CN105503489A - Inorganic halide containing ether solution - Google Patents
Inorganic halide containing ether solution Download PDFInfo
- Publication number
- CN105503489A CN105503489A CN201510972712.4A CN201510972712A CN105503489A CN 105503489 A CN105503489 A CN 105503489A CN 201510972712 A CN201510972712 A CN 201510972712A CN 105503489 A CN105503489 A CN 105503489A
- Authority
- CN
- China
- Prior art keywords
- solution
- halide
- zinc
- ether
- organic
- 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
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910001502 inorganic halide Inorganic materials 0.000 title claims abstract description 6
- 239000011701 zinc Substances 0.000 claims abstract description 21
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 20
- -1 zinc halide Chemical class 0.000 claims description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical group CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 239000001307 helium Substances 0.000 claims 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 238000006352 cycloaddition reaction Methods 0.000 abstract description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 abstract 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 10
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 8
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 6
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 6
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 235000011089 carbon dioxide Nutrition 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 229940059936 lithium bromide Drugs 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 229940102001 zinc bromide Drugs 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B31/00—Reduction in general
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
- C07B37/10—Cyclisation
-
- 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
- C07F3/06—Zinc compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention discloses an inorganic halide containing ether solution. The solution is mainly used for organic synthesis, can serve as a catalyst for a cycloaddition reaction and can be used for preparing a zinc reagent for a carbon-carbon coupling reaction or preparing enolate of zinc and a selective reducing reagent.
Description
Technical field
The present invention relates to organic synthesis field, is a kind of preparation and application thereof of the halide anhydrous aether solution for organic synthesis specifically.
Background technology
Organic zinc reagent or organolithium reagent are a kind of excellent organometallic reagents.The linked reaction of organic zinc reagent and halogenated aromatic can increase carbochain, and its reaction conditions is gentle, and yield is higher, and by product is less and toxicity is little.Zinc halide can react with corresponding organic-magnesium generation convert metals, generates corresponding organic zinc reagent; After carbonyl compound and alkali generation deprotonation are reacted, can react with zinc halide generation convert metals, generate the enolate of corresponding zinc; Can also as the catalyzer of cycloaddition reaction, as catalysis conjugated dienes compound and the addition reaction of carbonyl compound initial ring; Preparation optionally goes back original reagent, as NaBH
4with ZnBr
2reaction generates selective reduction reagent Zn (BH
4)
2.
Zinc halide and lithium halide powder easily absorb water and carbonic acid gas in atmosphere, at once the generation of side reaction is caused for organic synthesis, therefore be necessary zinc halide and lithium halide pressed powder to be dissolved among anhydrous ethereal solution, then be applied to eaily among different organic syntheses or catalyzed reaction.
Summary of the invention
Be applied to easily among organic synthesis in order to zinc halide and lithium halide can be made; reduce or avoid absorbing the moisture among air and carbonic acid gas; thus reduce the generation of side reaction, be necessary zinc halide and lithium halide solid particulate or powder dissolution among anhydrous organic ether solution.
For achieving the above object, technical scheme of the present invention is:
Among the container first organic ether solution being joined stirring, among organic ether solution, pass into the N that volume content is greater than 99.999% at once
2, Ar or He, simultaneously among ethereal solution, add molecular sieve again, carry out the process removing minor amount of water, process 1-12h, the dehydration completing ethereal solution, except after process, takes out solid-state molecular sieve, then at protective gas N
2, Ar or He protection under among the anhydrous aether solution stirred, add a certain amount of zinc halide and lithium halide solid particulate, until zinc halide and lithium halide dissolve, not exclusively can carry out suitable heating to solution if dissolved, temperature is generally at 10-150
owithin the scope of C.
Excellent results of the present invention is:
Halogenide solid particulate is dissolved among anhydrous organic ether, avoids and contact and the moisture absorption or carbonic acid gas with air among chemical reaction, thus avoid or reduce the generation of side reaction in organic reaction, be conveniently applied among chemical reaction.
Ethereal solution is prepared into by being dissolved in by halogenide solid particulate among anhydrous organic ether solution, avoid the water in halide mixture pellet absorption air or carbonic acid gas, and can be applied among organic chemical reactions easily, improve selectivity and the yield of main chemical reaction.
1. the anhydrous aether solution of the halide adopting the present invention to prepare, can be applied to easily among vitochemical building-up reactions, as C-C coupling reaction, the reactions such as cyclisation catalytic addition, can also prepare the enolate of zinc and optionally go back original reagent.
2. the anhydrous aether solution of the halide adopting the present invention to prepare, effectively can improve selectivity and the yield of main chemical reaction.
Embodiment
Embodiment 1
1L dibutyl ether organic solution poured among the there-necked flask that volume is 2L, among dibutyl ether solution, pass into the high-purity argon gas that volume content is 99.999%, flow is 300mlmin
-1, among solution, put into 5A type sieve particle about 50 grams simultaneously, slowly stir, after about 0.5h, salvage sieve particle, among dried dibutyl ether solution, add dry zinc bromide and lithiumbromide, quality is respectively 150 and 70 grams, constantly carries out magnetic agitation, and oil bath is heated to about 50
oc, until the solid particulate of zinc bromide and lithiumbromide dissolves completely, is then cooled to room temperature, and be prepared into the anhydrous dibutyl ether solution containing zinc bromide and lithiumbromide, wherein the content of water is 0.02%.
Embodiment 2
Pour among the there-necked flask of 5L by 3L phenyl ether organic solution, among phenyl ether solution, pass into the high pure nitrogen that volume content is 99.999%, flow is 500mlmin
-1, among solution, put into 4A type sieve particle 150 grams, magnetic agitation simultaneously, after about 1h, salvage sieve particle, then among dried phenyl ether solution, add dry zinc iodide and lithium iodide, quality is 320 grams, constantly stirs, and is heated to about 80
oc, until the solid particulate of zinc iodide and lithium iodide dissolves completely, is then cooled to room temperature, and be prepared into the anhydrous phenyl ether solution containing zinc iodide and lithium iodide, wherein the content of water is 0.03%.
Embodiment 3
Pour among there-necked flask by 1L anhydrous tetrahydro furan organic solution, pass into the high pure nitrogen that volume content is 99.999% among tetrahydrofuran solution, flow is 500mlmin
-1, among solution, put into 4A type sieve particle 100 grams, magnetic agitation, after about 2h, among dried tetrahydrofuran solution, add dry zinc chloride and lithium chloride, quality is 90 grams, constantly stirs, and oil bath is heated to about 40 simultaneously
oc, until the solid particulate of zinc bromide and lithiumbromide dissolves completely, is then cooled to room temperature, salvages sieve particle, is prepared into the anhydrous tetrahydrofuran solution of Containing Zinc Chloride and lithium chloride, and wherein the content of water is 0.11%.
Embodiment 4
Pour among there-necked flask by 3L methyl tertiary butyl ether organic solution, pass into the high-purity argon gas that volume content is 99.999% among t-butyl methyl ether solution, flow is 1000mlmin
-1, among solution, put into 10X type sieve particle 120 grams, magnetic agitation simultaneously, after about 1h, salvage sieve particle, among dried t-butyl methyl ether solution, add zinc fluoride and lithium fluoride, quality is 100 grams, constantly stirs, and is heated to about 35
oc, until the solid particulate of zinc fluoride and lithium fluoride dissolves completely, is then cooled to room temperature, and be prepared into the anhydrous methyl tertbutyl ether solution of fluorinated zinc and lithium fluoride, wherein the content of water is 0.05%.
Claims (9)
1., containing an ethereal solution for inorganic halides, it is characterized in that: this solution is the organic ether solution containing inorganic halides.
2. organic ether according to claim 1, is characterized in that: described organic ether is dibutyl ether, phenyl ether, tetrahydrofuran (THF), methyl tertiary butyl ether.
3. halogenide according to claim 1, is characterized in that: described halogenide is zinc halide and lithium halide, and halogen ion is F
-, Cl
-, Br
-and I
-.
4. ethereal solution according to claim 1, is characterized in that: in ethereal solution, the mass content of water is below 0.13%.
5. the lithium halide according to claim 1 or 3, is characterized in that: the mass content of described lithium halide is between 0.1-30%.
6. the zinc halide according to claim 1 or 3, is characterized in that: the mass content of described zinc halide is between 0.2-30%.
7. the ethereal solution preparation method containing inorganic halides according to claim 1; it is characterized in that: zinc halide and lithium halide solid particulate are slowly joined among the organic ether solution in stirring; and post-heating, until zinc halide and lithium halide solid particulate dissolve completely.
8. preparation method according to claim 7, is characterized in that: organic ether solution be prepared in the protection of protective gas under carry out, stir speed (S.S.) is 5-300 rev/min, and Heating temperature is 10-150
oc.
9. the preparation method according to claim 7 or 8, is characterized in that: protective gas be volume content higher than 99.999% high pure nitrogen, argon gas or helium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510972712.4A CN105503489A (en) | 2015-12-23 | 2015-12-23 | Inorganic halide containing ether solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510972712.4A CN105503489A (en) | 2015-12-23 | 2015-12-23 | Inorganic halide containing ether solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105503489A true CN105503489A (en) | 2016-04-20 |
Family
ID=55711868
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510972712.4A Pending CN105503489A (en) | 2015-12-23 | 2015-12-23 | Inorganic halide containing ether solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105503489A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080258319A1 (en) * | 2005-10-14 | 2008-10-23 | Sebastian Lang | Method for Preparing Diorganomagnesium-Containing Synthesis Means |
| US20100184977A1 (en) * | 2005-09-12 | 2010-07-22 | Paul Knochel | Nickel or Iron Catalysed Carbon-Carbon Coupling Reaction of Arylenes, Alkenes and Alkines |
| WO2012085168A1 (en) * | 2010-12-22 | 2012-06-28 | Ludwig-Maximilians-Universität München | Organozinc complexes and processes for making and using the same |
-
2015
- 2015-12-23 CN CN201510972712.4A patent/CN105503489A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100184977A1 (en) * | 2005-09-12 | 2010-07-22 | Paul Knochel | Nickel or Iron Catalysed Carbon-Carbon Coupling Reaction of Arylenes, Alkenes and Alkines |
| US20080258319A1 (en) * | 2005-10-14 | 2008-10-23 | Sebastian Lang | Method for Preparing Diorganomagnesium-Containing Synthesis Means |
| WO2012085168A1 (en) * | 2010-12-22 | 2012-06-28 | Ludwig-Maximilians-Universität München | Organozinc complexes and processes for making and using the same |
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Legal Events
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|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160420 |