CN1128126C - Process for synthesizing alpha-arylnaphthalene and its derivative - Google Patents
Process for synthesizing alpha-arylnaphthalene and its derivative Download PDFInfo
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- CN1128126C CN1128126C CN 01107679 CN01107679A CN1128126C CN 1128126 C CN1128126 C CN 1128126C CN 01107679 CN01107679 CN 01107679 CN 01107679 A CN01107679 A CN 01107679A CN 1128126 C CN1128126 C CN 1128126C
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- China
- Prior art keywords
- derivative
- alpha
- arylnaphthalene
- aryl
- method described
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- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 8
- 238000006471 dimerization reaction Methods 0.000 claims abstract description 4
- 150000002940 palladium Chemical class 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- -1 aryl ethane Chemical compound 0.000 claims description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 9
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 8
- 239000012530 fluid Substances 0.000 claims description 6
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical group [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 239000002798 polar solvent Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000010189 synthetic method Methods 0.000 claims description 3
- YLIAWYPQYFNYRS-UHFFFAOYSA-N C#C.C1=CC=CC2=CC=CC=C21 Chemical group C#C.C1=CC=CC2=CC=CC=C21 YLIAWYPQYFNYRS-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 abstract description 7
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 abstract 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract 1
- 230000026030 halogenation Effects 0.000 abstract 1
- 238000005658 halogenation reaction Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000002512 chemotherapy Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- IYDMICQAKLQHLA-UHFFFAOYSA-N 1-phenylnaphthalene Chemical compound C1=CC=CC=C1C1=CC=CC2=CC=CC=C12 IYDMICQAKLQHLA-UHFFFAOYSA-N 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- KFASDXAXYZEKNM-UHFFFAOYSA-N 6-methyl-1-(4-methylphenyl)naphthalene Chemical compound C1=CC(C)=CC=C1C1=CC=CC2=CC(C)=CC=C12 KFASDXAXYZEKNM-UHFFFAOYSA-N 0.000 description 1
- BLJLOSJXZCESDI-UHFFFAOYSA-N acetylene toluene Chemical group C#C.CC1=CC=CC=C1 BLJLOSJXZCESDI-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for synthesizing alpha-aryl naphthalene and a derivative thereof. Aryl acetylene and a derivative thereof are adopted by the method, and then, the alpha-aryl naphthalene and the derivative thereof are obtained thorough palladium catalyzing dimerization reaction. The method of the present invention comprises the following specific steps: aryl acetylene or the derivative of the aryl acetylene, a divalent palladium salt and halogenation copper are added into an organic compound with low polarity according to the molar ratio of 1:0.05 to 1:1 to 20; when the mixture is stirred at the room temperature of-100 DEG C and reacts for 2 to 24 hours, a product is filtered, washed and recrystallized to obtain pure alpha-aryl naphthalene and a derivative thereof. The present invention has the advantages of moderate reaction conditions, short time, simple operation, high yield and high product purity, and the regioselectivity is single.
Description
The present invention relates to the synthetic method of a kind of alpha-arylnaphthalene and derivative thereof, especially the novel method of synthetic alpha-arylnaphthalene of regiospecificity and derivative thereof.
Aromatic ring structure is medicine, spices and macromolecular important component part and basic framework.Mainly contain following several in the synthetic technology of relevant alpha-arylnaphthalene and derivative thereof:
(1), synthesizes alpha-arylnaphthalene and derivative (Org.Syntheses Coll.Vol.1,729 1941 and references in it) thereof with naphthalene or compound with naphthalene skeleton;
(2), be that raw material adopts synthetic alpha-arylnaphthalene of photochemical method and derivative (Ariella Evenzaharand Nicholas J.Turro, J.Am.Chem.Soc., 1998,120,1835-1841 and references in it) thereof with aryl ethane;
(3), be that raw material adopts synthetic alpha-arylnaphthalene of thermochemical method and derivative (Jinchao Yang and JohnG.Verkade, Organometallics, 2000,19,893-900 and references in it) thereof with aryl ethane.
In aforesaid method, wherein method (1) is though can make reaction reach regiospecific, and reactions steps is many and complicated, and some reaction or condition harshness or overall yield are low.And method (2) is difficult to reach regiospecific, and most applications is that alpha-arylnaphthalene and derivative thereof are by product.Method (3) then must comparatively high temps and must some special catalyzer, and this method does not reach synthetic alpha-arylnaphthalene of regiospecific and derivative thereof equally.
The purpose of this invention is to provide the novel method of a kind of synthetic alpha-arylnaphthalene and derivative thereof, it is simple to operate, the productive rate height, and product chemo-selective height and regioselectivity are single-minded.
The method of synthetic alpha-arylnaphthalene provided by the invention and derivative thereof is to adopt aryl ethane and derivative thereof to react through the palladium catalytic dimerization to obtain alpha-arylnaphthalene and derivative thereof.Concrete implementation step comprises: the mol ratio by 1: 0.05～1: 1～20 in low polar organic compound adds aryl ethane or derivatives thereof, divalence palladium salt and copper halide, ℃ following stirring reaction is 2～24 hours in room temperature～100, and product washs recrystallization after filtration and gets purified alpha-arylnaphthalene and derivative thereof.
The substrate scope that the present invention two aggregates into alpha-arylnaphthalene and derivative thereof is wide, having substituent derivative on various aryl ethanes and the aromatic nucleus thereof and all can be suitable for, especially can be to be with derivative, naphthalene acetylene and the derivative thereof that is no more than 4 substituting groups at most and has an ortho position unsubstituted at least on phenylacetylene and the benzene thereof.
Solvent for use of the present invention is a low polar solvent, can be low polarity alkane, aromatic hydrocarbons and supercutical fluid, and reaction effect is best when especially being reaction medium with normal hexane, Skellysolve A, benzene, alkylbenzene or supercritical carbon dioxide fluid.
Copper halide especially can be CuCl among the present invention
2And CuBr
2
Aryl ethane or derivatives thereof, divalence palladium salt and copper halide are pressed 1: 0.05～1: 1～20 mol ratio adding in the reaction, and from economic angle and reaction times and effect consideration, the mol ratio with 1: 0.05～0.25: 1～6 is reacted and was advisable in 2～10 hours.
Products therefrom is α position aryl substituent naphthalene and derivative thereof, productive rate 〉=95%, and product purity reaches more than 98% (GC).Wherein the structure of product be according to product nuclear-magnetism (
1H NMR,
13C NMR), IR, MS etc. compare with the known spectra data to determine.
Provided by the invention is that catalyzer prepares the alpha-arylnaphthalene novel method with aryl ethane regiospecific dimerization with divalence palladium salt-copper halide, reaction times is short, the reaction conditions gentleness, operation is simple, productive rate height (〉=95%), product purity also high (being no less than 98%), reaction solvent is recyclable and reusable, especially use this green medium of supercritical carbon dioxide fluid as reaction medium, help " greenization " of industry.The maximum difference of method provided by the present invention and forefathers' method is the use of catalyzer and the use of solvent (especially having used this green medium of supercritical carbon dioxide fluid).The common reaction conditions of forefathers' method is complicated and harsh, and so not only reaction product complexity, and product zone and chemo-selective are difficult to control.And the method for our invention to adopt divalence palladium-copper halide be catalyzer, chemo-selective height not only, product is single, and regioselectivity also reaches single-minded.
Embodiment 1
In the round-bottomed flask of 25mL, add earlier 10mL benzene, add then phenylacetylene (102mg, 1mmol), PdCl
2(10mg), CuBr
2(224mg, 1mmol).At room temperature stirring reaction reacted completely after 10 hours, filtered, and (2 * 5mL) wash 2 times solid part with ether.Distillation gets crude product after removing filtrate.Recrystallization gets more purified α-phenylnaphthalene.Output is 102mg, and productive rate is 100%, and product purity reaches more than 98% (GC).
Embodiment 2
In the round-bottomed flask of 25mL, add earlier 10mL toluene, add then to methylbenzene acetylene (116mg, 1mmol), PdBr
2(15mg), CuCl
2(96mg, 1mmol).At room temperature stirring reaction reacted completely after 10 hours, filtered, and (2 * 5mL) wash 2 times solid part with ether.Distillation gets crude product after removing filtrate.It is 116mg that recrystallization gets more purified 1-p-methylphenyl-6-methylnaphthalene output, and productive rate is 100%, and product purity reaches more than 98% (GC).
Embodiment 3
In the autoclave of 25mL, add earlier phenylacetylene (102mg, 1mmol), PdCl
2(10mg), CuBr
2(224mg 1mmol), charges into carbonic acid gas (14MPa) then., react completely after 12 hours at 40 ℃ of following stirring reactions, filter, (2 * 5mL) wash 2 times solid part with ether.Solid be cuprous bromide (white powder, 99.5mg, 2mmol).Distillation gets crude product after removing filtrate.Crystallization gets more purified α-phenylnaphthalene.Output is 102mg, and productive rate is 100%, and product purity reaches more than 98% (GC).
Claims (6)
1, the synthetic method of a kind of alpha-arylnaphthalene and derivative thereof, reaction obtains alpha-arylnaphthalene and derivative thereof through the palladium catalytic dimerization to it is characterized in that adopting aryl ethane and derivative thereof, concrete implementation step comprises: the mol ratio by 1: 0.05～1: 1～20 in low polar organic compound adds aryl ethane or derivatives thereof, divalence palladium salt and copper halide, ℃ following stirring reaction is 2～24 hours in room temperature～100, and product washs recrystallization after filtration and gets purified alpha-arylnaphthalene and derivative thereof.
2,, it is characterized in that described aryl ethane and derivative thereof are to be with derivative or naphthalene acetylene and the derivative thereof that is no more than 4 substituting groups at most and has an ortho position unsubstituted at least on phenylacetylene and the benzene thereof according to the method described in the claim 1.
3,, it is characterized in that described low polar solvent is low polarity alkane, aromatic hydrocarbons or supercutical fluid according to the method described in claim 1 or 2.
4,, it is characterized in that described low polar solvent is normal hexane, Skellysolve A, benzene, alkylbenzene or supercritical carbon dioxide fluid according to the method described in the claim 3.
5,, it is characterized in that described copper halide is CuCl according to the method described in claim 1 or 2
2And CuBr
2
6, according to the method described in claim 1 or 2, it is characterized in that described mol ratio is 1: 0.05～0.25: 1～6, the described reaction times is 2～10 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01107679 CN1128126C (en) | 2001-03-28 | 2001-03-28 | Process for synthesizing alpha-arylnaphthalene and its derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01107679 CN1128126C (en) | 2001-03-28 | 2001-03-28 | Process for synthesizing alpha-arylnaphthalene and its derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1317472A CN1317472A (en) | 2001-10-17 |
| CN1128126C true CN1128126C (en) | 2003-11-19 |
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ID=4656594
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01107679 Expired - Fee Related CN1128126C (en) | 2001-03-28 | 2001-03-28 | Process for synthesizing alpha-arylnaphthalene and its derivative |
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| Country | Link |
|---|---|
| CN (1) | CN1128126C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100427455C (en) * | 2006-09-15 | 2008-10-22 | 华南理工大学 | Preparation method for 1,3,5-trisubstituent benzene derivative |
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2001
- 2001-03-28 CN CN 01107679 patent/CN1128126C/en not_active Expired - Fee Related
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| Publication number | Publication date |
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