CN108623429A - A method of preparing 1,1 '-dinaphthalenes - Google Patents
A method of preparing 1,1 '-dinaphthalenes Download PDFInfo
- Publication number
- CN108623429A CN108623429A CN201810767030.3A CN201810767030A CN108623429A CN 108623429 A CN108623429 A CN 108623429A CN 201810767030 A CN201810767030 A CN 201810767030A CN 108623429 A CN108623429 A CN 108623429A
- Authority
- CN
- China
- Prior art keywords
- dinaphthalene
- reaction
- bmim
- ionic liquid
- samarium
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims abstract description 17
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002608 ionic liquid Substances 0.000 claims abstract description 16
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 13
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 13
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 butyl methyl tetrafluoroborate Chemical compound 0.000 claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 7
- 229960003280 cupric chloride Drugs 0.000 claims abstract description 5
- 239000011541 reaction mixture Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000004090 dissolution Methods 0.000 claims abstract description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical group C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 claims description 5
- 238000006578 reductive coupling reaction Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 claims description 2
- YMRPKBLFDBUOAJ-UHFFFAOYSA-N 5-butyl-2-methyl-1h-imidazole Chemical class CCCCC1=CN=C(C)N1 YMRPKBLFDBUOAJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- KYCQOKLOSUBEJK-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCN1C=C[N+](C)=C1 KYCQOKLOSUBEJK-UHFFFAOYSA-M 0.000 claims 1
- XREPTGNZZKNFQZ-UHFFFAOYSA-M 1-butyl-3-methylimidazolium iodide Chemical compound [I-].CCCCN1C=C[N+](C)=C1 XREPTGNZZKNFQZ-UHFFFAOYSA-M 0.000 claims 1
- 150000003851 azoles Chemical class 0.000 claims 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 238000005580 one pot reaction Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 abstract description 9
- 238000004064 recycling Methods 0.000 abstract description 4
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 abstract 1
- 238000004440 column chromatography Methods 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 229940090668 parachlorophenol Drugs 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- KWXLUINFEWUOHF-UHFFFAOYSA-N CC=1NC=CN1.ClC(CCC)O Chemical compound CC=1NC=CN1.ClC(CCC)O KWXLUINFEWUOHF-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910006130 SO4 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 150000005171 halobenzenes Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of to promote the method that 1 halogen naphthalene coupling reaction prepares 1,1 ' dinaphthalenes under cupric salt catalysis in ionic liquid using samarium metal.By 1 bromonaphthalene in ionic liquid [bmim] [BF under stirring4] mixed dissolution in (butyl methyl tetrafluoroborate), then sequentially add samarium metal powder, anhydrous cupric chloride powder.Reaction system carries out under the conditions of anhydrous.It is stirred at room temperature down until the reaction is complete.Obtained reaction mixture carries out ionic liquid recycling.Purified on column chromatography isolated 1,1 ' dinaphthalene recrystallize to obtain sterling, yield 70 98%.
Description
Technical field
The invention belongs to transition metal-catalyzed synthesis fields, and in particular to a kind of to be synthesized using cupric salt catalysis 1- halogen naphthalenes
The method of 1,1 '-dinaphthalenes.
Background technology
1,1 '-dinaphthalenes compounds are organic synthesis intermediates important in chemical industry, in catalysis, pharmacy, chiral are closed
At had a wide range of applications in, light-sensitive material [document 1. opens beautiful, Zheng Tucai, Mu Zhongyue, waits Chemical Manufactures and technology, 2014,
21(03):31-44+9.].Synthesis for it, studies in China are relatively fewer.Usually with the method ratio of the coupling reaction of 1- halogen naphthalenes
More typically, need noble metal for example palladium class compound for catalysis carry out 1- halogen naphthalene cross-couplings come synthesize [document 2.Nising C F,
Schmid U K,Nieger M,The Journal of Organic Chemistry,2004,69:6830-6833.].Separately
Outside, Grignard Reagent is also one of method from the reaction of coupling type, but such methods usually require relative complex operating condition
[3. Jinpeng of Tang of document, Tang Yu, Yang Jun wait organic chemistry, 2013,33 (05):1010-1014. document 4.Lee A S-Y et
al.Journal of the Chinese Chemical Society,2012,59(3):452-454.].Suzuki types are coupled
Reaction be also commonly used for synthesizing this kind of compound [document 5.Yaghi O M, et al.PCT Int Appl 2011014503,
2011-02].We use nickel chloride or cuprous iodide that can be coupled a variety of halogenated hydrocarbons under samarium metal promotion in recent years, but not
There is the coupling [Qingdao the coupling reaction research section of the refined shining transition metal-catalyzed lower samarium metal interventions of of 6. Xiao of document for realizing 1- halogen naphthalenes
Skill university, 2017.].
Traditional chemical reacts and its relevant chemical industry is main source that the world today seriously pollutes, pollution it is very big
Part comes from a large amount of effumability organic solvent used in reaction process, such as benzene, chloralkane, alcohol, ketone.For
The pollution of organic solvent, it is important research content to find green and substitute solvent.Wherein, it is organic anti-to make solvent progress for ionic liquid
Should be it is current substitute a kind of important method in solvent technology [7. Jiang of document is average, Li Xiaoting, cold inflammation, and chemical industry is waited to be in progress, 2014,
33(11):2815-2828.]。
The invention discloses one kind in a small amount of ion liquid solvent, and chlorination copper catalysis promotes 1- halogen naphthalene one using samarium metal
The method that coupling reaction prepares 1,1 '-dinaphthalene is walked, this method is there is not yet domestic and foreign literature is reported.
Invention content
Make the 1- halogen naphthalenes be coupled in ionic liquid to prepare the simplicity of 1,1 '-dinaphthalenes the purpose of the present invention is to provide a kind of
Method.
Technical scheme is as follows：
In anhydrous cupric salt and in the presence of [bmim] salt (butyl methyl imidazole salts), using samarium metal by 1- halogen naphthalene room temperatures
Lower reductive coupling is 1,1 '-dinaphthalene, and reaction formula is shown below：
In formula, X preferred Cl, Br, I, SO4；The preferred BF of X '4,PF6,Cl,Br,I。
Specific technical solution is：By 1- chloronaphthalenes in ionic liquid [bmim] [BF under stirring4] (butyl methyl imidazoles tetrafluoro boron
Hydrochlorate) in mixed dissolution, then sequentially add samarium metal powder, anhydrous cupric chloride powder.Wherein, ionic liquid dosage is 1- chloronaphthalenes
2-20 times of the mass ratio of dosage；Samarium powder dosage is 0.5-5 times of the molar ratio of 1- chloronaphthalene dosages；Anhydrous cupric chloride dosage is used for samarium powder
0.05-0.5 times of the molar ratio of amount；Reaction system carries out under the conditions of anhydrous.
It is stirred at room temperature down until the reaction is complete.Obtained reaction mixture carries out ionic liquid recycling, and residue is after
After processing, isolated 1,1 '-dinaphthalene sterling of chromatographic column, yield 70-98%.
The advantages and positive effects of the present invention：
Synthetic route of the present invention is simple and efficient, and only need to can be obtained 1,1 '-dinaphthalene by single step reaction, and operating procedure is few,
Without separation of intermediates, last handling process is simple, and product is easily isolated, and greatly simplifies operation and requires；The present invention reacts item
Part is easily achieved, and does not need the conditions such as low temperature, high temperature, illumination, pressure, strong acid and strong base, and the cupric salt that use cost is cheap
Catalyst is made, the particular/special requirements such as living things catalysis, precious metal catalyst are avoided；Cupric salt can get even well as catalyst
Join effect, reason thinks to may be the dissolving in ionic liquid [bmim] Cl (chlorobutanol methylimidazole) due to cupric salt
Property it is preferable, and compared with the reagents such as cuprous iodide, copper chloride property price stabilization is cheap, avoids and uses relatively expensive and molecule
Larger iodine is measured, Atom economy is good；Samarium metal used shows excellent reactivity in the present invention, makes parachlorophenol smoothly also
Original coupling is 1,1 '-dinaphthalene, and magnesium metal, zinc etc. are difficult to realize such conversion under condition of similarity in contrast, since samarium is dilute
The rare earth resources of earth metal, China account for 90% of the world or more, therefore effective exploitation utilizes rare earth metal to China with great
Meaning；Parachlorophenol used is of low cost in halobenzene phenol in the present invention but relatively prepared by relatively inert, usually generation coupling reaction
The relatively difficult either yield of dinaphthalene is relatively low or reaction condition is complicated, therefore the present invention is reduced in cost and had simplifying technique
Significant technological progress；Ionic liquid used in the present invention be novel green solvent can abundant recovery, and thus
So that reaction cost is further declined, and ionic liquid dosage be far less than usual organic solvent dosage, about 1/10, this both made
Technical process is simplified, and improves the concentration of reaction system to intensified response effect.
Specific implementation mode
Following synthesis example is used for further illustrating the present invention, but is not intended to limit the present invention.
Example 1
The samarium metal powder of 3g brand-news, anhydrous cupric chloride 0.26g, magnetic agitation are sequentially added into dry reaction vessel.
Then 1- chloronaphthalenes 4.1g, 10mL are sequentially added and removes water dry butyl methyl tetrafluoroborate in advance.Reaction is at room temperature
It carries out, darkens in reaction mixture 5h, the reaction was continued 12h.Reaction solution is extracted with ethyl acetate, post-treated to obtain 1,1 '-
Dinaphthalene crude product.Then further pillar layer separation and by recrystallization purifying, obtains 1,1 '-dinaphthalene, yield 92%.
White solid, 142-144 DEG C of of fusing point1HNMR(500MHz,CDCl3)δppm 7.24-7.31(1H,m),7.39
(1H,d,J3(H)=8.2Hz), 7.42-7.52 (2H, m), 7.58 (1H, t, J3(H)=7.6Hz), 7.91-7.98 (2H, m),13C NMR(62.5MHz,CDCl3):125.5,125.9,126.1,126.7,127.9,128.0,128.3,133.0,133.6,
138.6.
Dichloromethane is added in raffinate after ethyl acetate extraction, passes through stirring, standing, transfer, merging, evaporation recycling
After solvent, the ionic liquid of recycling is obtained.
Example 2
By 1 method of example, tetrafluoroborate is replaced using butyl methyl imidazoles chlorate, obtains 1,1 '-dinaphthalene, yield
87%.
Example 3
By 1 method of example, [bmim] [BF4] after reusing 5 times, it still can preferably realize the conversion of substrate, obtain
To 1,1 '-dinaphthalene, yield 82%.
Claims (8)
1. a kind of method of 1,1 '-dinaphthalene of synthesis, it is characterised in that under cupric salt catalysis, metal is used in ionic liquid
Samarium promotes one step reductive coupling reaction of 1- halogen naphthalene to prepare 1,1 '-dinaphthalene, and preparation process includes the following steps：
By 1- halogen naphthalenes mixed dissolution in ionic liquid under stirring, samarium metal powder, anhydrous cupric salt powder are then sequentially added；
Reaction system carries out under the conditions of anhydrous, is stirred at room temperature down until the reaction is complete；Obtained reaction mixture carries out ion
Liquids recovery, after residue is post-treated, pillar layer separation obtains 1,1 '-dinaphthalene sterling.
2. a kind of method of 1,1 '-dinaphthalene of synthesis according to claim 1, it is characterised in that used ionic liquid is used
Amount is 2-20 times of the mass ratio of 1- halogen naphthalene dosages；Samarium powder dosage is 0.5-5 times of the molar ratio of 1- halogen naphthalene dosages；Anhydrous cupric chloride is used
Amount is 0.05-0.5 times of the molar ratio of samarium powder dosage.
3. a kind of method of 1,1 '-dinaphthalene of synthesis according to claim 1, it is characterised in that used cupric salt is
The one or more of copper chloride, copper bromide, cupric iodide, copper sulphate.
4. a kind of method of 1,1 '-dinaphthalene of synthesis according to claim 1, it is characterised in that used 1- halogen naphthalene is 1-
Chloronaphthalene.
5. a kind of method of 1,1 '-dinaphthalene of synthesis according to claim 1, it is characterised in that used ionic liquid is
Butyl methyl imidazole salts [bmim] X.
6. a kind of method of 1,1 '-dinaphthalene of synthesis according to claim 1, it is characterised in that used butyl methyl miaow
Azoles salt [bmim] X is [bmim] BF4,[bmim]PF6, one or more of [bmim] Cl, [bmim] Br, [bmim] I.
7. a kind of method of 1,1 '-dinaphthalene of synthesis according to claim 1, it is characterised in that used reductive coupling gold
It is samarium to belong to.
8. a kind of method of 1,1 '-dinaphthalene of synthesis according to claim 1, it is characterised in that reaction process is one kettle way one
Step reaction, reaction temperature is room temperature, and reaction dissolvent can recycle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810767030.3A CN108623429B (en) | 2018-07-12 | 2018-07-12 | Method for preparing 1, 1' -binaphthyl |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810767030.3A CN108623429B (en) | 2018-07-12 | 2018-07-12 | Method for preparing 1, 1' -binaphthyl |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108623429A true CN108623429A (en) | 2018-10-09 |
| CN108623429B CN108623429B (en) | 2021-05-04 |
Family
ID=63690012
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810767030.3A Active CN108623429B (en) | 2018-07-12 | 2018-07-12 | Method for preparing 1, 1' -binaphthyl |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108623429B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265147A (en) * | 2008-05-08 | 2008-09-17 | 上海交通大学 | Method for preparing biaryl |
-
2018
- 2018-07-12 CN CN201810767030.3A patent/CN108623429B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265147A (en) * | 2008-05-08 | 2008-09-17 | 上海交通大学 | Method for preparing biaryl |
Non-Patent Citations (5)
| Title |
|---|
| K. YASAMUT ET AL.，: ""A modified Cu(0)-Cu(I)-mediated Caryl-Caryl Ullmann coupling for the synthesis of biaryls"", 《TETRAHEDRON》 * |
| X.L. ZHENG ET AL.，: ""Coupling reaction of aryl halides promoted by NiCl2/PPh3 /Sm0"", 《J. CHEM. RESEARCH》 * |
| 申永存等: ""联萘二甲酸的合成与拆分"", 《武汉理工大学学报（交通科学与工程版）》 * |
| 肖淑焕: ""过渡金属催化下金属钐介入的偶联反应研究"", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
| 蒋平平等: ""离子液体制备及其化工应用进展"", 《化工进展》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108623429B (en) | 2021-05-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109320496B (en) | Selenocyanization reagent and preparation method and application thereof | |
| CN108715574A (en) | A method of synthesis '-biphenyl diphenol | |
| CN107141207B (en) | Synthetic method of 3 '-acyl-2, 4' -dihydroxy benzophenone compound | |
| CN109096126B (en) | Deuterium labeled D9Synthesis method of clenbuterol hydrochloride | |
| CN108623429A (en) | A method of preparing 1,1 '-dinaphthalenes | |
| Guijarro et al. | Structure–Reactivity Relationship in the Reaction of Highly Reactive Zinc with Alkyl Bromides | |
| CN111574444A (en) | Preparation method of bedaquiline | |
| CN110183456A (en) | A kind of synthetic method of 2- arylindazoles succinimide spiro-compound | |
| CN108947801A (en) | 4- chlorobenzoic acid prepares biphenyl dicarboxylic acid in ionic liquid | |
| CN104909982A (en) | Method for synthesizing benzyl bromide compound directly from isotope labeled benzene rings | |
| CN110041274B (en) | Method for preparing 5-fluoroalkyl triazole compound by air oxidation multi-component one-pot method | |
| CN107936034B (en) | Benzyloxy dibenzo [b, f] dislikes English in heptan cyclopropylene acid compounds and intermediate and its application | |
| CN112194559A (en) | Synthesis method of chiral and achiral 2,2' -dihalogenated biaryl compounds | |
| CN105777666A (en) | Preparation method of iodine atom-substituted methylic fluorobenzene and heterocyclic compound | |
| CN106278856A (en) | A kind of synthetic method replacing benzfluorenone compounds | |
| CN105348094A (en) | Acyl chloride and alkyne addition product and preparing method thereof | |
| CN108658803A (en) | A kind of synthetic method of N, N- dialkyl group diphenylpropanamide | |
| CN104311377A (en) | Synthesis method of biphenyl compounds | |
| CN110015960A (en) | The preparation method and application of 1,3- bis- (4,4- methyl formate phenyl) acetone | |
| WO2023097696A1 (en) | Method for synthesizing (1r)-1-(2,2-dimethyl-4h-1,3-benzodioxin-6-yl)-2-nitroethanol | |
| CN107382782A (en) | A kind of synthetic method of polyaryl substituted naphthol derivative | |
| CN112110824B (en) | Method for preparing 2-bromo-5-fluoroaniline | |
| CN116037152B (en) | Palladium copper-cuprous oxide core-shell nano-cage catalyst and preparation method and application thereof | |
| CN107501234A (en) | A kind of oil-source rock correlation and preparation method thereof | |
| CN110452138B (en) | Method for preparing N-phenyl-3-methylsulfonyl propionamide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Qi Yan Inventor after: Song Bin Inventor after: Liu Yongjun Inventor after: Liu Shufeng Inventor before: Liu Yongjun Inventor before: Liu Shufeng Inventor before: Song Bin Inventor before: Qi Yan |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240812 Address after: 256100 Yiyuan Economic Development Zone, Zibo City, Shandong Province Patentee after: SHANDONG XINQUAN PHARMACEUTICAL Co.,Ltd. Country or region after: China Address before: No. 53, Zhengzhou Road, North District, Qingdao, Shandong Patentee before: QINGDAO University OF SCIENCE AND TECHNOLOGY Country or region before: China |