S1,2,3,4- trichloronitrobenzene：To pumping into the sulfuric acid of 250g 98% and 2179g 1,2 in nitration reaction kettle,
3- trichloro-benzenes, opens stirring, and temperature of reaction kettle is risen into 50 DEG C, after treating that 1,2,3- trichloro-benzenes all dissolve, is pumped into toward head tank
Well mixed 749g98% sulfuric acid and the nitric acid of 875g 95%, nitric acid and 1, the mol ratio of 2,3- trichloro-benzenes is 1.10：1, sulfuric acid
Dehydration value DVS is 3.5.Nitration mixture is added drop-wise in nitration reaction kettle, time for adding is 30min, after completion of dropping, reaction temperature
It is 55 DEG C to spend, insulation reaction 2.5h；After reaction terminates, stratification, sulfuric acid layer is gone to reclaim kettle distillation treatment rear enclosure use, and the bed of material is used
Water washing, branch vibration layer obtains the trichloronitrobenzene crude products of 2688g 2,3,4-, is directly used in lower step and feeds intake；
The preparation of the chloro- 6- nitroanilines of S2,2,3- bis-：3500g chlorobenzenes, 10752g ammoniacal liquor and warp are pumped into toward autoclave
2,3,4- trichloronitrobenzenes prepared by S1 steps, the mass percent concentration of ammoniacal liquor is 35%, 2,3,4- trichloronitrobenzenes and ammonia
The weight ratio of water is 1：4.Stirring is opened, reaction temperature is 130 DEG C, insulation reaction 7h, and after reaction terminates, logical cooling water makes reaction solution
Room temperature is cooled to, is layered in feed liquid press filtration to layering kettle, chlorobenzene layer is used through Distillation recovery rear enclosure, and calcium oxide is added in ammoniacal liquor layer,
After ammonium ion therein is converted into free ammonia, then carry out heating evaporation；Free ammonia in steam is returned after being absorbed with water and prepared
The burden process of the chloro- 6- nitroanilines of 2,3- bis-；Filter cake obtains target product through 40-60 DEG C of hot wash to neutrality after drying
The chloro- 6- nitroanilines of 2,3- bis-.
The yield of DCONA is 98.9%.Obtained DCONA in the present embodiment is done into liquid phase detection, liquid chromatogram is obtained such as
Shown in Fig. 1, the appearance time of DCONA is 6.26min, and it is 97.4% to use area normalization method to calculate product purity.
Embodiment 3
The preparation method of the chloro- 6- nitroanilines of 2,3- bis- is comprised the following steps：
The preparation of S1,2,3,4- trichloronitrobenzene：To pumping into the sulfuric acid of 400g 98% and 2724g 1,2 in nitration reaction kettle,
3- trichloro-benzenes, opens stirring, and temperature of reaction kettle is risen into 55 DEG C,；After treating that 1,2,3- trichloro-benzenes all dissolve, pumped into toward head tank
Well mixed 1009g98% sulfuric acid and the nitric acid of 1143g 95%, nitric acid and 1, the mol ratio of 2,3- trichloro-benzenes is 1.15：1, sulphur
Sour dehydration value DVS is 3.9.Nitration mixture is added drop-wise in nitration reaction kettle, time for adding is 30min, after completion of dropping, reaction
Temperature is 60 DEG C, insulation reaction 2h；After reaction terminates, stratification, sulfuric acid layer is gone to reclaim kettle distillation treatment rear enclosure use, and the bed of material is used
Water washing, branch vibration layer obtains the trichloronitrobenzene crude products of 3373g 2,3,4-, is directly used in lower step and feeds intake；
The preparation of the chloro- 6- nitroanilines of S2,2,3- bis-：4000 chlorobenzenes, 10121g ammoniacal liquor and warp are pumped into toward autoclave
2,3,4- trichloronitrobenzenes prepared by S1 steps, the mass percent concentration of ammoniacal liquor is 40%, 2,3,4- trichloronitrobenzenes and ammonia
The weight ratio of water is 1：3.Stirring is opened, reaction temperature is 145 DEG C, insulation reaction 5h, and after reaction terminates, logical cooling water makes reaction solution
Room temperature is cooled to, is layered in feed liquid press filtration to layering kettle, chlorobenzene layer is used through Distillation recovery rear enclosure, and calcium oxide is added in ammoniacal liquor layer,
After ammonium ion therein is converted into free ammonia, then carry out heating evaporation；Free ammonia in steam is returned after being absorbed with water and prepared
The burden process of the chloro- 6- nitroanilines of 2,3- bis-；Filter cake obtains target product through 40-60 DEG C of hot wash to neutrality after drying
The chloro- 6- nitroanilines of 2,3- bis-.
The DCONA product liquid chromatograies purity for obtaining is 97.9%, and yield is 99.2%.
In sum, with 1,2,3- trichloro-benzenes are raw material to the present invention, and through nitrification, ammonification two-step reaction synthesizes DCONA, should
Sulfuric acid and ammonia in method can be recycled well by treatment, environmental protection；The technological reaction condition is relatively warm
It it is 120-150 DEG C with, aminating reaction temperature, the reaction time is 5-10h, the DCONA chromatographic purities of acquisition are up to more than 97%, yield
>=98%.
The DCONA samples of present invention synthesis are carried out into hydrogen nuclear magnetic resonance analysis of spectrum, Fig. 2 is as a result seen, its proton nmr spectra
Chemical shift be 8.02 (d, J=9.3Hz, 1H), 7.55 (s, 2H), 6.90 (d, J=9.3Hz, 1H).
Specific embodiment described herein is only to the spiritual explanation for example of the present invention.Technology neck belonging to of the invention
The technical staff in domain can be made various modifications or supplement to described specific embodiment or be replaced using similar mode
Generation, but without departing from spirit of the invention or surmount scope defined in appended claims.
Claims (10)
1.2,3- bis- chloro- 6- nitroanilines, it is characterised in that the chemical shift of its proton nmr spectra is 8.02 (d, J=
9.3Hz, 1H), 7.55 (s, 2H), 6.90 (d, J=9.3Hz, 1H).
2. one kind 2, the preparation method of the chloro- 6- nitroanilines of 3- bis-, it is characterised in that the preparation method is comprised the following steps：
The preparation of S1,2,3,4- trichloronitrobenzene：To sulfuric acid and 1 is pumped into nitration reaction kettle, 2,3- trichloro-benzenes will react kettle temperature
Degree rises to 45-55 DEG C, after treating that 1,2,3- trichloro-benzenes all dissolve, well mixed sulfuric acid and nitric acid is pumped into toward head tank, will
Nitration mixture is added drop-wise in nitration reaction kettle, after completion of dropping, insulation reaction, and after question response terminates, stratification, sulfuric acid layer goes to reclaim
Kettle distillation treatment rear enclosure is used, and the bed of material is washed with water, obtains 2,3,4- trichloronitrobenzene crude products；
The preparation of the chloro- 6- nitroanilines of S2,2,3- bis-：Organic solvent, ammoniacal liquor are pumped into toward autoclave and is prepared through S1 steps
2,3,4- trichloronitrobenzenes, insulation reaction after reaction terminates, is cooled to room temperature, and feed liquid press filtration is layered to being layered in kettle, organic
Layer through Distillation recovery rear enclosure use, ammoniacal liquor layer it is recovered treatment rear enclosure use, filter cake through 40-60 DEG C of hot wash to neutrality, after drying
Obtain the chloro- 6- nitroanilines of target product 2,3- bis-.
3. the preparation method of one kind chloro- 6 nitroanilines of 2,3- bis- according to claims 2, it is characterised in that step S1
In the mol ratio of nitric acid and 1,2,3- trichloro-benzenes be (1.05-1.15):1, dehydrating value of sulfuric acid DVS are 3-5.
4. the preparation method of one kind chloro- 6 nitroanilines of 2,3- bis- according to claims 2, it is characterised in that step S1
In insulation reaction temperature be 50-60 DEG C, the reaction time is 2-3h.
5. the preparation method of one kind chloro- 6 nitroanilines of 2,3- bis- according to claims 2, it is characterised in that step S2
Middle organic solvent is one or more in benzene, chlorobenzene, dimethylbenzene, chloroform.
6. the preparation method of one kind chloro- 6 nitroanilines of 2,3- bis- according to claims 2, it is characterised in that step S2
Middle 2,3,4- trichloronitrobenzenes are 1 with the weight ratio of ammoniacal liquor：(3-8).
7. the preparation method of one kind chloro- 6 nitroanilines of 2,3- bis- according to claims 2 or 6, it is characterised in that institute
The mass percent concentration for stating ammoniacal liquor is 25-50%.
8. the preparation method of one kind chloro- 6 nitroanilines of 2,3- bis- according to claims 2, it is characterised in that step S2
In insulation reaction temperature be 120-150 DEG C, the reaction time is 5-10h.
9. the preparation method of one kind chloro- 6 nitroanilines of 2,3- bis- according to claims 2, it is characterised in that step S2
Described in recovery ammoniacal liquor layer step it is as follows：After adding alkaline matter that the ammonium ion in ammoniacal liquor layer is converted into free ammonia, then enter
Row heating evaporation；Free ammonia in steam returns to the burden process for preparing the chloro- 6- nitroanilines of 2,3- bis- after being absorbed with water.
10. the preparation method of one kind chloro- 6 nitroanilines of 2,3- bis- according to claims 9, it is characterised in that described
Alkaline matter be one or more in calcium oxide, calcium hydroxide, NaOH.
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| CN114230471A (en) * | 2021-11-09 | 2022-03-25 | 河北科技大学 | A kind of preparation method of 3,4-dichloro-2-fluoroaniline |
| CN114349647A (en) * | 2021-10-29 | 2022-04-15 | 陕西菲尔特化工有限公司 | Synthetic method of aclonifen |
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| CN111646907A (en) * | 2020-06-18 | 2020-09-11 | 常州沃腾化工科技有限公司 | Preparation method of 2, 3-dichloro-6-nitroaniline |
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| CN114349647A (en) * | 2021-10-29 | 2022-04-15 | 陕西菲尔特化工有限公司 | Synthetic method of aclonifen |
| CN114349647B (en) * | 2021-10-29 | 2024-01-09 | 陕西菲尔特化工有限公司 | Synthesis method of aclonifen |
| CN114230471A (en) * | 2021-11-09 | 2022-03-25 | 河北科技大学 | A kind of preparation method of 3,4-dichloro-2-fluoroaniline |
| CN114230471B (en) * | 2021-11-09 | 2024-01-26 | 河北科技大学 | Preparation method of 3, 4-dichloro-2-fluoroaniline |
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