CN106349035A - Method for preparing 2'-fluoroacetophenone - Google Patents
Method for preparing 2'-fluoroacetophenone Download PDFInfo
- Publication number
- CN106349035A CN106349035A CN201610674571.2A CN201610674571A CN106349035A CN 106349035 A CN106349035 A CN 106349035A CN 201610674571 A CN201610674571 A CN 201610674571A CN 106349035 A CN106349035 A CN 106349035A
- Authority
- CN
- China
- Prior art keywords
- solution
- tertiary butyl
- butyl ether
- reaction
- methyl tertiary
- 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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- QMATYTFXDIWACW-UHFFFAOYSA-N 1-(2-fluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC=C1F QMATYTFXDIWACW-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 15
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011777 magnesium Substances 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 8
- 238000010992 reflux Methods 0.000 claims abstract description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims abstract description 8
- RAAGZOYMEQDCTD-UHFFFAOYSA-N 2-fluorobenzoyl chloride Chemical compound FC1=CC=CC=C1C(Cl)=O RAAGZOYMEQDCTD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 230000000977 initiatory effect Effects 0.000 claims abstract description 5
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 239000010410 layer Substances 0.000 claims abstract description 4
- 239000012044 organic layer Substances 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000009835 boiling Methods 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000012467 final product Substances 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims abstract 5
- 238000002360 preparation method Methods 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 235000011149 sulphuric acid Nutrition 0.000 claims description 5
- 239000001117 sulphuric acid Substances 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000284 extract Substances 0.000 claims description 2
- 238000004508 fractional distillation Methods 0.000 claims description 2
- 238000006396 nitration reaction Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract 2
- 238000005336 cracking Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- -1 aromatic heterocycle acyl chlorides Chemical class 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- VIZORQUEIQEFRT-UHFFFAOYSA-N Diethyl adipate Chemical compound CCOC(=O)CCCCC(=O)OCC VIZORQUEIQEFRT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000007984 tetrahydrofuranes Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 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
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/02—Magnesium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing 2'-fluoroacetophenone. The method includes sequentially adding magnesium chips, ethyl alcohol and carbon tetrachloride solution into a reaction vessel, initiating reaction, adding methyl tertiary butyl ether into solution and continuously stirring the solution; mixing diethyl malonate and methyl tertiary butyl ether with each other to obtain mixed liquid and dropwise adding the mixed liquid into the stirred solution at the dropwise adding speed under the control so that the mixed liquid can be boiling; carrying out reflux on solution until the magnesium chips disappear so as to obtain reaction solution; mixing fluorobenzoyl chloride and methyl tertiary butyl ether with each other to obtain solution and adding the solution into the reaction solution to obtain solution; carrying out heating reflux on the solution until the solution is difficult to stir, slowly dropwise adding sulfuric acid into the solution under cooling conditions, cracking all solid, acquiring organic layers by means of separation, extracting water layers, concentrating solvents to obtain leftover, adding solution with mixed liquid and water into the leftover and carrying out reflux; regulating alkali in solution and extracting, drying and fractionating the solution to obtain a final product. The method has the advantages of mild reaction, high yield and environmental friendliness.
Description
Technical field
The present invention relates to aromatic heterocycle acyl chlorides changes into the preparation method of ketone, particularly a kind of preparation of o-fluoro acetophenone
Method.
Background technology
O-fluoro acetophenone is numerous medicine, the intermediate of pesticide field.Currently in industrialized method, the overwhelming majority
Enterprise have selected fluorine in amino diazotising.The method is serious to equipment corrosion, and waste water color is deep, and intractability is big, and diazonium
Salt needs high temperature thermal decomposition, generates a large amount of white cigarettes, serious environment pollution.With the raising of national life level, environmental consciousness plus
By force, this synthetic method has arrived the edge being eliminated.Synthetic method reaction according to the present invention is gentle, and high income, to ring
Border is friendly, is the optimised process replacing old technique.
Original synthetic method:
Above method is method industrial at present, and it is greatly unfavorable that nitro reduction all brings to equipment or environment or operation
Impact.Conventional reducing agent is all to environmentally undesirable, and high-pressure hydrogenation then has potential safety hazard, and high to equipment requirements.Except this
Outside, amino becomes fluorine to be needed first to become diazol with fluoboric acid, then thermally decomposes again.Fluoboric acid corrosion reacting kettle, especially enamel
Kettle, can only be reacted in the kettle of lining plastic (fluorine), and the kettle of this material is also wanted in diazol thermal decomposition, therefore to equipment requirements pole
High.With the raising of national environmental consciousness, enterprise is forced to eliminate backward production technology or method.
Content of the invention
The present invention provides a kind of preparation method of o-fluoro acetophenone, right in the preparation process of existing o-fluoro acetophenone to solve
Equipment requirements are high, shortcoming big for environment pollution.
Detailed technology scheme of the present invention is:
A kind of preparation method of o-fluoro acetophenone, described preparation method comprises the following steps: the first step, anti-
Answer and in container, sequentially add magnesium chips, dehydrated alcohol and carbon tetrachloride solution, initiation reaction；
Second step, after initiation reaction, adds methyl tertiary butyl ether(MTBE) in the solution of step one, ceaselessly stirs；
3rd step, diethyl malonate is mixed with ethanol and methyl tertiary butyl ether(MTBE), is obtained mixed liquor；
4th step, the mixed liquor in step 3 is added drop-wise in the mixed liquor in step 2, controls rate of addition to make step
Mixed liquor boiling in two；
5th step, the mixed liquor in step 4 is carried out backflow until magnesium chips disappears；
6th step, o-fluoro-benzoyl chloride is mixed with methyl tertiary butyl ether(MTBE), obtains solution, and this solution is added to step
In rapid five reaction solution, control speed, so that o-fluoro-benzoyl chloride and methyl tertiary butyl ether(MTBE) is dripped in 15 minutes；
7th step, the mixed liquor in step 6 is heated to reflux to difficult stirring, in the case of cooling, is slowly added dropwise sulfur
Acid, cracks all solids, separates organic layer, aqueous layer extracted, after concentrated solvent, adds nitration mixture form with water in the remnant obtaining
Solution, be back to no carbon dioxide release；
8th step, alkali tune at 5 DEG C of the mixed liquor in step 7 extracts drying, fractional distillation, obtains final product.
Further, described in described step 7, sulphuric acid can be replaced with acetic acid.
Further, the container to step 7 for the described step one and reaction condition require to carry out in anhydrous conditions.
Further, alkali tune method described in described step 8 is to adjust acid-base value using 20% sodium hydroxide solution.
Further, described methyl tertiary butyl ether(MTBE) can be replaced with oxolane.
The Advantageous Effects that the present invention is reached are: the reaction of this preparation method is gentle, and high income is environmentally friendly, very
Good has reached industrial requirement, is not only applicable to o-fluoro acetophenone, other aromatic heterocycle acyl chlorides are changed into the reaction of ketone
Also generally applicable.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not used to
Limit the present invention.
The reaction equation of the present invention is as follows:
The present invention has catered to new situations instantly, makes this product can continue to keep surging market supply.From the third two
Diethyl phthalate, magnesium powder, ethanol, hydrochloric acid and o-fluoro-benzoyl chloride react, and obtain o-fluoro acetophenone, and reaction is gentle, and high income, to ring
Border is friendly.The present invention has reached industrial requirement well.Now illustrated with example:
Embodiment one
Add 10.8kg magnesium chips, 10 liters of absolute ethanol and 1 liter of anhydrous carbon tetrachloride in the reactor of 1000l, if instead
Answer not immediate response, can of short duration heat, after reaction causes and continues a few minutes, add absolute methyl tertiary butyl ether(MTBE)
300 liters, and careful heated and stirred；Start Deca by 70.4kg diethyl malonate, 40 liters of absolute ethanol and 50 liters of methyl- tert fourths
Base ether mixed liquor, rate of addition is to keep seething with excitement (can heat if necessary) rapidly in bottle；Add after finishing, be heated to reflux 3 hours,
Disappear to nearly all magnesium chips, solution gray；Deca 63.4kg o-fluoro-benzoyl chloride and 100 liters of methyl tertiary butyl ether(MTBE)s composition
Solution, 15min interpolation finishes, and continues to be heated to reflux till the difficult stirring of green solution retrogradation, and cooling is slowly added to
The dilute sulfuric acid of 440kg10%, all solids all dissolve, and separate Organic substance, and water layer is extracted with dichloromethane, merge organic layer,
Washing, reclaims dichloromethane, adds the solution being made up of 120 liters of glacial acetic acid, 15.2 liters of concentrated sulphuric acids and 80 liters of water in remnant,
It is heated to reflux 4 hours, till no carbon dioxide is released, be cooled to less than 5 DEG C, be neutralized to alkali with 20% sodium hydroxide solution
Property, with dichloromethane extraction 4 times, merge, water washed reservoir, be dried, concentrate dichloromethane, bed material vacuum fractionation obtains product 46kg,
Yield 83%.
Embodiment two
Methyl tertiary butyl ether(MTBE) in example one is all changed into oxolane, other raw material ingredient proportion identical situations
Under, obtain product 50kg, yield 90%.
This method sulphuric acid and acetic acid and do not select hydrochloric acid or nitric acid, be it is noted that place, no high-temperature high-voltage reaction, third
The diethyl adipate solvent requirement absolute required with the reaction of magnesium powder.
It is an advantage of the current invention that not being only applicable to o-fluoro acetophenone, the anti-of ketone is changed into other aromatic heterocycle acyl chlorides
Should be also general.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.
The present invention does not address part and is applied to prior art.
Claims (5)
1. a kind of preparation method of o-fluoro acetophenone is it is characterised in that described preparation method comprises the following steps:
The first step, sequentially adds magnesium chips, ethanol and carbon tetrachloride solution, initiation reaction in reaction vessel；
Second step, after initiation reaction, adds methyl tertiary butyl ether(MTBE) in the solution of step one, ceaselessly stirs；
3rd step, diethyl malonate is mixed with ethanol and methyl tertiary butyl ether(MTBE), is obtained mixed liquor；
4th step, the mixed liquor in step 3 is added drop-wise in the mixed liquor in step 2, controls rate of addition to make in step 2
Mixed liquor boiling；
5th step, the mixed liquor in step 4 is carried out backflow until magnesium chips disappears；
6th step, o-fluoro-benzoyl chloride is mixed with methyl tertiary butyl ether(MTBE), obtains solution, and this solution is added to step 5
Reaction solution in, control speed, so that o-fluoro-benzoyl chloride and methyl tertiary butyl ether(MTBE) has been added in 15 minutes；
7th step, the mixed liquor in step 6 is heated to reflux to difficult stirring, in the case of cooling, is slowly added dropwise sulphuric acid, breaks
Solution all solids, separate organic layer, aqueous layer extracted, after concentrated solvent, by the remnant obtaining plus nitration mixture is molten with what water formed
Liquid, is back to no carbon dioxide and releases；
8th step, alkali tune at 5 DEG C of the mixed liquor in step 7 extracts drying, fractional distillation, obtains final product.
2. o-fluoro acetophenone according to claim 1 preparation method it is characterised in that: sulphuric acid described in described step 7
Available acetic acid replaces.
3. o-fluoro acetophenone according to claim 1 preparation method it is characterised in that: in described step one to step 7
Container and reaction condition require carry out in anhydrous conditions.
4. o-fluoro acetophenone according to claim 1 preparation method it is characterised in that: alkali tune described in described step 8
Method is to adjust acid-base value using 20% sodium hydroxide solution.
5. o-fluoro acetophenone according to claim 1 preparation method it is characterised in that: described methyl tertiary butyl ether(MTBE) can use
Oxolane replaces.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610674571.2A CN106349035A (en) | 2016-08-17 | 2016-08-17 | Method for preparing 2'-fluoroacetophenone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610674571.2A CN106349035A (en) | 2016-08-17 | 2016-08-17 | Method for preparing 2'-fluoroacetophenone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106349035A true CN106349035A (en) | 2017-01-25 |
Family
ID=57844250
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610674571.2A Pending CN106349035A (en) | 2016-08-17 | 2016-08-17 | Method for preparing 2'-fluoroacetophenone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106349035A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1781894A (en) * | 2004-12-01 | 2006-06-07 | 大连绿源药业有限责任公司 | Process for preparing 3, 3-dimethyl -2-pentanone |
-
2016
- 2016-08-17 CN CN201610674571.2A patent/CN106349035A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1781894A (en) * | 2004-12-01 | 2006-06-07 | 大连绿源药业有限责任公司 | Process for preparing 3, 3-dimethyl -2-pentanone |
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Application publication date: 20170125 |