CN1535944A - Chemical method for sythesizing dipheny ether compound - Google Patents
Chemical method for sythesizing dipheny ether compound Download PDFInfo
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- CN1535944A CN1535944A CNA031162223A CN03116222A CN1535944A CN 1535944 A CN1535944 A CN 1535944A CN A031162223 A CNA031162223 A CN A031162223A CN 03116222 A CN03116222 A CN 03116222A CN 1535944 A CN1535944 A CN 1535944A
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- ether compound
- diphenyl ether
- phenol
- ionic liquid
- positively charged
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- -1 dipheny ether compound Chemical class 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000000126 substance Substances 0.000 title claims description 8
- 239000002608 ionic liquid Substances 0.000 claims abstract description 30
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 11
- 150000001450 anions Chemical class 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- 239000012429 reaction media Substances 0.000 claims abstract description 5
- 230000035484 reaction time Effects 0.000 claims abstract description 4
- 150000002500 ions Chemical class 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims description 2
- 239000003814 drug Substances 0.000 abstract description 3
- 150000001768 cations Chemical class 0.000 abstract 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 238000010924 continuous production Methods 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 238000005580 one pot reaction Methods 0.000 abstract 1
- 239000000575 pesticide Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 238000004821 distillation Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000005484 Bifenox Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- HHMCAJWVGYGUEF-UHFFFAOYSA-N Fluorodifen Chemical compound C1=CC([N+](=O)[O-])=CC=C1OC1=CC=C(C(F)(F)F)C=C1[N+]([O-])=O HHMCAJWVGYGUEF-UHFFFAOYSA-N 0.000 description 2
- SUSRORUBZHMPCO-UHFFFAOYSA-N MC-4379 Chemical compound C1=C([N+]([O-])=O)C(C(=O)OC)=CC(OC=2C(=CC(Cl)=CC=2)Cl)=C1 SUSRORUBZHMPCO-UHFFFAOYSA-N 0.000 description 2
- NUFNQYOELLVIPL-UHFFFAOYSA-N acifluorfen Chemical compound C1=C([N+]([O-])=O)C(C(=O)O)=CC(OC=2C(=CC(=CC=2)C(F)(F)F)Cl)=C1 NUFNQYOELLVIPL-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- CONWAEURSVPLRM-UHFFFAOYSA-N lactofen Chemical compound C1=C([N+]([O-])=O)C(C(=O)OC(C)C(=O)OCC)=CC(OC=2C(=CC(=CC=2)C(F)(F)F)Cl)=C1 CONWAEURSVPLRM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DGRVQOKCSKDWIH-UHFFFAOYSA-N 1-chloro-2-(trifluoromethyl)benzene Chemical class FC(F)(F)C1=CC=CC=C1Cl DGRVQOKCSKDWIH-UHFFFAOYSA-N 0.000 description 1
- TZGFQIXRVUHDLE-UHFFFAOYSA-N 1-chloro-2-nitro-4-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(C(F)(F)F)=CC=C1Cl TZGFQIXRVUHDLE-UHFFFAOYSA-N 0.000 description 1
- WFQDTOYDVUWQMS-UHFFFAOYSA-N 1-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C=C1 WFQDTOYDVUWQMS-UHFFFAOYSA-N 0.000 description 1
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 1
- ZGGSVBWJVIXBHV-UHFFFAOYSA-N 2-chloro-1-(4-nitrophenoxy)-4-(trifluoromethyl)benzene Chemical compound C1=CC([N+](=O)[O-])=CC=C1OC1=CC=C(C(F)(F)F)C=C1Cl ZGGSVBWJVIXBHV-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- 244000026610 Cynodon dactylon var. affinis Species 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- LCAUVFVOLNRVKG-UHFFFAOYSA-N methyl 5-fluoro-2-nitrobenzoate Chemical class COC(=O)C1=CC(F)=CC=C1[N+]([O-])=O LCAUVFVOLNRVKG-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QULYNCCPRWKEMF-UHFFFAOYSA-N parachlorobenzotrifluoride Chemical compound FC(F)(F)C1=CC=C(Cl)C=C1 QULYNCCPRWKEMF-UHFFFAOYSA-N 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- IPBVNPXQWQGGJP-UHFFFAOYSA-N phenyl acetate Chemical compound CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229960004839 potassium iodide Drugs 0.000 description 1
- 235000007715 potassium iodide Nutrition 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The chemical synthesis method of diphenyl ether compound adopts the room temp. ionic liquid formed from N-alkylpyridine cation or 1,3-dialkylimidazole cation and fluorine-containing anion as reaction medium, uses phenol and aromatic halohydrocarbon as reaction mass, and adopts continuous process or one-pot process under the basic condition to synthesize diphenyl ether compound. As compared with traditional synthesis method said invented method has the advantages of moderate reaction condition, short reaction time, high product yield and good quality, etc. Said diphenyl ether compound is a kind is important medicine and pesticide product or organic intermediate body, so that it has extensive application.
Description
Technical field
The present invention relates to a kind of chemical synthesis process of diphenyl ether compound.Present method is applicable to that by N-alkyl pyridine positively charged ion or 1 ionic liquid at room temperature that 3-dialkylimidazolium positively charged ion and fluo anion are formed is as reaction medium, and phenol and aromatic halohydrocarbon synthesize the occasion of diphenyl ether compound as reactant under alkaline condition.
Background technology
Diphenyl ether compound is important organic synthesis intermediate of a class or product, is widely used in fields such as medicine and agricultural chemicals.Its prior synthesizing method is normally carried out (J.B.Hendrickson, C.Kandall, Tetrahedron Lett., 1970,5,343 in aprotic polar solvent such as acetone, acetonitrile, dimethyl formamide, methyl-sulphoxide or tetramethylene sulfone; R.A.W.Johnstone, M.E.Rose, Tetrahedron, 1979,35,2169; A.Mckillop, J.C.Fiaud, R.P.Hug, Tetrahedron, 1974,30,1379; H.H.Freedaman, R.A.Duboes, Tetrahedron Lett., 1975,38,3251.), need to add little amount of catalyst such as potassiumiodide, Tetrabutyl amonium bromide etc. sometimes to promote reaction.However, thus still existing long, reaction solvent of reaction times and catalyzer to be difficult to recycle causes environmental pollution, reaction solvent to problems such as operator's poisonous and harmfuls.
Ionic liquid at room temperature is called " planner's solvent " again, is meant the material that is made of ion that is in a liquid state under near temperature room temperature or the room temperature.Over past ten years, because ion liquid specific composition more and more causes Synthetic Organic Chemistry worker's extensive concern.Compare with traditional organic solvent, water, supercutical fluid, ionic liquid has that liquid wide ranges, soluble end are wide, zero vapour pressure, good stability, acid-basicity can be in harmonious proportion superiority such as electrochemical window is wide.Just because of ion liquid peculiar property, in many building-up reactionss of having reported are used, ionic liquid has shown high selectivity, good reaction activity and certain catalytic performance, and after reaction is finished, product can be by simply coming down in torrents, distill or choosing with the mode of the immiscible organic solvent extraction of ionic liquid and separate, ionic liquid promptly can recycle through simple process, and does not influence reactivity worth.Ionic liquid is considered to the novel dissolvent (T.Welton, Chem.Rev., 1999,99,2071 that have significant application value in the synthetic and cleaner production of a kind of green; D.B.Zhao, M.Wu, Y.Kou et al., Catalysis Today, 2002,74,157.).
Summary of the invention
The objective of the invention is to overcome the shortcoming that exists in traditional synthetic method, a kind of chemical synthesis process of diphenyl ether compound of eco-friendly, high-efficient simple is provided.
The chemical synthesis process of diphenyl ether compound of the present invention, it is characterized in that adopting by N-alkyl pyridine positively charged ion or 1, the ionic liquid at room temperature that 3-dialkylimidazolium positively charged ion and fluo anion are formed is as reaction medium, phenol and aromatic halohydrocarbon are as reactant, the synthetic diphenyl ether compound of continuous processing or one kettle way under alkaline condition, raw materials used molar mass ratio is: phenol: aromatic halohydrocarbon: alkali=1: 0.8～1.2: 1～1.2, temperature of reaction is 20-80 ℃, reaction times is 0.5-3 hour, and the chemical structural formula of institute's synthetic diphenyl ether compound is:
Wherein: R
1, R
2And R
3Be selected from H, NO
2, Me, AcO, CF
3, Cl and F; R
4, R
5, R
6And R
7Be selected from H, NO
2, CF
3, Cl, F and COOCH
3, and to have a group at least be NO
2Or CF
3Chemical equation is:
Described by N-alkyl pyridine or 1, fluo anion is selected from BF in the ionic liquid at room temperature that 3-dialkylimidazolium positively charged ion and fluo anion are formed
4 -Or PF
6 -Or CF
3COO
-Or CF
3SO
3 -, the chain length of alkyl is C
1-C
8, N-alkyl pyridine positively charged ion or 1,3-dialkylimidazolium positively charged ion is 1: 1 with the molar mass ratio of fluo anion, ion liquid consumption is 0.5～1.5L/mol phenol.
The chemical structural formula of described phenol is:
Wherein: R
1, R
2And R
3Be selected from H, NO
2, Me, AcO, CF
3, Cl and F.
The chemical structural formula of described aromatic halohydrocarbon is:
Wherein: R
4, R
5, R
6And R
7Be selected from H, NO
2, CF
3, Cl, F and COOCH
3, and to have a group at least be NO
2Or CF
3X is selected from F or Cl or Br.
Described alkali is selected from NaOH or KOH or Ba (OH)
2Or Na
2CO
3Or K
2CO
3, be best usually with KOH.
Described continuous processing operation steps is: earlier phenol and alkali are reacted the corresponding salt of generation in ionic liquid, and then the adding aromatic halohydrocarbon reacts the generation diphenyl ether compound; The one kettle way operation steps is: phenol, alkali and aromatic halohydrocarbon are added in the reactor simultaneously react, directly prepare diphenyl ether compound.
The chemical synthesis process of the diphenyl ether compound that we are bright, its key problem in technology is to be reaction medium with the ionic liquid at room temperature, and phenol and aromatic halohydrocarbon are as reactant, and continuous processing or one kettle way synthesize diphenyl ether compound under alkaline condition.Its advantage is: 1) reaction conditions gentleness, and easy to operate, good product quality, yield height.2) ionic liquid can recycle repeatedly, can reduce the pollution to environment effectively, to operator also safety.It is a kind of method of efficient, eco-friendly synthetic diphenyl ether compound.In view of diphenyl ether compound is the important medicine of a class and Pesticidal products or organic synthesis intermediate, the present invention has the wide industrial application prospect.
Embodiment
Representative instance of the present invention is as follows, but the present invention is not limited to these compounds:
Wherein, the 1st, weedicide fluorodifen Fluorodifen (DE2200479, DE2619489); The 4th, weedicide Nitrofluorfen (US3888932); The 5th, weedicide fluoroglycofenethyl Fluoroglycofen and lactofen Lactofen (US4259510, intermediate US4262152); The 6th, the important intermediate of weedicide acifluorfen Acifluorfen (US4093446); The 8th, weedicide bifenox Bifenox (US3652645).
Embodiment 1. preparation compounds 1
P-NP (0.84g, 6mmol), KOH (0.35g, 82%, 6mmol) and ionic liquid BMImPF
6(4mL) join successively in the 20mL twoport round-bottomed flask, in 60 ℃ of reactions 15 minutes, nitro-(1.13g 5mmol), reacted under vigorous stirring 2 hours 4-trifluoromethyl chlorobenzene again to drip 2-then from dropping funnel under mechanical stirring.(3 * 10mL), 5% alkaline solution 10mL washes once reaction mixture, is washed to neutrality, anhydrous MgSO with the toluene extraction
4Drying, distillation is desolvated and is obtained compound 1 (1.48g, yield 82%).
Embodiment 2. preparation compounds 2
To acetyl phenol (0.75g, 5.5mmol), Na
2CO
3(0.64g, 99.8%, 6mmol) with ionic liquid HMImPF
6(4mL) 25 ℃ were reacted 5 minutes down, added 2 in three batches then, 6-dinitrobenzene-4-trifluoromethyl chlorobenzene (1.35g, 5mmol), in 25 ℃ of following stirring reactions 0.5 hour, reaction mixture was with toluene extraction (3 * 10mL), 5% alkaline solution 10mL washes once, is washed to neutrality, anhydrous MgSO
4Drying, distillation is desolvated and is obtained compound 2 (1.68g, yield 91%).
Embodiment 3. preparation compounds 3
Phenol (0.48g, 5mmol), NaOH (0.25g, 95%, 6mmol) and ionic liquid EMImCF
3CO
2(4mL) join successively in the 20mL twoport round-bottomed flask, stir and to make most of material dissolution, add then 2-nitro-4-trifluoromethyl chlorobenzene (1.13g, 5mmol), under vigorous stirring in 50 ℃ of reactions 2 hours.Post-treating method by similar embodiment 1 obtains compound 3 (1.11g, yield 90%).
Embodiment 4. preparation compounds 4
2-chloro-4-trifloro methyl phenol (0.98g, 5mmol), KOH (0.35g, 82%, 6mmol), p-fluoronitrobenzene (0.71g, 5mmol) and ionic liquid HMImBF
4(4mL) in 60 ℃ of reactions 3 hours.With toluene extractive reaction thing, be washed to neutrality, anhydrous CaCl
2Drying, distillation is desolvated and is obtained compound 4 (1.24g, yield 78%).
Embodiment 5. preparation compounds 5
2-chloro-4-trifloro methyl phenol (0.98g, 5mmol), K
2CO
3(0.84g, 99%, 6mmol) with ionic liquid EMImCF
3SO
3(4mL) join successively in the 20mL twoport round-bottomed flask, in 30 ℃ of reactions 30 minutes, (0.99g 5mmol), reacted 2.5 hours in 30 ℃ again from dropping funnel Dropwise 5-fluoro-2-nitrobenzoic acid methyl esters then under mechanical stirring.Reaction mixture fully extracts with ether, is washed to neutrality, anhydrous MgSO
4Drying, distillation is desolvated and is obtained compound 5 (1.68g, yield 90%).
Embodiment 6. preparation compounds 6
M-methyl phenol (0.54g, 5mmol), Ba (OH)
2(0.45g, 96%, 2.5mmol) with ionic liquid BMImBF
4(4mL) join successively in the 20mL twoport round-bottomed flask, under mechanical stirring,, add 3 then in 60 ℃ of reactions 15 minutes, 4-two chlorobenzotrifluorides (1.08g, 5mmol), 80 ℃ were reacted 2 hours down, post-treating method by similar embodiment 1 obtains compound 6 (0.96g, yield 67%).
Embodiment 7. preparation compounds 7
Ortho chloro phenol (0.64g, 5mmol), KOH (0.35g, 82%, 6mmol), 3-chloro-4-fluoro-oil of mirbane (0.89g, 5mmol) and BMImPF
6(4mL) add successively in the reaction flask, then 80 ℃ of down reactions 2 hours, the post-treating method by similar embodiment 1 obtains compound 7 (0.87g, yield 61%).
Embodiment 8. preparation compounds 8
2,4 dichloro phenol (0.81g, 5mmol) replace among the embodiment 5 to 2-chloro-4-trifloro methyl phenol, obtain compound 8 (1.33g, yield 78%) by similar method.
Embodiment 9. preparation compounds 9
P-NP (0.84g, 6mmol), K
2CO
3(0.84g, 99%, 6mmol) with ionic liquid BPyBF
4(4mL) in 25 ℃ of reactions 15 minutes, add 2 then, (1.04g, 5mmol), in 60 ℃ of reactions 2 hours, the post-treating method by similar embodiment 1 obtained compound 9 (1.37g, yield 90%) to the 4-dinitrochlorobenzene.
Embodiment 1O. ionic liquid recycles experiment
With the remaining ionic liquid layer in extraction back among the embodiment 1, add 10mL water and stirred 10 minutes, standing separation, ionic liquid layer was 80 ℃ of following vacuum-dryings 4 hours, and the ionic liquid of recovery can be directly used in reaction next time.React according to embodiment 1, ionic liquid can be recycled more than 5 times at least, resultingly the results are shown in Table 1.
Table 1 ionic liquid recycles experiment
| Cycle index | ?1 | ?2 | ?3 | ?4 | ?5 | |
| Reclaim the ionic liquid scale of construction (g) | 20 | ?19.5 | ?19.1 | ?18.6 | ?18.2 | ?17.8 |
| Product yield (%) | 82 | ?86 | ?85 | ?84 | ?84 | ?82 |
Claims (6)
1. the chemical synthesis process of a diphenyl ether compound, it is characterized in that adopting by N-alkyl pyridine positively charged ion or 1, the ionic liquid at room temperature that 3-dialkylimidazolium positively charged ion and fluo anion are formed is as reaction medium, phenol and aromatic halohydrocarbon are as reactant, the synthetic diphenyl ether compound of continuous processing or one kettle way under alkaline condition, raw materials used molar mass ratio is: phenol: aromatic halohydrocarbon: alkali=1: 0.8～1.2: 1～1.2, temperature of reaction is 20-80 ℃, reaction times is 0.5-3 hour, and the chemical structural formula of institute's synthetic diphenyl ether compound is:
Wherein: R
1, R
2And R
3Be selected from H, NO
2, Me, AcO, CF
3, Cl and F; R
4, R
5, R
6And R
7Be selected from H, NO
2, CF
3, Cl, F and COOCH
3, and to have a group at least be NO
2Or CF
3
2. synthetic method as claimed in claim 1 is characterized in that by N-alkyl pyridine or 1, and fluo anion is selected from BF in the ionic liquid at room temperature that 3-dialkylimidazolium positively charged ion and fluo anion are formed
4 -Or PF
6 -Or CF
3COO
-Or CF
3SO
3 -, the chain length of alkyl is C
1-C
8, N-alkyl pyridine positively charged ion or 1,3-dialkylimidazolium positively charged ion is 1: 1 with the molar mass ratio of fluo anion, ion liquid consumption is 0.5～1.5L/mol phenol.
3. the method for claim 1 is characterized in that the chemical structural formula of used phenol is:
Wherein: R
1, R
2And R
3Be selected from H, NO
2, Me, AcO, CF
3, Cl and F.
4. the method for claim 1 is characterized in that the chemical structural formula of used aromatic halohydrocarbon is:
Wherein: R
4, R
5, R
6And R
7Be selected from H, NO
2, CF
3, Cl, F and COOCH
3, and to have a group at least be NO
2Or CF
3X is selected from F or Cl or Br.
5. the method for claim 1 is characterized in that used alkali is selected from NaOH or KOH or Ba (OH)
2Or Na
2CO
3Or K
2CO
3, be best usually with KOH.
6. the method for claim 1 is characterized in that the continuous processing operation steps is: earlier phenol and alkali are reacted the corresponding salt of generation in ionic liquid, and then the adding aromatic halohydrocarbon reacts the generation diphenyl ether compound; The one kettle way operation steps is: phenol, alkali and aromatic halohydrocarbon are added in the reactor simultaneously react, directly prepare diphenyl ether compound.
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|---|---|---|---|
| CN 03116222 CN1211338C (en) | 2003-04-03 | 2003-04-03 | Chemical method for sythesizing dipheny ether compound |
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|---|---|---|---|
| CN 03116222 CN1211338C (en) | 2003-04-03 | 2003-04-03 | Chemical method for sythesizing dipheny ether compound |
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|---|---|
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| CN1211338C CN1211338C (en) | 2005-07-20 |
Family
ID=34320274
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|---|---|---|---|
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|---|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100488932C (en) * | 2006-03-17 | 2009-05-20 | 中国海洋大学 | Diphenylether compound, its preparation and use |
| CN102030655A (en) * | 2010-10-21 | 2011-04-27 | 上虞颖泰精细化工有限公司 | Synthesis method of diphenyl ether derivate, combined production method of oxyfluorfen and acifluorfen and synthesis method of oxyfluorfen |
| CN102898290A (en) * | 2012-09-06 | 2013-01-30 | 浙江工业大学 | Synthesis method for herbicide intermediate 1,3-bis(2-chloro-4-trifluoromethylphenoxy)benzene |
| CN104086377A (en) * | 2014-07-07 | 2014-10-08 | 太仓博亿化工有限公司 | Synthesis method of polymethoxy substituted diphenyl ether compound |
| CN105601519A (en) * | 2016-02-01 | 2016-05-25 | 北京颖泰嘉和生物科技股份有限公司 | Preparation method of acifluorfen |
| WO2017069834A3 (en) * | 2015-08-04 | 2018-03-01 | California Institute Of Technology | Organic synthesis applications of non-aqueous fluoride salt solutions |
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| CN111153772A (en) * | 2020-01-08 | 2020-05-15 | 安徽禾宸化学科技有限公司 | Preparation method for constructing diphenyl ether structure compound |
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2003
- 2003-04-03 CN CN 03116222 patent/CN1211338C/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100488932C (en) * | 2006-03-17 | 2009-05-20 | 中国海洋大学 | Diphenylether compound, its preparation and use |
| CN102030655A (en) * | 2010-10-21 | 2011-04-27 | 上虞颖泰精细化工有限公司 | Synthesis method of diphenyl ether derivate, combined production method of oxyfluorfen and acifluorfen and synthesis method of oxyfluorfen |
| CN102030655B (en) * | 2010-10-21 | 2013-03-27 | 上虞颖泰精细化工有限公司 | Synthesis method of diphenyl ether derivate, combined production method of oxyfluorfen and acifluorfen and synthesis method of oxyfluorfen |
| CN102898290A (en) * | 2012-09-06 | 2013-01-30 | 浙江工业大学 | Synthesis method for herbicide intermediate 1,3-bis(2-chloro-4-trifluoromethylphenoxy)benzene |
| CN104086377A (en) * | 2014-07-07 | 2014-10-08 | 太仓博亿化工有限公司 | Synthesis method of polymethoxy substituted diphenyl ether compound |
| WO2017069834A3 (en) * | 2015-08-04 | 2018-03-01 | California Institute Of Technology | Organic synthesis applications of non-aqueous fluoride salt solutions |
| US10468722B2 (en) | 2015-08-04 | 2019-11-05 | California Institute Of Technology | Organic synthesis applications of non-aqueous fluoride salt solutions |
| US10720666B2 (en) | 2015-08-04 | 2020-07-21 | California Institute Of Technology | Non-aqueous fluoride salts, solutions, and their uses |
| US11069921B2 (en) | 2015-08-04 | 2021-07-20 | California Institute Of Technology | Non-aqueous fluoride salts, solutions, and their uses |
| US11398645B2 (en) | 2015-08-04 | 2022-07-26 | California Institute Of Technology | Organic synthesis applications of non-aqueous fluoride salt solutions |
| US11830983B2 (en) | 2015-08-04 | 2023-11-28 | California Institute Of Technology | Non-aqueous fluoride salts, solutions, and their uses |
| CN105601519A (en) * | 2016-02-01 | 2016-05-25 | 北京颖泰嘉和生物科技股份有限公司 | Preparation method of acifluorfen |
| CN109574851A (en) * | 2018-11-27 | 2019-04-05 | 浙江工业大学上虞研究院有限公司 | A kind of method that ionic liquid-catalyzed Chlorobenzene Nitration prepares dinitrofluorobenzene |
| CN111153772A (en) * | 2020-01-08 | 2020-05-15 | 安徽禾宸化学科技有限公司 | Preparation method for constructing diphenyl ether structure compound |
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