CN109369414A - A method of preparing the chloro- 2,4 difluorobenzene amine of Teflubenzuron intermediate 3,5- bis- - Google Patents
A method of preparing the chloro- 2,4 difluorobenzene amine of Teflubenzuron intermediate 3,5- bis- Download PDFInfo
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- CN109369414A CN109369414A CN201811357924.1A CN201811357924A CN109369414A CN 109369414 A CN109369414 A CN 109369414A CN 201811357924 A CN201811357924 A CN 201811357924A CN 109369414 A CN109369414 A CN 109369414A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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Abstract
The invention discloses a kind of methods for preparing the chloro- 2,4 difluorobenzene amine of Teflubenzuron intermediate 3,5- bis-: i.e. by raw material 3,5- bis- chloro- 2,4- difluoro nitrobenzene (II) prepares the chloro- 2,4 difluorobenzene amine (I) of 3,5- bis- of high-content in the presence of dehalogenation inhibitors, catalyst through hydrogen reducing.Synthesising method reacting condition of the invention is mild, is easy to control, and selectivity is high, and the three wastes are few, good product purity, high income, meet the demand for development of cleaning procedure, are very suitable for industrialized production.
Description
Technical field
The invention belongs to agricultural chemical insecticides to synthesize field, and in particular to a kind of to prepare Teflubenzuron intermediate 3,5- bis- chloro- 2,
The method of 4- difluoroaniline.
Background technique
3,5- bis- chloro- 2,4- difluoroanilines are the key intermediates of Insecticide Triflubenzuron, and Teflubenzuron is public by German Bayer
JelaiV Ferok company discovery belonging to department, obtains exploitation by Mitsubishi Chemical Industries Company and independent management produces and sells power
Process for preparation of benzoylurea compounds, registered in November 7 nineteen ninety；
The insecticide is with 30-150g (a.i.)/ha to Aleyrodidae, Diptera, Coleoptera, Hymenoptera, Lepidoptera and wood louse
The larva of section has preventive effect.For wild cabbage, citrus, cotton, grape, a kind of fruit, such as apple, pear, etc., potato, drupe, sorghum, soybean, trees, tobacco,
Vegetables.It can inhibit the development of juvenile stage insect, hinder decortication.A kind of suspending agent (150g/L) catches many parasitic insects
Feeding habits insect and spider are without effect.This product can also be used in the migratory locusts for preventing and treating most of juvenile stages.
Teflubenzuron is extremely low to people and animals' toxicity, and raw medicine is acute to rats and mice to be all larger than 5000mg/Kg through HLD；To rat acute
Percutaneous LD50Greater than 2000mg/Kg；It is 5038mg/M to rat sucking La；The medicament has a slight stimulation to lagophthalmos and skin, and two
Year feeding trial action-less dose are as follows: rat 5.38mg/Kg/d, dog 3.15mg/Kg/d.Through chronic toxicity, carcinogenicity and cause prominent
Denatured test shows that Teflubenzuron is fool proof to people and animals, to the LC of carp and trout50Greater than 500mg/L.
Teflubenzuron is a kind of novel process for preparation of benzoylurea compounds, and benzoyl urea compound is as the most important chitin of insect
Matter synthetic inhibitor obtains excellent effect with its unique insecticidal activity in terms of crop protection, especially removes to organic phosphorus, quasi-
Entomogenous fungi ester, 3 insecticides of carbamate have generated the pest controling effect of resistance more preferably.
Study the chloro- 2,4 difluorobenzene amine of key intermediate 3,5- bis- of Teflubenzuron, exploitation has product content height, quality
Good, high income and environmental-friendly catalytic hydrogenating reduction technique, are the clearer production technologies to attract attention at present.To further opening
The preparation method of hair Teflubenzuron has positive meaning.
Preparation for chloro- 2, the 4- difluoroaniline of 3,5- bis-, primary synthetic methods reported in the literature are as follows:
Iron powder reducing method under one, acid condition
Patent EP052833 is disclosed by chloro- 2, the 4- difluoro nitrobenzene of 3,5- bis-, in water/acetic acid in the mixed solvent 95-100
Iron powder reducing under the conditions of DEG C, alkali neutralization, steam distillation, then extracted with methylene chloride, it is concentrated to get fluoro- 3, the 5- dichloro of 2,4- bis-
Aniline；
Patent CN105801429A is disclosed with 1,2,3- trichloro-benzenes as starting material, and chloro- 2, the 4- difluoro of 3,5- bis- is made
After nitrobenzene, restore to obtain chloro- 2, the 4- difluoroaniline of 3,5- bis- with iron powder/ammonium chloride, synthetic method is as follows:
Patent CN1683318A disclose with iron powder ethyl alcohol in water mixed solvent, restored in the presence of acetic acid, ammonium chloride
The chloro- 2,4- difluoro nitrobenzene of 3,5- bis- obtains the chloro- 2,4 difluorobenzene amine of 3,5- bis-；
Lu Yang etc. is also through chloro- 2, the 4- difluoro nitrobenzene of 3,5- bis-, using iron powder in ethyl alcohol water mixed solvent, in vinegar
The chloro- 2,4 difluorobenzene amine of 3,5- bis- is made in the reduction chloro- 2,4- difluoro nitrobenzene of 3,5- bis- in the presence of acid, ammonium acetate；
Liu Changchun etc. report chloro- 2, the 4- difluoro nitrobenzene of 3,5- bis- be also use iron powder for reducing agent in water, ammonium chloride
In the presence of reduction obtain compound of formula I；
Iron powder reducing method under acid condition is the main side for producing chloro- 2, the 4- difluoroaniline of 3,5- bis- both at home and abroad at present
Method；Although the method has the advantages that production is easy to control, side reaction is few, selectivity is high and good product quality, the separation of product
It is mostly obtained by the way of organic solvent extraction or steam distillation, steam distillation separation can consume mass energy, generate
A large amount of waste water has in distillation process a large amount of tar to generate, and product loss is larger, and actual yield is lower；Organic solvent extraction is led
Severe operational environment is caused, active carbon decoloring, recrystallization is needed, also brings along environmental pollution；In short, iron powder reducing method is to environment
Seriously polluted, it is more that there are the three wastes, long flow path, and a large amount of iron cements are difficult to handle, and three-protection design expense is high, and severe operational environment etc. lacks
Point, is unfavorable for industrialized production.
Two, catalytic hydrogenation process
Patent CN102617360A is disclosed with the chloro- 3- fluoronitrobenzene bottoms of 2,4- bis- for starting material, first through chlorine
Change, be fluorinated obtained chloro- 2, the 4- difluoro nitrobenzene of 3,5- bis- then using 5% palladium carbon as catalyst and is with ammonium formate in methyl alcohol
Hydrogen source restores and chloro- 2, the 4- difluoroaniline of 3,5- bis-, yield 95.4% is made；3,5- bis- chloro- 2,4- difluoro nitrobenzenes in DMF,
Respectively using Raney's nickel and 5% palladium carbon as catalyst, chloro- 2, the 4- difluoroaniline of 3,5- bis- is made in hydro-reduction, and yield is respectively
93% and 95%, product assay and dehalogenated by-product content are not reported；
Through actual experiment, it is found that the method actual selection is poor, side reaction is more, have a large amount of dehalogenated products, coloured product compared with
Difference, purity is low, causes yield relatively low, is unfavorable for industrialized production.
Patent CN1683318A is disclosed with 2,4- difluoro nitrobenzene as starting material, and chloro- 2, the 4- bis- of 3,5- bis- is first made
Fluoronitrobenzene, and in solvent DMF, in the presence of Raney's nickel or palladium-carbon catalyst plus chloro- 2, the 4- difluoro of 3,5- bis- is made in hydrogen
Aniline, yield are respectively 90.6% and 93.2%, and product assay and dehalogenated by-product content are not reported.Synthetic route is as follows:
A large amount of dehalogenated by-products are equally had during above-mentioned hydro-reduction to generate, and are caused under equipment corrosion and product purity
Drop, yield is relatively low, and coloured product is poor, is unfavorable for industrialized production.
Patent CN1310162A is disclosed with chloro- 2, the 4- difluoro nitrobenzene of 3,5- bis-, directly using Pd/C as catalyst,
Chloro- 2, the 4- difluoroaniline of 3,5- bis- is made in 3MPa, 60 DEG C of hydro-reductions, and yield 95.1%, product assay and dehalogenated by-product contain
Amount is not also reported；It necessarily has a large amount of dehalogenated by-products according to the principle of the reaction, in reduction process to generate, product purity is big
It is big to reduce, it makes troubles to product separation, is unfavorable for industrialized production.
Catalytic hydrogenation process says there is apparent advantage in terms of the three wastes；But the selectivity of catalytic hydrogenation process is poor,
Side reaction is more, is easy to happen dehalogenation, contains the nitro for containing multiple halogens in multiple nitros or molecule in especially same molecule
Compound, compound 3 as described herein, chloro- 2, the 4- difluoro nitrobenzene of 5- bis- is such；
In consideration of it, above-mentioned related chloro- 2, the 4- difluoro nitrobenzene of 3,5- bis- reported in the literature is reduced into chloro- 2, the 4- bis- of 3,5- bis-
The method of fluoroaniline, all existing defects to a certain extent all do not report product assay although yield can be accomplished higher, real
Border product purity, color are poor, and especially dehalogenated by-product is more.
The present invention prevents the generation of by-product, passes through research, screening 3% to improve catalyst to the selectivity of reaction
Platinum carbon be hydrogenation catalyst, while joined specific a small amount of co-catalyst and inhibiting dehalogenated by-product, substantially increase product
The purity of 3,5- bis- chloro- 2,4- difluoroanilines is convenient for industrialized production without purifying.
Summary of the invention
The object of the invention is primarily to solve the chloro- 2,4- difluoro nitrobenzene reduction synthesis 3,5- bis- of existing 3,5- bis- chloro-
Three-waste pollution present in 2,4 difluorobenzene amine method is high, dehalogenation is not easily purified, causes that high production cost, product colour be poor, nothing
The technical problems such as method large-scale production provide a kind of synthetic method of new chloro- 2,4- difluoroaniline of 3,5- bis-.
In order to achieve the above object, the technical scheme is that
A kind of to prepare Teflubenzuron intermediate 3, the method for chloro- 2, the 4- difluoroaniline of 5- bis- includes the following steps:
The chloro- 2,4- difluoro nitrobenzene of 3,5- bis- hydrogenates for 0~100 DEG C in the presence of dehalogenation inhibitors, hydrogenation catalyst
Reduction reaction obtains reduzate, refilters, and washing, extraction is concentrated up to chloro- 2, the 4- difluoroaniline of 3,5- bis-；Above-mentioned reaction equation
It is as follows:
Preferably, the dehalogenation inhibitors are phosphoric acid；Further, the concentration of the phosphoric acid is 0.1~85%；More into one
Step, the concentration of the phosphoric acid is 75~85%.
Preferably, the catalyst is Pt/C；Further, the concentration of the Pt/C is 1~10%.
Preferably, the molar ratio of chloro- 2, the 4- difluoro nitrobenzene of 3, the 5- bis- and dehalogenation inhibitors is 1:0.01~0.2；
Further, the molar ratio of chloro- 2, the 4- difluoro nitrobenzene of 3, the 5- bis- and dehalogenation inhibitors is 1:0.05~0.1.
Preferably, the molar ratio of chloro- 2, the 4- difluoro nitrobenzene of 3, the 5- bis- and catalyst is 1:0.0001~0.01；Into
One step, the molar ratio of chloro- 2, the 4- difluoro nitrobenzene of 3, the 5- bis- and catalyst is 1:0.0005~0.001.
Preferably, the hydro-reduction reaction temperature is 20~100 DEG C；Further, the hydro-reduction reaction temperature
It is 75~80 DEG C.
Preferably, the hydro-reduction reaction time is 0.5~24 hour；Further, when the hydro-reduction reacts
Between be 4~6 hours；
Preferably, reaction dissolvent is methanol, ethyl alcohol or isopropanol in the hydro-reduction reaction；The 3,5- bis- chloro- 2,
The mass ratio of 4- difluoro nitrobenzene and reaction dissolvent is 1:7~10.
Preferably, the hydro-reduction reaction pressure is 1.0~2.5MPa, preferably 1.0~1.5MPa.
Using the method reaction condition temperature provided by the invention for preparing the chloro- 2,4 difluorobenzene amine of Teflubenzuron intermediate 3,5- bis-
Be easy to control, selectivity is high, and the three wastes are few, good product purity, high income, meet the demand for development of cleaning procedure, are very suitable to
In industrialized production.
Specific embodiment
Embodiment 1
In the stainless steel autoclave for the 500ml for equipping logical hydrogen mouth, cooling circulating water, pressure gauge and electric heater unit
In, methanol 160g, chloro- 2, the 4- difluoro nitrobenzene 22.8g (0.1mol) of compound (II) 3,5- bis- is added, 3% platinum is added in stirring
Carbon 0.80g, 85% phosphoric acid 0.85g (0.007mol), then with 20g methanol flushing pipe, close kettle；Wherein the mole of platinum carbon calculates
Mode is 0.80* (1-60% is aqueous) * 3% butt platinum content/195.078 platinum molecular weight=0.0000492mol；
It is first passed through hydrogen and replaces 2~3 times to 0.2~0.4MPa of internal pressure, afterwards logical hydrogen to 1.0~1.5MPa of internal pressure, and control
75~80 DEG C of temperature is stirred to react, and during which to be added hydrogen and no longer be declined to pressure.HPLC monitoring raw material (II) disappears or contains substantially
Amount is lower than 0.5%；6h is reacted, reaction solution filters, and filter residue is washed 2 times with methanol, each 10ml；Solid platinum carbon recovery；
Filtrate decompression recycles methanol to a large amount of faint yellow solids and most do is precipitated；Stirring instills water 50g, quickly 30 points of stirring
Clock slowly cools to 0~5 DEG C of crystallization 1h, and filtering is drained, and solid is washed till neutrality again with water digging, then with water 10g rinsing, 50 DEG C often
Pressure dry off-white color to white powdery solids, weight: 19.0g, content 97.2%；Yield: 96.0%.
1HNMR (400MHz, CDCl3) δ ppm:6.70-6.75 (m, 1H), 3.74 (s, 2H).
Embodiment 2
In the stainless steel autoclave for the 500ml for equipping logical hydrogen mouth, cooling circulating water, pressure gauge and electric heater unit
In, ethyl alcohol 230g, chloro- 2, the 4- difluoro nitrobenzene 22.8g (0.1mol) of compound (II) 3,5- bis- is added, 3% platinum is added in stirring
Carbon 0.80g (0.0000492mol), 75% phosphatase 11 .31g (0.01mol), then with 20g ethyl alcohol flushing pipe, close kettle；
It is first passed through hydrogen and replaces 2~3 times to 0.2~0.4MPa of internal pressure, afterwards logical hydrogen to 1.5~2.0MPa of internal pressure, and control
75~80 DEG C of temperature is stirred to react, and during which to be added hydrogen and no longer be declined to pressure.HPLC monitoring raw material (II) disappears or contains substantially
Amount is lower than 0.5%；4h is reacted, reaction solution filters, and filter residue is washed 2 times with methanol, each 10ml；Solid platinum carbon recovery；
Decompression filtrate recycling ethanol to a large amount of faint yellow solids are precipitated dry to the greatest extent；Stirring instills water 50g, quickly 30 points of stirring
Clock slowly cools to 0~5 DEG C of crystallization 1h, and filtering is drained, and solid is washed till neutrality again with water digging, then with water 10g rinsing, 50 DEG C often
Pressure dry off-white color to white powdery solids, weight: 19.0g, content 96.9%；Yield: 95.9%.
1HNMR (400MHz, CDCl3) δ ppm:6.70-6.75 (m, 1H), 3.74 (s, 2H).
Embodiment 3:
In the stainless steel autoclave for the 500ml for equipping logical hydrogen mouth, cooling circulating water, pressure gauge and electric heater unit
In, methanol 160g, chloro- 2, the 4- difluoro nitrobenzene 22.8g (0.1mol) of compound (II) 3,5- bis- is added, 3% platinum is added in stirring
Carbon 1.62g (0.001mol), then with 20g methanol flushing pipe, close kettle；
Hydrogen is first passed through to internal pressure 0.2-0.4MPa displacement 2-3 times, logical hydrogen to internal pressure 1.0-1.5MPa, and temperature control afterwards
75-80 DEG C is stirred to react, and during which to add hydrogen and no longer decline to pressure.It is low that HPLC monitors raw material (II) disappearance or content substantially
In 0.5%；15h is reacted, reaction solution filters, and filter residue is washed 2 times with methanol, each 10ml.Solid platinum carbon recovery；
Filtrate decompression recycles methanol to a large amount of faint yellow solids and most do is precipitated；Stirring instills water 50g, quickly 30 points of stirring
Clock slowly cools to 0-5 DEG C of crystallization 1h, and filtering is drained, and solid is washed till neutrality again with water digging, then with water 10g rinsing, 50 DEG C often
Pressure dries to obtain light brown powder shape solid, weight: 18.0g, content 91.8%, yield: 90.9%.
In the case where other reaction conditions are constant, test is compared to the condition in production method of the invention, is obtained
The result arrived is as shown in the table:
As seen from the above table: selecting 3%Pt/C as main hydrogenation catalyst in technical solution of the present invention, when using 85%
Compound I purity, the color that phosphoric acid obtains when being dehalogenation inhibitors are preferable；Lead to product I when using other dehalogenation inhibitors
It needs by further separating and purifying, cumbersome, colour-difference, content decline, production cost greatly improves, and is unfavorable for big
The industrial production of scale, yield are greatly reduced；When being restored using other hydrogenation catalysts, since dehalogenation generates other
By-product, the yield and purity of product can all glide, and be unfavorable for the generation of product.
What has been described above is only a preferred embodiment of the present invention, it is noted that for those of ordinary skill in the art
For, without departing from the concept of the premise of the invention, various modifications and improvements can be made, these belong to the present invention
Protection scope.
Claims (10)
1. a kind of prepare Teflubenzuron intermediate 3, the method for chloro- 2, the 4- difluoroaniline of 5- bis-, it is characterised in that include the following steps:
The chloro- 2,4- difluoro nitrobenzene of 3,5- bis- 0~100 DEG C of generation hydro-reduction in the presence of dehalogenation inhibitors, hydrogenation catalyst
Reaction, obtains reduzate, refilters, and washes, and extraction is concentrated up to chloro- 2, the 4- difluoroaniline of 3,5- bis-；Above-mentioned reaction equation is as follows:
2. preparing Teflubenzuron intermediate 3, the method for chloro- 2, the 4- difluoroaniline of 5- bis- as described in claim 1, feature exists
In the dehalogenation inhibitors are phosphoric acid.
3. preparing Teflubenzuron intermediate 3, the method for chloro- 2, the 4- difluoroaniline of 5- bis- as claimed in claim 2, feature exists
In the concentration of the phosphoric acid is 75~85%.
4. preparing Teflubenzuron intermediate 3, the method for chloro- 2, the 4- difluoroaniline of 5- bis- as described in claim 1, feature exists
In the molar ratio of chloro- 2, the 4- difluoro nitrobenzene of 3, the 5- bis- and dehalogenation inhibitors is 1:0.05~0.1.
5. preparing Teflubenzuron intermediate 3, the method for chloro- 2, the 4- difluoroaniline of 5- bis- as described in claim 1, feature exists
In the molar ratio of 3, the 5- bis- chloro- 2,4- difluoro nitrobenzene and catalyst are as follows: 0.0001-0.01.
6. preparing Teflubenzuron intermediate 3, the method for chloro- 2, the 4- difluoroaniline of 5- bis- as described in claim 1, feature exists
In the hydro-reduction reaction temperature is 20~100 DEG C.
7. preparing Teflubenzuron intermediate 3, the method for chloro- 2, the 4- difluoroaniline of 5- bis- as described in claim 1, feature exists
In the hydro-reduction reaction time is 0.5~24 hour.
8. preparing Teflubenzuron intermediate 3, the method for chloro- 2, the 4- difluoroaniline of 5- bis- as described in claim 1, feature exists
In reaction dissolvent is methanol, ethyl alcohol or isopropanol in the hydro-reduction reaction.
9. preparing Teflubenzuron intermediate 3, the method for chloro- 2, the 4- difluoroaniline of 5- bis- as claimed in claim 8, feature exists
In the mass ratio of chloro- 2, the 4- difluoro nitrobenzene of 3, the 5- bis- and reaction dissolvent is 1:7~10.
10. preparing Teflubenzuron intermediate 3, the method for chloro- 2, the 4- difluoroaniline of 5- bis- as described in claim 1, feature exists
In the hydro-reduction reaction pressure is 1.0~2.5MPa.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63290850A (en) * | 1987-05-25 | 1988-11-28 | Nippon Kayaku Co Ltd | Production of fluorinated aromatic amine |
| CN1310162A (en) * | 2000-02-24 | 2001-08-29 | 大连绿源实业有限公司 | 2,4,6-trichloro-3,5-difluoro acetophenone and its preparation |
| CN101811973A (en) * | 2010-04-23 | 2010-08-25 | 浙江工业大学 | Method for synthesizing halogen aromatic amines by high-selectivity liquid phase hydrogenation under the condition of no solvent |
| CN102617360A (en) * | 2012-03-01 | 2012-08-01 | 江西吉翔医药化工有限公司 | Synthetic method of 3, 5-dichloro-2, 4-difluoroaniline |
| CN105418439A (en) * | 2015-11-17 | 2016-03-23 | 山东沾化天九化工有限公司 | Method and device for producing 3-chlorine-4-fluoroaniline |
| CN106905104A (en) * | 2017-01-03 | 2017-06-30 | 浙江巍华化工有限公司 | A kind of synthetic method of the fluoride trifluoro toluene of 2 bromine 5 |
-
2018
- 2018-11-15 CN CN201811357924.1A patent/CN109369414B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63290850A (en) * | 1987-05-25 | 1988-11-28 | Nippon Kayaku Co Ltd | Production of fluorinated aromatic amine |
| CN1310162A (en) * | 2000-02-24 | 2001-08-29 | 大连绿源实业有限公司 | 2,4,6-trichloro-3,5-difluoro acetophenone and its preparation |
| CN101811973A (en) * | 2010-04-23 | 2010-08-25 | 浙江工业大学 | Method for synthesizing halogen aromatic amines by high-selectivity liquid phase hydrogenation under the condition of no solvent |
| CN102617360A (en) * | 2012-03-01 | 2012-08-01 | 江西吉翔医药化工有限公司 | Synthetic method of 3, 5-dichloro-2, 4-difluoroaniline |
| CN105418439A (en) * | 2015-11-17 | 2016-03-23 | 山东沾化天九化工有限公司 | Method and device for producing 3-chlorine-4-fluoroaniline |
| CN106905104A (en) * | 2017-01-03 | 2017-06-30 | 浙江巍华化工有限公司 | A kind of synthetic method of the fluoride trifluoro toluene of 2 bromine 5 |
Non-Patent Citations (1)
| Title |
|---|
| 陆阳: "苯甲酰脲类杀虫剂伏虫隆合成新工艺", 《现代农药》 * |
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