CN103497088A - Method for preparing octafluoronaphthalene - Google Patents
Method for preparing octafluoronaphthalene Download PDFInfo
- Publication number
- CN103497088A CN103497088A CN201310478055.9A CN201310478055A CN103497088A CN 103497088 A CN103497088 A CN 103497088A CN 201310478055 A CN201310478055 A CN 201310478055A CN 103497088 A CN103497088 A CN 103497088A
- Authority
- CN
- China
- Prior art keywords
- preparation
- bromide
- octafluoro naphthalene
- solvent
- reaction
- 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.)
- Pending
Links
Abstract
The invention discloses a method for preparing octafluoronaphthalene, and belongs to the field of organic chemistry. The method includes enabling octachloronaphthalene and fluoride salt to react so as to generate the octafluoronaphthalene. Preferably, solvents and/or catalysts can be added into a reaction system. The method has the advantages of simplicity in process, high yield, good product quality, suitability for industrial production and the like.
Description
Technical field
the present invention relates to a kind of preparation method of octafluoro naphthalene, belong to organic chemistry filed.
Background technology
The octafluoro naphthalene is a kind of important industrial chemicals, and the application in material and catalyst field is more and more extensive.There is now several method to synthesize the octafluoro naphthalene.1991, it was raw material with Octadecafluorodec Ahydronaphthalene that the people such as Marsella have reported a kind of in United States Patent (USP) (US 5026929A), prepared the technique of octafluoro naphthalene through the sodium Metal 99.5 reduction.This technique need use dangerous high sodium Metal 99.5 as reductive agent, and need in glove box, operate, and security risk is high, and poor operability is difficult for amplifying and produces.1996, the people such as Kiplnger reported a kind of with titanium metal complex compound and mercury chloride as composite catalyst prepare the octafluoro naphthalene technique (
j. Am. Chem. Soc.1996,118,7,1805-1806.).But this technique titanium metal complex compound used is expensive, and Toxicity of Mercury Chloride is larger.The people such as Ricciardi in 2000, reported a kind of with manganese metal complex and mercury chloride as composite catalyst prepare the octafluoro naphthalene technique (
inorganic Chemistry.2000,39,7,1618-1620.).But exist and top same shortcoming, manganese metal complex used is expensive, and Toxicity of Mercury Chloride is larger.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method who is suitable for industrialized octafluoro naphthalene, its production cost is low, and production technique is simple.
For achieving the above object, the technical scheme that the present invention takes is: the preparation method of octafluoro naphthalene of the present invention is: take Octachloronaphthalene and fluoride salt as raw material reaction generation octafluoro naphthalene.
Preferably, fluoride salt of the present invention be in Sodium Fluoride, Potassium monofluoride, cesium fluoride any or appoint several mixtures.
Preferably, the present invention can react under heating condition, and preferably temperature of reaction is 50
oc to 260
oc.
Preferably, also be added with solvent in the system of reaction of the present invention.Wherein, Octachloronaphthalene is dissolved in solvent, and fluoride salt is dissolved in fully or is partially soluble in solvent simultaneously.
Preferably, solvent of the present invention is a kind of or several mixture in ketones solvent, amide solvent, sulfone kind solvent, sulfoxide type solvent, alcoholic solvent.
Preferably, also can be added with catalyzer in the system of reaction of the present invention.
Preferably, catalyzer of the present invention is Bromide and/or iodized salt.
Preferably, Bromide of the present invention be in lithiumbromide, Sodium Bromide, Potassium Bromide, cesium bromide, magnesium bromide any or appoint several combinations; Described iodized salt be in lithium iodide, sodium iodide, potassiumiodide, cesium iodide, magnesium iodide any or appoint several combinations.
Compared with prior art, the invention has the beneficial effects as follows: its preparation technology has that technique is simple, safety, does not use expensive catalyst, is applicable to the advantages such as suitability for industrialized production.As preferred version of the present invention, in reaction, can add Bromide and/or iodized salt as catalyzer, because the bromine negative ion existed in reaction process, iodine negative ion specific activity fluorine anion are high, and its replace the carbon that forms after naphthalene chlorine in ring-bromine key, carbon-iodine bond than carbon-chlorine key a little less than, thereby reach the effect that catalyzed reaction is carried out.
Embodiment
Below by example, the invention will be further described, but do not limit the present invention.
Embodiment 1:
Add 500g acetone in reaction flask, 20ml water and 100g Octachloronaphthalene, slowly add the 100g Sodium Fluoride.After adding, under nitrogen protection, reaction solution is warming up to backflow.After having reacted, reaction solution is cooled to room temperature, adds 3L water, stir 30 minutes, filter to obtain octafluoro naphthalene 46g.mp:?87-88?
oC。
19F-NMR?(CCl
4,?400?MHz):?δ?-145.8?(4F,?s),?-154.5?(4F,?s)。
Embodiment 2:
Add 500g acetone in reaction flask, 20ml water and 100g Octachloronaphthalene, the 5g sodium iodide, slowly add the 100g Sodium Fluoride.After adding, under nitrogen protection, reaction solution is warming up to 50
oc.After having reacted, reaction solution is cooled to room temperature, adds 3L water, stir 30 minutes, filter to obtain octafluoro naphthalene 35g.mp:?86-88?
oC。
Embodiment 3
Add 500g ethanol and 100g Octachloronaphthalene in reaction flask, slowly add the 100g Sodium Fluoride.After adding, under nitrogen protection, reaction solution is warming up to backflow.After having reacted, reaction solution is cooled to room temperature, adds 3L water, stir 30 minutes, filter to obtain octafluoro naphthalene 43g.mp:?86-87?
oC。
Embodiment 4
Add 500g ethanol and 100g Octachloronaphthalene in reaction flask, the 5g potassiumiodide, slowly add the 100g Sodium Fluoride.After adding, under nitrogen protection, reaction solution is warming up to backflow.After having reacted, reaction solution is cooled to room temperature, adds 3L water, stir 30 minutes, filter to obtain octafluoro naphthalene 45g.mp:?86-87?
oC。
Embodiment 5
Add 600ml dimethyl formamide and 100g Octachloronaphthalene in reaction flask, slowly add the 100g Sodium Fluoride.After adding, reaction solution is warming up to backflow.After having reacted, reaction solution is cooled to room temperature, adds 3L water, stir 30 minutes, filter to obtain octafluoro naphthalene 50g.mp:?86.5-88?
oC。
Embodiment 6
Add the 600ml N,N-DIMETHYLACETAMIDE in reaction flask, 20ml water, and 100g Octachloronaphthalene, slowly add the 378g cesium fluoride.After adding, reaction solution is heated up to 160
oc.After having reacted, reaction solution is cooled to room temperature, adds 3L water, stir 30 minutes, filter to obtain octafluoro naphthalene 53g.mp:?87-88?
oC。
Embodiment 7
Add 600ml dimethyl sulfoxide (DMSO) and 100g Octachloronaphthalene in reaction flask, slowly add the 139g Potassium monofluoride.After adding, reaction solution is warming up to backflow.After having reacted, reaction solution is cooled to room temperature, adds 3L water, stir 30 minutes, filter to obtain octafluoro naphthalene 45g.mp:?86.5-87.5?
oC。
Embodiment 8
Add 600g dimethyl sulfone and 100g Octachloronaphthalene in reaction flask, slowly add the 100g Sodium Fluoride.After adding, be warming up in confined conditions 260
oc.After having reacted, reaction solution is cooled to room temperature, adds 3L water, stir 30 minutes, filter to obtain product octafluoro naphthalene 41g.mp:?86-87?
oC。
Embodiment 9
Add 400g methyl alcohol and 100g Octachloronaphthalene in reaction flask, the 5g potassiumiodide, slowly add the 100g Sodium Fluoride.After adding, reaction solution is warming up to backflow.After having reacted, reaction solution is cooled to room temperature, adds 3L water, stir 30 minutes, filter to obtain octafluoro naphthalene 45g.mp:?86.5-88?
oC。
Embodiment 10
Add 500g Isosorbide-5-Nitrae-dioxane and 100g Octachloronaphthalene in reaction flask, the 5g potassiumiodide, slowly add the 100g Sodium Fluoride.After adding, be warming up to backflow.After having reacted, reaction solution is cooled to room temperature, adds 3L water, stir 30 minutes, filter to obtain octafluoro naphthalene 35g.mp:?86.5-87.5?
oC。
Embodiment 11
Add 500g Isosorbide-5-Nitrae-dioxane in reaction flask, 20ml water, and 100g Octachloronaphthalene, the 5g magnesium iodide, slowly add the 100g Sodium Fluoride.After adding, reaction solution is warming up to backflow.After having reacted, reaction solution is cooled to room temperature, adds 3L water, stir 30 minutes, filter to obtain octafluoro naphthalene 32g.mp:?86-87?
oC。
Embodiment 12
Add the 400g tetrahydrofuran (THF) in reaction flask, water, and 100g Octachloronaphthalene, the 5g potassiumiodide, slowly add the 100g Sodium Fluoride.After adding, reaction solution is warming up to backflow.After having reacted, reaction solution is cooled to room temperature, is evaporated to dryly, add 3L water, stir 30 minutes, filter to obtain octafluoro naphthalene 36g.mp:?85-87?
oC。
Embodiment 13
Add 500g ethanol and 100g Octachloronaphthalene in reaction flask, the 5g Potassium Bromide, slowly add the 100g Sodium Fluoride.After adding, under nitrogen protection, reaction solution is warming up to backflow.After having reacted, reaction solution is cooled to room temperature, adds 3L water, stir 30 minutes, filter to obtain octafluoro naphthalene 32g.mp:?86-87?
oC。
Embodiment 14
Add 500g ethanol and 100g Octachloronaphthalene in reaction flask, the 5g Sodium Bromide, slowly add the 139g Potassium monofluoride.After adding, under nitrogen protection, reaction solution is warming up to backflow.After having reacted, reaction solution is cooled to room temperature, adds 3L water, stir 30 minutes, filter to obtain octafluoro naphthalene 35g.mp:?86.5-88?
oC。
It should be noted that, in the present invention, catalyzer can be in lithiumbromide, Sodium Bromide, Potassium Bromide, cesium bromide, magnesium bromide, lithium iodide, sodium iodide, potassiumiodide, cesium iodide, magnesium iodide any or appoint several combinations.Because the bromine negative ion existed in reaction process, iodine negative ion specific activity fluorine anion are high, and its replace the carbon that forms after naphthalene chlorine in ring-bromine key and carbon-iodine bond than carbon-chlorine key a little less than, thereby reach the effect that catalyzed reaction is carried out.
Claims (8)
1. the preparation method of an octafluoro naphthalene, is characterized in that: take Octachloronaphthalene and fluoride salt as raw material reaction generation octafluoro naphthalene.
2. the preparation method of octafluoro naphthalene according to claim 1 is characterized in that: described fluoride salt be in Sodium Fluoride, Potassium monofluoride, cesium fluoride any or appoint several mixtures.
3. the preparation method of octafluoro naphthalene according to claim 1 and 2, it is characterized in that: the temperature of reaction of described reaction is 50
oc to 260
oc.
4. the preparation method of octafluoro naphthalene according to claim 1 and 2, is characterized in that: also be added with solvent in the system of described reaction.
5. the preparation method of octafluoro naphthalene according to claim 4 is characterized in that: described solvent is a kind of in ketones solvent, amide solvent, sulfone kind solvent, sulfoxide type solvent, alcoholic solvent or appoints several mixtures.
6. the preparation method of octafluoro naphthalene according to claim 1 and 2, is characterized in that: also be added with catalyzer in the system of described reaction.
7. the preparation method of octafluoro naphthalene according to claim 6, it is characterized in that: described catalyzer is Bromide and/or iodized salt.
8. the preparation method of octafluoro naphthalene according to claim 7 is characterized in that: described Bromide is a kind of in lithiumbromide, Sodium Bromide, Potassium Bromide, cesium bromide or magnesium bromide or appoints several mixtures; Described iodized salt is a kind of or several mixture in lithium iodide, sodium iodide, potassiumiodide, cesium iodide or magnesium iodide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310478055.9A CN103497088A (en) | 2013-10-14 | 2013-10-14 | Method for preparing octafluoronaphthalene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310478055.9A CN103497088A (en) | 2013-10-14 | 2013-10-14 | Method for preparing octafluoronaphthalene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103497088A true CN103497088A (en) | 2014-01-08 |
Family
ID=49862378
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310478055.9A Pending CN103497088A (en) | 2013-10-14 | 2013-10-14 | Method for preparing octafluoronaphthalene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103497088A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108101729A (en) * | 2018-01-24 | 2018-06-01 | 金学芳 | A kind of synthetic method of seven fluoronaphthalene of compound 2- bromines |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6147426A (en) * | 1984-08-15 | 1986-03-07 | Nippon Shokubai Kagaku Kogyo Co Ltd | Production of fluorinated cyclic hydrocarbon |
| CN1238748A (en) * | 1996-11-22 | 1999-12-15 | 阿尔伯麦尔公司 | Halogen exchange reactions and uses thereof |
-
2013
- 2013-10-14 CN CN201310478055.9A patent/CN103497088A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6147426A (en) * | 1984-08-15 | 1986-03-07 | Nippon Shokubai Kagaku Kogyo Co Ltd | Production of fluorinated cyclic hydrocarbon |
| CN1238748A (en) * | 1996-11-22 | 1999-12-15 | 阿尔伯麦尔公司 | Halogen exchange reactions and uses thereof |
Non-Patent Citations (2)
| Title |
|---|
| S. Z. KUSOV ET AL.: "Synthesis of octafluoronaphthalene in the presence of crown ethers", 《IZVESTIYA SIBIRSKOGO OTDELENIYA AKADEMII NAUK SSSR, SERIYA KHIMICHESKIKH NAUK》, no. 3, 31 December 1986 (1986-12-31), pages 81 - 83 * |
| 吕早生 等: "卤素交换氟化技术研究进展", 《广州化工》, vol. 39, no. 19, 31 December 2011 (2011-12-31) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108101729A (en) * | 2018-01-24 | 2018-06-01 | 金学芳 | A kind of synthetic method of seven fluoronaphthalene of compound 2- bromines |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Martins et al. | Organic electrosynthesis: electrochemical alkyne functionalization | |
| Zeng et al. | Recent Advances in the One‐Step Synthesis of Distally Fluorinated Ketones | |
| Lu et al. | Relay cooperation of K 2 S 2 O 8 and O 2 in oxytrifluoromethylation of alkenes using CF 3 SO 2 Na | |
| Wu et al. | Three-dimensional covalent organic framework with tty topology for enhanced photocatalytic hydrogen peroxide production | |
| Liu et al. | Electroreductive Cross‐Electrophile Coupling (eXEC) Reactions | |
| Gao et al. | Efficient conversion of CO2 with olefins into cyclic carbonates via a synergistic action of I2 and base electrochemically generated in situ | |
| Wang et al. | Fixation of CO2 by electrocatalytic reduction to synthesis of dimethyl carbonate in ionic liquid using effective silver-coated nanoporous copper composites | |
| Wang et al. | Electrosynthesis of cyclic carbonates from CO2 and diols in ionic liquids under mild conditions | |
| CN104292145A (en) | Preparation method of 6-bromoindole derivative | |
| CN106914276A (en) | It is a kind of for acetylene add hcl reaction without mercury catalyst and preparation method | |
| CN109402659B (en) | Green synthesis method of alpha-thioenamine compound | |
| CN107829105A (en) | A kind of method of electrochemistry formated α acyloxy ketone | |
| Zeng et al. | Recent advances in green fluorine chemistry | |
| Yang et al. | Palladium-catalyzed directing group-assisted C8-triflation of naphthalenes | |
| CN108660478A (en) | A kind of electrochemical preparation method of alkenyl sulfone compound | |
| CN103497088A (en) | Method for preparing octafluoronaphthalene | |
| CN109126874B (en) | Bifunctional mixed type polyacid-based composite material and preparation method and application thereof | |
| CN108586267B (en) | A kind of preparation method of tri- fluorin benzyl amine of 2,4,6- | |
| Chen et al. | Hydrogen bonding network assisted regio-and stereo-controlled hydrohalogenations of sulfonyl alkynes | |
| CN103834426A (en) | Method for producing liquefied oil by directly hydro-liquefy coal in presence of ionic liquid | |
| Song et al. | Pentacoordinate Phosphoranes as Versatile Reagents in Fluoroalkylation Reactions | |
| CN104275210A (en) | Catalytic system for preparing 2, 5-furan dicarboxaldehyde by using 5-hydroxymethyl furfural and application thereof | |
| HU0700757D0 (en) | Process for producing pharmaceutical intermediers | |
| DE602004013279D1 (en) | ACID TRIPHOSPHATES OF FOUR QUALITY METALS | |
| CN102496713A (en) | Method for reducing free acid content in lithium hexafluorophosphate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Huang Jian Inventor after: Tan Xianghui Inventor after: Zhou Chen Inventor after: Sun Yanping Inventor after: Gao Zhiwei Inventor after: Shao Yongqi Inventor after: Luo Linfeng Inventor before: Huang Jian Inventor before: Tan Xianghui Inventor before: Zhou Chen Inventor before: Sun Yanping Inventor before: Gao Zhiwei Inventor before: Shao Yongqi Inventor before: Luo Linfeng |
|
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140108 |