CN105315142A - Industrial production method for 2, 6-difluorobenzaldehyde - Google Patents
Industrial production method for 2, 6-difluorobenzaldehyde Download PDFInfo
- Publication number
- CN105315142A CN105315142A CN201510803543.1A CN201510803543A CN105315142A CN 105315142 A CN105315142 A CN 105315142A CN 201510803543 A CN201510803543 A CN 201510803543A CN 105315142 A CN105315142 A CN 105315142A
- Authority
- CN
- China
- Prior art keywords
- difluorobenzaldehyde
- difluorobenzaldehydes
- preparing process
- tetramethylene sulfone
- industrialized preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- SOWRUJSGHKNOKN-UHFFFAOYSA-N 2,6-difluorobenzaldehyde Chemical compound FC1=CC=CC(F)=C1C=O SOWRUJSGHKNOKN-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000009776 industrial production Methods 0.000 title abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 43
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims abstract description 26
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Inorganic materials [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims abstract description 24
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims abstract description 23
- DMIYKWPEFRFTPY-UHFFFAOYSA-N 2,6-dichlorobenzaldehyde Chemical compound ClC1=CC=CC(Cl)=C1C=O DMIYKWPEFRFTPY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004334 fluoridation Methods 0.000 claims abstract description 14
- 235000003270 potassium fluoride Nutrition 0.000 claims abstract description 12
- 239000011698 potassium fluoride Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 239000000575 pesticide Substances 0.000 abstract 1
- -1 potassium fluoride halogens Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- WDBAXYQUOZDFOJ-UHFFFAOYSA-N 2,3-difluorobenzaldehyde Chemical class FC1=CC=CC(C=O)=C1F WDBAXYQUOZDFOJ-UHFFFAOYSA-N 0.000 description 1
- VBYKMBNKTAXKJZ-UHFFFAOYSA-N C1=CC=CC=C1C1=CC=CC=C1.N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical class C1=CC=CC=C1C1=CC=CC=C1.N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 VBYKMBNKTAXKJZ-UHFFFAOYSA-N 0.000 description 1
- HRYILSDLIGTCOP-UHFFFAOYSA-N N-benzoylurea Chemical class NC(=O)NC(=O)C1=CC=CC=C1 HRYILSDLIGTCOP-UHFFFAOYSA-N 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an industrial production method for 2, 6-difluorobenzaldehyde and relates to the technical field of production of pesticide, medicine and liquid crystal raw materials. 2, 6-dichlorobenzaldehyde serves as the raw material, tetrabutylammonium chloride serves as a catalyst, sulfolane and methylbenzene serve as media, and potassium fluoride halogens are synthesized into 2, 6-difluorobenzaldehyde through exchange and fluoridation. According to the method, a fluoridation reaction is conducted under the water-free and oxygen-free condition, and by means of the method, an industrial product which is high in quality and synthesis conversion rate can be obtained.
Description
Technical field
The present invention relates to the production technical field of agricultural chemicals, medicine, liquid crystal raw material, be specifically related to the production technical field of 2,6-difluorobenzaldehyde.
Background technology
2,6-difluorobenzaldehyde, molecular formula: C
7h
4f
20, molecular weight is 142.10, and finished product is weak yellow liquid or solid.2,6-difluorobenzaldehyde is a kind of important Organic Chemicals, is the intermediate of medicine, agricultural chemicals, liquid crystal material, may be used for synthesizing new antiviral and process for preparation of benzoylurea compounds, can also synthesizing fluoro ten phenylbenzene porphyrins.
The synthetic method of 2,6-existing difluorobenzaldehydes has: electrochemical process, chemical method, fluorination method etc., but the defect that the production of various 2,6-difluorobenzaldehydes exists above is: production control difficulty, yields poorly, cost is high, can not be applicable to the market requirement.
Summary of the invention
The present invention seeks to propose a kind of be easy to production control, output high can the method for suitability for industrialized production 2,6-difluorobenzaldehyde.
The present invention is with 2,6-dichlorobenzaldehyde for raw material, and its spy is: under oxygen free condition, and 2,6-dichlorobenzaldehyde, tetrabutylammonium chloride, tetramethylene sulfone and the reaction of anhydrous potassium fluoride mixed fluoride are obtained 2,6-difluorobenzaldehyde.
For the series of problems do not had at present in industrialized preparing process and technology, the present invention with 2,6-dichlorobenzaldehyde for raw material, take tetrabutylammonium chloride as catalyzer, with tetramethylene sulfone and toluene for medium, by Potassium monofluoride halogen-exchange fluorination synthesis 2,6-difluorobenzaldehyde.The present invention carries out fluoridation under anhydrous, anaerobic conditions, can be obtained the Industrial products of high quality, high Synthesis conversion by the method.
Further, the mass ratio that feeds intake of 2,6-dichlorobenzaldehydes of the present invention, tetrabutylammonium chloride, anhydrous potassium fluoride and tetramethylene sulfone is 1: 0.1 ~ 0.4: 1 ~ 2: 4.Consider the problem of cost of material, this technique adopts " anhydrous potassium fluoride " conduct " excessive 1-5% raw material ", makes 2,6-dichlorobenzaldehyde complete reaction.Tetramethylene sulfone is as reaction carriers, and tetrabutylammonium chloride, as catalysts, draws this " most economical " feed ratio by test.By above proportioning, fluoridation speed is fast, and selectivity reaches 90%, achieves good reaction effect.
More preferably: the mass ratio that feeds intake of described 2,6-dichlorobenzaldehydes, tetrabutylammonium chloride, anhydrous potassium fluoride and tetramethylene sulfone is 1: 0.2: 2: 4.
Concrete steps of the present invention are:
1) heat up after in a kettle., tetramethylene sulfone being dissolved in toluene and remove water and toluene;
2) under nitrogen protection, in reactor, add anhydrous potassium fluoride, tetrabutylammonium chloride and 2,6-dichlorobenzaldehyde and carry out fluoridation;
3) under vacuum condition, the compound after fluoridation is distilled, distillate the mixture of 2,6-difluorobenzaldehyde and tetramethylene sulfone;
4), under vacuum condition, the mixture of 2,6-difluorobenzaldehyde and tetramethylene sulfone is carried out rectifying, obtains 2,6-difluorobenzaldehyde.
Through above step, toluene and the tetramethylene sulfone of active loss are almost nil, are beneficial to production energy-saving.
In addition, the temperature condition of fluoridation of the present invention is 140 ~ 160 DEG C.The temperature condition of preferred fluoridation is 150 ~ 155 DEG C.As temperature of reaction is too high, by-product increases yield and declines, and the too low reaction times extends, and polymerization easily occurs yield also can be caused to reduce.In this temperature range, reaction yield is best, can ensure to reach processing requirement.
The temperature removing water and toluene that heats up is 110 ~ 130 DEG C.Due to toluene boiling point: 110.6 DEG C, at this temperature, refluxing toluene, the moisture in system and methylbenzene azeotropic layering, thus reach the object of dehydration.
The vacuum condition of step 3) is-0.098MPa.Under vacuo, the boiling point of material reduced, has reduced, saved energy consumption.The crude product of 2,6-difluorobenzaldehyde can be distilled out rapidly with this understanding, reduce high temperature and bring coking to be polymerized the risk causing by product significantly to increase.
The vacuum condition of step 4) is-0.098MPa.Under vacuo, the boiling point of material reduced, has reduced, saved energy consumption.Meanwhile, avoid at high temperature, material produces coking, the phenomenon that by product significantly increases.
Embodiment
One, get the raw materials ready: take tetramethylene sulfone 400kg, anhydrous potassium fluoride 200kg, tetrabutylammonium chloride 20kg respectively, toluene 50kg, 2,6-dichlorobenzaldehyde 100kg.
Two, production stage
1, in a kettle., tetramethylene sulfone is mixed with toluene, be then warming up to 110 ~ 130 DEG C, remove water in raw material, and then steam toluene, obtain pure tetramethylene sulfone.
2, anhydrous potassium fluoride, tetrabutylammonium chloride and 2 is added again fluoridizing in still, 6-dichlorobenzaldehyde, drive with nitrogen and fluoridize still and include oxygen air, after sealing, pass into steam to the chuck fluoridizing still, make to fluoridize feed liquid in still and be warming up to 150 ~ 155 DEG C and carry out fluoridation, reaction is about through 3-4h, control terminal 2,6-difluorobenzaldehyde ﹥ 85%.
3, under-0.098MPa vacuum condition, the compound after fluoridation is distilled, distillate the mixture of 2,6-difluorobenzaldehyde and tetramethylene sulfone.Remaining tetramethylene sulfone can steam under the high vacuum of 200Pa, to reuse.
4, under-0.098MPa vacuum condition, the mixture of 2,6-difluorobenzaldehyde and tetramethylene sulfone is carried out rectifying, obtains 2,6-difluorobenzaldehyde, remaining tetramethylene sulfone can steam under the high vacuum of 200Pa, to reuse.
Claims (9)
- The industrialized preparing process of 1.2,6-difluorobenzaldehyde, with 2,6-dichlorobenzaldehyde is raw material, it is characterized in that: under oxygen free condition, by 2,6-dichlorobenzaldehyde, tetrabutylammonium chloride, tetramethylene sulfone and the reaction of anhydrous potassium fluoride mixed fluoride obtain 2,6-difluorobenzaldehyde.
- 2. the industrialized preparing process of 2,6-difluorobenzaldehydes according to claim 1, is characterized in that: the mass ratio that feeds intake of described 2,6-dichlorobenzaldehydes, tetrabutylammonium chloride, anhydrous potassium fluoride and tetramethylene sulfone is 1: 0.1 ~ 0.4: 1 ~ 2: 4.
- 3. the industrialized preparing process of 2,6-difluorobenzaldehydes according to claim 2, is characterized in that the mass ratio that feeds intake of described 2,6-dichlorobenzaldehydes, tetrabutylammonium chloride, anhydrous potassium fluoride and tetramethylene sulfone is 1: 0.2: 2: 4.
- 4. the industrialized preparing process of 2,6-difluorobenzaldehydes according to claim 1 or 2 or 3, is characterized in that comprising the following steps:1) heat up after in a kettle., tetramethylene sulfone being dissolved in toluene and remove water and toluene;2) under nitrogen protection, in reactor, add anhydrous potassium fluoride, tetrabutylammonium chloride and 2,6-dichlorobenzaldehyde and carry out fluoridation;3) under vacuum condition, the compound after fluoridation is distilled, distillate the mixture of 2,6-difluorobenzaldehyde and tetramethylene sulfone;4), under vacuum condition, the mixture of 2,6-difluorobenzaldehyde and tetramethylene sulfone is carried out rectifying, obtains 2,6-difluorobenzaldehyde.
- 5. the industrialized preparing process of 2,6-difluorobenzaldehydes according to claim 4, is characterized in that the temperature condition of described fluoridation is 140 ~ 160 DEG C.
- 6. the industrialized preparing process of 2,6-difluorobenzaldehydes according to claim 5, is characterized in that the temperature condition of described fluoridation is 150 ~ 155 DEG C.
- 7. the industrialized preparing process of 2,6-difluorobenzaldehydes according to claim 4, the temperature removing water and toluene that it is characterized in that heating up in described step 1) is 110 ~ 130 DEG C.
- 8. the industrialized preparing process of 2,6-difluorobenzaldehydes according to claim 4, is characterized in that the vacuum condition of described step 3) is-0.098MPa.
- 9. the industrialized preparing process of 2,6-difluorobenzaldehydes according to claim 4, is characterized in that the vacuum condition of described step 4) is-0.098MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510803543.1A CN105315142A (en) | 2015-11-20 | 2015-11-20 | Industrial production method for 2, 6-difluorobenzaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510803543.1A CN105315142A (en) | 2015-11-20 | 2015-11-20 | Industrial production method for 2, 6-difluorobenzaldehyde |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105315142A true CN105315142A (en) | 2016-02-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510803543.1A Pending CN105315142A (en) | 2015-11-20 | 2015-11-20 | Industrial production method for 2, 6-difluorobenzaldehyde |
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| CN (1) | CN105315142A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651120A (en) * | 2019-01-25 | 2019-04-19 | 河北海力香料股份有限公司 | A kind of preparation method of 4- (4- formvlphenoxv) benzaldehyde |
| CN112409169A (en) * | 2020-12-01 | 2021-02-26 | 连云港杰瑞药业有限公司 | Method for preparing polyfluorinated aromatic hydrocarbon |
| CN116178121A (en) * | 2022-12-09 | 2023-05-30 | 浙江巍华新材料股份有限公司 | Preparation method of 2,4, 5-trifluoro-benzaldehyde |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5191126A (en) * | 1991-07-16 | 1993-03-02 | Hoechst Aktiengesellschaft | Process for the preparation of difluorobenzaldehydes |
| CN1244139A (en) * | 1997-01-23 | 2000-02-09 | 阿温提斯研究技术两合公司 | Amidophosphonium-salt-containing catalyst for halogen-fluorine exchange reactions |
-
2015
- 2015-11-20 CN CN201510803543.1A patent/CN105315142A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5191126A (en) * | 1991-07-16 | 1993-03-02 | Hoechst Aktiengesellschaft | Process for the preparation of difluorobenzaldehydes |
| CN1244139A (en) * | 1997-01-23 | 2000-02-09 | 阿温提斯研究技术两合公司 | Amidophosphonium-salt-containing catalyst for halogen-fluorine exchange reactions |
Non-Patent Citations (2)
| Title |
|---|
| 汪嵘等: "2 , 6 - 二氟苯甲醛的合成", 《江苏化工》 * |
| 龚启孙等: "2,6-二氟苯甲醛的合成", 《浙江化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651120A (en) * | 2019-01-25 | 2019-04-19 | 河北海力香料股份有限公司 | A kind of preparation method of 4- (4- formvlphenoxv) benzaldehyde |
| CN112409169A (en) * | 2020-12-01 | 2021-02-26 | 连云港杰瑞药业有限公司 | Method for preparing polyfluorinated aromatic hydrocarbon |
| CN112409169B (en) * | 2020-12-01 | 2023-08-15 | 山东金吉利新材料有限公司 | Method for preparing polyfluoroaromatic hydrocarbon |
| CN116178121A (en) * | 2022-12-09 | 2023-05-30 | 浙江巍华新材料股份有限公司 | Preparation method of 2,4, 5-trifluoro-benzaldehyde |
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