CN104529786B - The synthetic method of the fluoro- 2 '-nitrobiphenyl of 3,4,5- tri- - Google Patents
The synthetic method of the fluoro- 2 '-nitrobiphenyl of 3,4,5- tri- Download PDFInfo
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Abstract
The present invention provides a kind of synthetic method of 3,4,5- tri- fluoro- 2 '-nitrobiphenyls, synthetic routes are as follows:Wherein, substituent group representated by-X is-Cl ,-Br ,-I, COOH ,-N2Cl、‑N2HSO4In any one；Its synthesis step includes: that 3,4,5- trifluoro phenyl boric acid of raw material, adjacent nitro substituted benzene are dissolved in solvent, and catalyst and acid binding agent are added by (1)；(2) it is stirred to react, until terminating；(3) it washes, extracts to obtain organic phase；(4) it is concentrated, recrystallizes to obtain 3,4,5- tri- fluoro- 2 '-nitrobiphenyls.The present invention uses a kind of Ms-Pd catalyst, and catalytic activity is high, and can realize it is multiple batches of apply, high income, product purity is high, and convenient post-treatment is environmentally protective.
Description
Technical field
The present invention relates to a kind of important intermediate for synthesizing fluorobenzene pyrrole bacterium amine more particularly to a kind of functional group's biphenol compounds
Synthesis, the synthetic method of specially 3,4,5- tri- fluoro- 2 '-nitrobiphenyls.
Background technique
Functional group's biphenol compound is widely used directly or indirectly in drug due to the physics of its own, chemical property
In the synthesis and preparation of pesticide, it is a kind of very important body compound, studies its synthetic method for the hair of related fields
Exhibition is of great significance.
Wherein, 3,4,5- tri- fluoro- 2 '-nitrobiphenyls are in field of fine chemical as a kind of functional group's biphenol compound
Important intermediate, it is particularly possible to the synthesis material as insecticide fluorobenzene pyrrole bacterium amine.Join about the fluoro- 2 '-nitro of 3,4,5- tri-
Benzene: its molecular formula are as follows: C12H6F3NO2；Chemical name are as follows: the fluoro- 2 '-nitrobiphenyl of 3,4,5- tri-；English name are as follows: 3,4,5-
Trifluoro-2'-nitrobiphenyl；No. CAS are as follows: 1056196-56-5；Structural formula are as follows:
The preparation method of the fluoro- 2 '-nitrobiphenyl of 3,4,5- tri- is mainly carried out by coupling reaction.It is synthesized about the intermediate
Document, report and data it is seldom, and some special, homemade catalyst are often used in practical synthesis process, it is right
In 3,4, the 5- tri- fluoro- large-scale production applications of 2 '-nitrobiphenyl, without notable contribution.Wherein, patent (PCT
2009156359), disclose it is a kind of with 2,2- dimethyl -1,3-, bis- diphenylphosphine propane (CAS:80326-98-3) be raw material,
PdCl2For catalyst, and the method for synthesizing above-mentioned biphenol compound under high temperature and pressure, still, the catalyst is without purchase
Source is cannot getting well as a result, moreover, synthetic environment needs usually because of catalyst problem during replicating its synthetic method
So high temperature, high pressure are difficult the large-scale application in plant produced.
Therefore, for may be implemented the synthetic method of the large-scale production of 3,4,5- tri- fluoro- 2 '-nitrobiphenyls, and can be with
The deficiencies in the prior art are solved, are always those skilled in the art's expectation, and never have the problem solved.
Summary of the invention
In order to solve the prior art existing defect in practical applications, solves current those skilled in the art and not yet capture
Difficulty, realize the fluoro- 2 '-nitrobiphenyl of 3,4,5- tri- large-scale production, the present invention provides one kind 3,4,5- tri- fluoro- 2 '-
The new and effective new synthetic method of nitrobiphenyl, wherein the catalytic activity of used catalyst is high, and multiple batches of set may be implemented
With；The synthetic method reaction step is short, operating condition is mild, spent acid is few.With synthetic method high income, good product purity,
The advantages that convenient post-treatment, cost of material are low, environmentally protective, the prospect with industrialized production.
The theme of the first aspect of the present invention is a kind of synthesis road of the synthetic method of the fluoro- 2 '-nitrobiphenyl of 3,4,5- tri-
Line, which is characterized in that are as follows:
Wherein, substituent group representated by-X is-Cl ,-Br ,-I, COOH ,-N2Cl、-N2HSO4In any one.
A kind of preferred embodiment of the synthetic route according to the present invention, wherein-X is preferably-I.
The theme of the second aspect of the present invention is a kind of synthetic method of 3,4,5- tri- fluoro- 2 '-nitrobiphenyls, and feature exists
In, including
Step 1: 3,4,5- trifluoro phenyl boric acid of raw material, adjacent nitro substituted benzene being dissolved in solvent, and catalyst is added and ties up
Sour agent；
Step 2: being stirred to react, until terminating；
Step 3: washing extracts to obtain organic phase；
Step 4: concentration obtains 3,4,5- tri- fluoro- 2 '-nitrobiphenyls.
A kind of preferred embodiment according to a second aspect of the present invention, in the step 1:
Wherein, any one of the solvent in protonic solvent, non-protonic solvent: the protonic solvent packet
Include methanol, ethyl alcohol, propyl alcohol, isopropanol, water, formic acid and acetic acid, preferably methanol；The non-protonic solvent includes N, N- diformazan
Base formamide, acetone, ethyl acetate, methylene chloride, ether, carbon tetrachloride, toluene, benzene, n-hexane, hexamethylene, tetrahydrofuran,
Chloroform, preferably toluene.
Wherein, the catalyst is noble metal catalyst, including PdCl2、Pd(PPh3)4, Ms-Pd (molecular sieve complex compound),
Pd/C、Pd(OAc)2、Pt/C、PtCl2, triphenylphosphine carbonyl hydrogenation Rh (I), two (triphenylphosphine) carbonyl radium chlorides, two (triphens
Base phosphine) palladium chloride, bis- (dibenzyl acetyl) palladiums, platinum dioxide, triphenylphosphine radium chloride, bis- (1,4- biphenyl phosphine) butyl dichloros
Change palladium (II), ruthenium charcoal (Ru/C), four (triphenylphosphine) platinum, any one in ruthenium trichloride, more preferably Ms-Pd catalyst.
Further, the preparation method of the Ms-Pd catalyst, comprising:
Step 1: by PdCl2It is added in organic solvent with 4A molecular sieve；
Step 2: stirring, until terminating；
Step 3: filtering, and filter cake is dried, obtain white powdery solids, as Ms-Pd catalyst.
Preferably, the 4A molecular sieve is dry through Muffle furnace, is 80-100 mesh；
Preferably, the organic solvent includes acetone, acetonitrile, any one or a few the mixed liquor in methanol；
Preferably, the mixing time is at least two days.
Wherein, the acid binding agent is inorganic base, any one in organic base: inorganic base includes sodium hydroxide, hydroxide
Potassium, sodium carbonate, potassium carbonate, any one in lithium hydroxide, more preferably potassium hydroxide；Organic base include triethylamine, pyridine,
Sodium methoxide, sodium ethoxide, tetrabutylammonium hydroxide, lithium alkylide, any one in lithium amide, more preferably pyridine.
Wherein, the usage amount of the catalyst is the 0.1%-10% of 3,4,5- tri- fluoro- 2 '-nitrobiphenyl weight, more excellent
It is selected as 0.5%.
A kind of preferred embodiment according to a second aspect of the present invention, in the step 2:
Wherein, the temperature being stirred to react is 0-100 DEG C, preferably 35-45 DEG C, more preferably 40 DEG C.
A kind of preferred embodiment according to a second aspect of the present invention, in the step 3:
Wherein, it is 2-10 that the terminal of the washing, which is the aqueous pH values of last time washing, more preferably 3-6.
A kind of preferred embodiment according to a second aspect of the present invention, in the step 4:
The mode being concentrated preferably by vacuum distillation.
The new synthetic method of of the present invention 3,4,5- tri- fluoro- 2 '-nitrobiphenyls, by adopting the above-described technical solution,
It has the following advantages and beneficial effects:
The new and effective synthetic method of (1) 3,4,5- tri- fluoro- 2 '-nitrobiphenyls, synthesis step is short, simple process, solvent
Cost decline is obvious；
(2) above-mentioned novel preparation method can realize continuous production, and multiple batches of reaction is applied, and catalyst activity is high, react item
Part is mild, three-waste free discharge, meet the requirement of environmental protection；
(3) technique post-processing is simple, and 3,4,5- tri- fluoro- 2 '-nitrobiphenyls can be obtained in extraction concentration, organic solvent purification
(purity 97%).
Specific embodiment
The present invention provides a kind of synthetic route of the synthetic method of 3,4,5- tri- fluoro- 2 '-nitrobiphenyls, feature exists
In, are as follows:
Wherein, substituent group representated by-X is-Cl ,-Br ,-I, COOH ,-N2Cl、-N2HSO4In any one, preferably
For-I.
The present invention also provides a kind of synthetic methods of 3,4,5- tri- fluoro- 2 '-nitrobiphenyls characterized by comprising
Step 1: 3,4,5- trifluoro phenyl boric acid of raw material, adjacent nitro substituted benzene being dissolved in solvent, and catalyst is added and ties up
Sour agent；
Step 2: being stirred to react, until terminating；
Step 3: washing extracts to obtain organic phase；
Step 4: concentration recrystallizes to obtain 3,4,5- tri- fluoro- 2 '-nitrobiphenyls.
A kind of preferred embodiment according to a second aspect of the present invention, in the step 1:
Wherein, any one of the solvent in protonic solvent, non-protonic solvent: the protonic solvent packet
Include methanol, ethyl alcohol, propyl alcohol, isopropanol, water, formic acid and acetic acid, preferably methanol；The non-protonic solvent includes N, N- diformazan
Base formamide, acetone, ethyl acetate, methylene chloride, ether, carbon tetrachloride, toluene, benzene, n-hexane, hexamethylene, tetrahydrofuran,
Chloroform, preferably toluene.
Wherein, the catalyst is noble metal catalyst, including PdCl2、Pd(PPh3)4, Ms-Pd (molecular sieve complex compound),
Pd/C、Pd(OAc)2、Pt/C、PtCl2, triphenylphosphine carbonyl hydrogenation Rh (I), two (triphenylphosphine) carbonyl radium chlorides, two (triphens
Base phosphine) palladium chloride, bis- (dibenzyl acetyl) palladiums, platinum dioxide, triphenylphosphine radium chloride, bis- (1,4- biphenyl phosphine) butyl dichloros
Change palladium (II), ruthenium charcoal (Ru/C), four (triphenylphosphine) platinum, any one in ruthenium trichloride, more preferably Ms-Pd catalyst.
Further, the preparation method of the Ms-Pd catalyst, comprising:
Step 1: by PdCl2It is added in organic solvent with 4A molecular sieve；
Step 2: stirring, until terminating；
Step 3: filtering, and filter cake is dried, obtain white powdery solids, as Ms-Pd catalyst.
Preferably, the 4A molecular sieve is dry through Muffle furnace, is 80-100 mesh；
Preferably, the organic solvent includes acetone, acetonitrile, any one or a few the mixed liquor in methanol；
Preferably, the mixing time is at least two days.
Wherein, the acid binding agent is inorganic base, any one in organic base: inorganic base includes sodium hydroxide, hydroxide
Potassium, sodium carbonate, potassium carbonate, any one in lithium hydroxide, more preferably potassium hydroxide；Organic base include triethylamine, pyridine,
Sodium methoxide, sodium ethoxide, tetrabutylammonium hydroxide, lithium alkylide, any one in lithium amide, more preferably pyridine.
Wherein, the usage amount of the catalyst is the 0.1%-10% of 3,4,5- tri- fluoro- 2 '-nitrobiphenyl weight, more excellent
It is selected as 0.5%.
A kind of preferred embodiment according to a second aspect of the present invention, in the step 2:
Wherein, the temperature being stirred to react is 0-100 DEG C, more preferably 40 DEG C.
Wherein, the reaction terminates to determine preferably by the method for liquid phase tracking raw material.
A kind of preferred embodiment according to a second aspect of the present invention, in the step 3:
Wherein, it is 2-10 that the terminal of the washing, which is the aqueous pH values of last time washing, more preferably 3-6.
A kind of preferred embodiment according to a second aspect of the present invention, in the step 4:
The mode being concentrated preferably by vacuum distillation.
The recrystallization is preferably n-hexane, and 3 obtained, 4,5- tri- fluoro- 2 '-nitrobiphenyls are pale yellow crystals solid,
78.1-78.3 DEG C of fusing point, liquid content is more than or equal to 97%.
Wherein, 3,4,5- tri- fluoro- 2 '-nitrobiphenyls analyze data:1H NMR(400MHz,CDCl3)δ8.00-8.05(m,
2H),7.90-7.75(m,1H),7.67-7.55(m,1H),7.27-7.14(m,2H)ppm；13C NMR(100MHz,CDCl3)δ
151.9,151.0,141.2,139.1,136.5,135.1,129.4,128.5,128.0,124.7,113.8,112.5ppm。
The technical solution of the new synthetic method of described 3,4,5- tri- fluoro- 2 '-nitrobiphenyls according to the present invention, enumerates embodiment
To be further explained and illustrate to it, to more fully understand the present invention.
Embodiment 1 --- about screening of catalyst
1, synthetic route:
2, synthetic method (being carried out according to table 1):
Step 1: opening up 4 reactions, 3,4,5- trifluoro phenyl boric acid of raw material, o-chloronitrobenzene are dissolved in solvent DMF, added
Enter acid binding agent triethylamine, and is separately added into catalyst Pt Cl2、Pd(OAc)2、Pd(PPh3)4, Ms-Pd, additional amount 0.5%；
Step 2: at 30 DEG C, being stirred to react, liquid phase tracks raw material after the reaction was completed, stops reaction；
Step 3: recycling design and catalyst, crude product is by washing, extracting to obtain organic phase；
Step 4: concentration, the optimal result that n-hexane is recrystallized to give 3,4,5- tri- fluoro- 2 '-nitrobiphenyls is 24.0g, light
Yellow crystalline solid, 78.1-78.3 DEG C of fusing point, liquid content 97%.1H NMR(400MHz,CDCl3)δ8.00-8.05(m,
2H),7.90-7.75(m,1H),7.67-7.55(m,1H),7.27-7.14(m,2H)ppm；13C NMR(100MHz,CDCl3)δ
151.9,151.0,141.2,139.1,136.5,135.1,129.4,128.5,128.0,124.7,113.8,112.5ppm。
3, result:
Table 1: the test result of catalyst screening
| Number | Catalyst | Acid binding agent | Temperature (DEG C) | Solvent | Yield |
| 1 | PtCl2 | Triethylamine | 30 | DMF | 75% |
| 2 | Pd(OAc)2 | Triethylamine | 30 | DMF | 64% |
| 3 | Pd(PPh3)4 | Triethylamine | 30 | DMF | 55% |
| 4 | Ms-Pd | Triethylamine | 30 | DMF | 88% |
Embodiment 2 --- the screening about-X
1, synthetic route:
2, synthetic method (being carried out according to table 2):
Step 1: opening up 3 reactions, 3,4,5- trifluoro phenyl boric acid of raw material, 3 kinds of adjacent nitro substituted benzenes are dissolved in solvent respectively
In methanol, and acid binding agent sodium bicarbonate and catalyst PdCl is added2, additional amount 0.5%；
Step 2: at 40 DEG C, being stirred to react, liquid phase tracks raw material after the reaction was completed, stops reaction；
Step 3: recycling design and catalyst, crude product is by washing, extracting to obtain organic phase；
Step 4: concentration obtains 3,4,5- tri- fluoro- 2 '-nitrobiphenyls.
3, result:
The test result of table 2:-X screening
| Number | -X | Catalyst | Acid binding agent | Temperature (DEG C) | Solvent | Yield |
| 1 | -Cl | PdCl2 | Sodium bicarbonate | 40 | Methanol | 90% |
| 2 | -Br | PdCl2 | Sodium bicarbonate | 40 | Methanol | 94% |
| 3 | -I | PdCl2 | Sodium bicarbonate | 40 | Methanol | 98% |
Embodiment 3 --- the screening about temperature
1, synthetic route:
2, synthetic method (being carried out according to table 3):
Step 1: 5 reactions are opened up, 3,4,5- trifluoro phenyl boric acid of raw material, o-chloronitrobenzene are dissolved in solvent DMF, and
Acid binding agent sodium bicarbonate and catalyst Ms-Pd, additional amount 0.5% is added；
Step 2: respectively at 0 DEG C, 20 DEG C, 40 DEG C, 60 DEG C, 80 DEG C, being stirred to react, liquid phase tracks raw material reaction and completes
Afterwards, stop reaction；
Step 3: recycling design and catalyst, crude product is by washing, extracting to obtain organic phase；
Step 4: concentration obtains 3,4,5- tri- fluoro- 2 '-nitrobiphenyls.
3, result:
Table 3: the test result of temperature screening
| Number | Temperature (DEG C) | Catalyst | Acid binding agent | Solvent | Yield |
| 1 | 0 | Ms-Pd | Sodium bicarbonate | DMF | 80% |
| 2 | 20 | Ms-Pd | Sodium bicarbonate | DMF | 83% |
| 3 | 40 | Ms-Pd | Sodium bicarbonate | DMF | 88% |
| 4 | 60 | Ms-Pd | Sodium bicarbonate | DMF | 90% |
| 5 | 80 | Ms-Pd | Sodium bicarbonate | DMF | 88% |
Specific embodiments of the present invention are described in detail above, but it is merely an example, the present invention is simultaneously unlimited
It is formed on particular embodiments described above.To those skilled in the art, any couple of present invention carries out equivalent modifications and
Substitution is also all among scope of the invention.Therefore, without departing from the spirit and scope of the invention made by equal transformation and
Modification, all should be contained within the scope of the invention.
Claims (6)
1. one kind 3,4, the synthetic method of the fluoro- 2 '-nitrobiphenyl of 5- tri-, which is characterized in that
Its synthetic route are as follows:
Wherein, substituent group representated by-X is-Cl ,-Br ,-I ,-COOH ,-N2Cl、-N2HSO4In any one；
Its synthesis step includes:
Step 1: 3,4,5- trifluoro phenyl boric acid of raw material, adjacent nitro substituted benzene are dissolved in solvent, and catalyst and acid binding agent are added,
The catalyst is molecular sieve complex compound Ms-Pd；
Step 2: being stirred to react, until terminating；
Step 3: washing extracts to obtain organic phase；
Step 4: concentration recrystallizes to obtain 3,4,5- tri- fluoro- 2 '-nitrobiphenyls；
The recrystallization uses hexane solution, 3 obtained, and 4,5- tri- fluoro- 2 '-nitrobiphenyls are pale yellow crystals solid, melts
78.1-78.3 DEG C of point, liquid content are more than or equal to 97%；
Wherein, in the step 2, the reaction temperature being stirred to react is 35-45 DEG C；
The washing in the step 3 refers to that aqueous pH values be 3-6.
2. the synthetic method of 3,4,5- tri- fluoro- 2 '-nitrobiphenyls according to claim 1, which is characterized in that-the X be-
I。
3. the synthetic method of 3,4,5- tri- fluoro- 2 '-nitrobiphenyls according to claim 1, which is characterized in that the step 1
In any one in protonic solvent, non-protonic solvent of the solvent,
Wherein, the protonic solvent is selected from methanol, ethyl alcohol, propyl alcohol, isopropanol, water, formic acid, acetic acid；Wherein, described non-proton
Property solvent be selected from n,N-Dimethylformamide, acetone, ethyl acetate, methylene chloride, ether, carbon tetrachloride, toluene, benzene, just oneself
Alkane, hexamethylene, tetrahydrofuran, chloroform.
4. the synthetic method of 3,4,5- tri- fluoro- 2 '-nitrobiphenyls according to claim 1, which is characterized in that the catalyst
For molecular sieve complex compound Ms-Pd, preparation method includes:
Step 1: by PdCl2It is added in organic solvent with 4A molecular sieve；
Step 2: stirring, until terminating；
Step 3: filtering, and filter cake is dried, obtain white powdery solids, as molecular sieve complex compound Ms-Pd；
Wherein, the 4A molecular sieve is dry through Muffle furnace, is 80-100 mesh；
Wherein, any one or a few mixed liquor of the organic solvent in acetone, acetonitrile, methanol；
Wherein, the mixing time of the stirring is at least two days.
5. the synthetic method of 3,4,5- tri- fluoro- 2 '-nitrobiphenyls according to claim 1, which is characterized in that the acid binding agent
It is inorganic base, any one in organic base:
Wherein, any one of the inorganic base in sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium hydroxide；
Wherein, the organic base is selected from triethylamine, pyridine, sodium methoxide, sodium ethoxide, tetrabutylammonium hydroxide, lithium alkylide, lithium amide
In any one.
6. the synthetic method of 3,4,5- tri- fluoro- 2 '-nitrobiphenyls according to claim 1, which is characterized in that the catalyst
Usage amount be the fluoro- 2 '-nitrobiphenyl weight of 3,4,5- tri- 0.1%-10%.
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| CN105399635B (en) * | 2015-12-15 | 2017-07-28 | 上海师范大学 | The method that microwave synthesizes the biphenyl of 2 nitro, 3 ', 4 ', 5 ' trifluoro 1,1 ' |
| CN107344913A (en) * | 2016-05-06 | 2017-11-14 | 上海泰禾国际贸易有限公司 | A kind of preparation method of tri- fluoro- 2 '-nitrobiphenyls of 3,4,5- |
| CN107488113B (en) * | 2016-06-13 | 2020-05-12 | 上海泰禾国际贸易有限公司 | Method for synthesizing o-aminobiphenyl compound |
| KR102550878B1 (en) * | 2016-08-22 | 2023-07-04 | 바스프 에스이 | Methods for preparing substituted biphenyls |
| CN106518755B (en) * | 2016-09-28 | 2019-04-26 | 江苏中邦制药有限公司 | A kind of method synthesizing 2,3- dichloropyridine |
| CN106986774B (en) * | 2017-05-11 | 2019-01-22 | 蚌埠中实化学技术有限公司 | A kind of preparation method of 2 nitro biphenyl |
| CN107382734A (en) * | 2017-07-21 | 2017-11-24 | 南通嘉禾化工有限公司 | The Suzuki coupling reactions of the ammino palladium chtalyst nitro-chlorobenzene of dichloro two |
| CN109956871B (en) * | 2017-12-25 | 2022-03-29 | 浙江省化工研究院有限公司 | Preparation method of 3,4, 5-trifluoro-2' -nitrobiphenyl |
| CN111606808A (en) * | 2020-06-09 | 2020-09-01 | 温州大学 | Synthetic method of 3 ', 4', 5 '-trifluoro-2-nitro-1, 1' -biphenyl |
| CN113185404B (en) * | 2021-04-30 | 2022-08-05 | 武汉大学 | 1, 2-biaxial chiral biaryl compound and preparation method and application thereof |
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