CN110003275B - Synthesis method of 4, 6-di (diphenylphosphine) phenazine compound - Google Patents
Synthesis method of 4, 6-di (diphenylphosphine) phenazine compound Download PDFInfo
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- CN110003275B CN110003275B CN201910328455.9A CN201910328455A CN110003275B CN 110003275 B CN110003275 B CN 110003275B CN 201910328455 A CN201910328455 A CN 201910328455A CN 110003275 B CN110003275 B CN 110003275B
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- -1 (diphenylphosphine) phenazine compound Chemical class 0.000 title claims abstract description 20
- 238000001308 synthesis method Methods 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- RYXZOQOZERSHHQ-UHFFFAOYSA-N [2-(2-diphenylphosphanylphenoxy)phenyl]-diphenylphosphane Chemical compound C=1C=CC=C(P(C=2C=CC=CC=2)C=2C=CC=CC=2)C=1OC1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RYXZOQOZERSHHQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- QHVNYFLBHSVOKR-UHFFFAOYSA-N (9-diphenylphosphanylphenazin-1-yl)-diphenylphosphane Chemical compound C1(=CC=CC=C1)P(C1=CC=CC2=NC3=CC=CC(=C3N=C12)P(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 QHVNYFLBHSVOKR-UHFFFAOYSA-N 0.000 claims abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 6
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 229940125904 compound 1 Drugs 0.000 claims description 4
- 229940125782 compound 2 Drugs 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 150000001540 azides Chemical class 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 4
- 238000010511 deprotection reaction Methods 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 125000001644 phenoxazinyl group Chemical class C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006138 lithiation reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010499 C–H functionalization reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 238000000607 proton-decoupled 31P nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
Classifications
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- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
- C07F9/6533—Six-membered rings
- C07F9/65335—Six-membered rings condensed with carbocyclic rings or carbocyclic ring systems
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a synthesis method of a 4, 6-bis (diphenylphosphino) phenazine compound, belonging to the field of organic synthesis. In an anhydrous and oxygen-free atmosphere, bis (2-diphenylphosphinophenyl) ether is used as a raw material to react with sodium azide, and then 4, 6-bis (diphenylphosphino) phenazine is synthesized through azide/intramolecular C-H ammoniation. The method has the advantages of few reaction steps, mild reaction conditions, simple operation and high yield, and plays a good role in promoting the application of the compounds in the field of catalysis.
Description
Technical Field
The invention belongs to the field of organic synthesis, relates to a synthesis method of an organic phosphine compound, and particularly relates to a synthesis method of a 4, 6-bis (diphenylphosphino) phenazine compound.
Technical Field
The coupling reaction participated by the organic phosphine catalyst is an effective means for forming C-C, C-N, C-S and other bonds in organic synthesis, and has very wide application in synthesizing natural products, functional materials, medicines, liquid crystal molecules and bioactive compounds. 4, 6-di (diphenylphosphine) phenazine is an important catalyst ligand, can react with a transition metal compound to generate a homogeneous catalyst, is widely applied to the field of industrial catalysis, and is particularly applied to coupling reaction in the field of organic synthesis. The 4, 6-bis (diphenylphosphino) phenazine compound has excellent electronic effect and steric effect due to the special electron-rich property and larger steric hindrance capability, and can form a complex with a special space structure and excellent catalytic performance with a plurality of metal salts. The ligand has good application in hydroformylation reaction, palladium-catalyzed carbon-hydrogen bond activation and carbon-chlorine bond coupling reaction and other reactions, so that the synthesis and property research of the ligand is always a research hotspot.
At present, the 4, 6-position modification of phenoxazines (Organometallics 2000, 19, 872; J. org. chem. 1989,54, 2159) is mainly carried out by N atom protection, N-butyllithium hydrogen abstraction, reaction with electrophilic reagents, and final deprotection to obtain 4, 6-disubstituted phenoxazines. The method has the main defects that most of adopted protecting groups are alkyl or phenethyl, on one hand, the positioning effect is poor, and lithiation can also occur at the 1-position and the 9-position of phenoxazine; on the other hand, the deprotection condition is harsh, and the palladium-carbon catalytic hydrogenation condition is needed for the deprotection. In view of the excellent catalytic activity of the compound after the action with metal, it is necessary to explore a more efficient and practical synthesis method of the 4, 6-bis (diphenylphosphino) phenazine compound.
Disclosure of Invention
The invention aims to provide a novel method for synthesizing a 4, 6-bis (diphenylphosphino) phenazine compound, which has the advantages of high yield, specific selectivity, mild reaction conditions and simple operation.
In order to achieve the above object, the reaction scheme of the present invention is as follows:
the reaction steps of the invention are as follows:
(1) under the protection of argon, adding a reaction solvent acetonitrile into a drying reactor, and then sequentially adding bis (2-diphenylphosphinophenyl) ether (compound 2), cuprous bromide and tert-butyl hydroperoxide [ (CH)3)3COOH]Aqueous solution of sodium azide, addingCarrying out thermal stirring reaction; (2) then adding [ (RhCp Cl ] into the system2)2]Heating and reacting silver hexafluoroantimonate; after the reaction is finished, cooling the reaction system to room temperature, extracting, drying and recrystallizing to obtain the target product 4, 6-bis (diphenylphosphino) phenazine compound (compound 1).
The bis (2-diphenylphosphinophenyl) ether is mixed with sodium azide, cuprous bromide and tert-butyl hydroperoxide [ (CH)3)3COOH]The molar ratio of (A) to (B) is 1:2 to 4:0.1 to 0.2:2 to 3.
The bis (2-diphenylphosphinophenyl) ether is reacted with [ (RhCp Cl ]2)2]The molar ratio of silver hexafluoroantimonate is 1: 0.02-0.05: 0.1-0.2.
The temperature in the step (2) is 70-100 DEG CoC。
The invention has the beneficial effects that: the defect of poor positioning effect is overcome, and the probability that lithiation occurs at 1-position and 9-position of phenoxazine is avoided; deprotection under the condition of palladium-carbon catalytic hydrogenation is avoided; the method adopts a one-pot two-step method, efficiently and practically synthesizes the 4, 6-di (diphenylphosphine) phenazine compound, the reaction condition is mild, the reaction steps are few, the operation is simple, and the yield can reach more than 85 percent.
Detailed Description
The following examples are provided to aid in the further understanding of the invention, but the invention is not limited thereto. Examples are as follows:
example 1:
under the protection of argon, 700 mL of acetonitrile serving as a reaction solvent is added into a dry reactor, and then 538 g of bis (2-diphenylphosphinophenyl) ether (compound 2), 14 g of cuprous bromide and tert-butyl hydroperoxide [ (CH)3)3COOH]180 g, 100 mL (130 g/100 mL) of aqueous solution of sodium azide, 30oStirring and reacting for 12 hours under the condition of C; adding [ (RhCp Cl ] into the system2)2]12 g of silver hexafluoroantimonate (34 g, 70 g)oC, reacting for 18 h; after the reaction is stopped, the reaction system is cooled to room temperature, extracted, dried and recrystallized to obtain 468 g (yield 85%) of the target product 4, 6-bis (diphenylphosphino) phenazine (compound 1).1H NMR (400 MHz, C6D6 )：δ 7.37 (m, 8 H), 6.98 ( m, 12 H), 6.25 ( m, 2 H ), 5.84 (d, 2 H), 4.23 (s, 1 H). 31P{1H}NMR (162 MHz, C6D6 ): δ -17.6. 13C{1H} NMR (100 MHz, C6D6 ): δ 145.9, 137.5, 134.2, 131.8, 128.5, 126.1, 125.7, 125.6, 113.5.
Example 2:
under the protection of argon, 700 mL of acetonitrile serving as a reaction solvent is added into a dry reactor, and then 538 g of bis (2-diphenylphosphinophenyl) ether (compound 2), 14 g of cuprous bromide and tert-butyl hydroperoxide [ (CH)3)3COOH]180 g, 100 mL (130 g/100 mL) of aqueous solution of sodium azide, 30oStirring and reacting for 12 hours under the condition of C; adding [ (RhCp Cl ] into the system2)2]12 g of silver hexafluoroantimonate 34 g, 100oC, reacting for 18 h; after the reaction is stopped, the reaction system is cooled to room temperature, extracted, dried and recrystallized to obtain 507 g (yield 92%) of the target product 4, 6-bis (diphenylphosphino) phenazine (compound 1).
Claims (4)
1. The synthesis method of the 4, 6-bis (diphenylphosphino) phenazine compound with the structural formula shown as 1 is characterized by being realized by the following method,
(1) under the protection of argon, adding a reaction solvent acetonitrile into a drying reactor, and then sequentially adding bis (2-diphenylphosphinophenyl) ether (compound 2), cuprous bromide and tert-butyl hydroperoxide [ (CH)3)3COOH]Heating and stirring the sodium azide aqueous solution for reaction; (2) then adding [ (RhCp Cl ] into the system2)2]Heating and reacting silver hexafluoroantimonate; after the reaction is finished, cooling the reaction system to room temperature, extracting, drying and recrystallizing to obtain a target product 4, 6-bis (diphenylphosphino) phenazine (compound 1);
2. the method of claim 1, wherein said bis (2-diphenylphosphinophenyl) ether is reacted with sodium azide, cuprous bromide and t-butyl hydroperoxide [ (CH) H ] (i) to form a 4, 6-bis (diphenylphosphino) phenazine compound3)3COOH]The molar ratio of (A) to (B) is 1:2 to 4:0.1 to 0.2:2 to 3.
3. The method of claim 1, wherein the bis (2-diphenylphosphinophenyl) ether is reacted with [ (RhCp. Cl.) to form a 4, 6-bis (diphenylphosphino) phenazine compound2)2]The molar ratio of silver hexafluoroantimonate is 1: 0.02-0.05: 0.1-0.2.
4. The method for synthesizing 4, 6-bis (diphenylphosphino) phenazine compound according to any one of claims 1 to 3, wherein the reaction temperature in step (2) is 70 to 100%oC。
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2332407C1 (en) * | 2007-05-21 | 2008-08-27 | Государственное образовательное учреждение высшего профессионального образования "Сибирский государственный технологический университет" | Method of 7,8-phtaloylacridone derivatives production |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2332407C1 (en) * | 2007-05-21 | 2008-08-27 | Государственное образовательное учреждение высшего профессионального образования "Сибирский государственный технологический университет" | Method of 7,8-phtaloylacridone derivatives production |
Non-Patent Citations (3)
| Title |
|---|
| Lewis Acid-Promoted Synthesis of Unsymmetrical and Highly Functionalized Carbazoles and Dibenzofurans from Biaryl Triazenes: Application for the Total Synthesis of Clausine C, Clausine R, and Clauraila A;Yang, Weijun et al;《Chemistry - A European Journal》;20111231;第17卷;第13665-13669页 * |
| NiXantphos: A Deprotonatable Ligand for Room-Temperature Palladium-Catalyzed Cross-Couplings of Aryl Chlorides;Zhang, Jiadi et al;《Journal of the American Chemical Society》;20141231;第136卷;第6276-6287页 * |
| Origin of the Bite Angle Effect on Rhodium Diphosphine Catalyzed Hydroformylation;Van der Veen et al;《Organometallics》;20001231;第19卷;第872-883页 * |
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