CN109096336B - A kind of preparation method and application of benzo phospha naphthalene derivatives - Google Patents
A kind of preparation method and application of benzo phospha naphthalene derivatives Download PDFInfo
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- CN109096336B CN109096336B CN201811169395.2A CN201811169395A CN109096336B CN 109096336 B CN109096336 B CN 109096336B CN 201811169395 A CN201811169395 A CN 201811169395A CN 109096336 B CN109096336 B CN 109096336B
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- 125000005605 benzo group Chemical group 0.000 title claims abstract description 30
- 150000002790 naphthalenes Chemical class 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 119
- -1 alkyl alkynes Chemical class 0.000 claims abstract description 29
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010949 copper Substances 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 11
- 239000011574 phosphorus Substances 0.000 claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 75
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 70
- 238000004809 thin layer chromatography Methods 0.000 claims description 25
- 238000004440 column chromatography Methods 0.000 claims description 24
- 238000000926 separation method Methods 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- XQFARSXVMYNQRL-UHFFFAOYSA-N acetylene chlorobenzene Chemical group C#C.ClC1=CC=CC=C1 XQFARSXVMYNQRL-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- MJBPUQUGJNAPAZ-UHFFFAOYSA-N Butine Natural products O1C2=CC(O)=CC=C2C(=O)CC1C1=CC=C(O)C(O)=C1 MJBPUQUGJNAPAZ-UHFFFAOYSA-N 0.000 claims description 8
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- CRFJRGSTIQFTQW-UHFFFAOYSA-N acetylene fluorobenzene Chemical group C#C.FC1=CC=CC=C1 CRFJRGSTIQFTQW-UHFFFAOYSA-N 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 5
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- MYBSUWNEMXUTAX-UHFFFAOYSA-N 1-ethynyl-2-methylbenzene Chemical group CC1=CC=CC=C1C#C MYBSUWNEMXUTAX-UHFFFAOYSA-N 0.000 claims description 4
- ZASXCTCNZKFDTP-UHFFFAOYSA-N 1-ethynyl-3-methoxybenzene Chemical group COC1=CC=CC(C#C)=C1 ZASXCTCNZKFDTP-UHFFFAOYSA-N 0.000 claims description 4
- RENYIDZOAFFNHC-UHFFFAOYSA-N 1-ethynyl-3-methylbenzene Chemical group CC1=CC=CC(C#C)=C1 RENYIDZOAFFNHC-UHFFFAOYSA-N 0.000 claims description 4
- XTKBMZQCDBHHKY-UHFFFAOYSA-N 1-ethynyl-4-(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC=C(C#C)C=C1 XTKBMZQCDBHHKY-UHFFFAOYSA-N 0.000 claims description 4
- KBIAVTUACPKPFJ-UHFFFAOYSA-N 1-ethynyl-4-methoxybenzene Chemical group COC1=CC=C(C#C)C=C1 KBIAVTUACPKPFJ-UHFFFAOYSA-N 0.000 claims description 4
- NHUBNHMFXQNNMV-UHFFFAOYSA-N 2-ethynylpyridine Chemical compound C#CC1=CC=CC=N1 NHUBNHMFXQNNMV-UHFFFAOYSA-N 0.000 claims description 4
- KSZVOXHGCKKOLL-UHFFFAOYSA-N 4-Ethynyltoluene Chemical group CC1=CC=C(C#C)C=C1 KSZVOXHGCKKOLL-UHFFFAOYSA-N 0.000 claims description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- UISZKHSCSVDZMV-UHFFFAOYSA-N acetylene nitrobenzene Chemical group C#C.[N+](=O)([O-])C1=CC=CC=C1 UISZKHSCSVDZMV-UHFFFAOYSA-N 0.000 claims description 4
- QDJZBFLFHUMZBE-UHFFFAOYSA-N acetylene;bromobenzene Chemical group C#C.BrC1=CC=CC=C1 QDJZBFLFHUMZBE-UHFFFAOYSA-N 0.000 claims description 4
- YVXHZKKCZYLQOP-UHFFFAOYSA-N hept-1-yne Chemical compound CCCCCC#C YVXHZKKCZYLQOP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- JPGRSTBIEYGVNO-UHFFFAOYSA-N methyl 4-ethynylbenzoate Chemical group COC(=O)C1=CC=C(C#C)C=C1 JPGRSTBIEYGVNO-UHFFFAOYSA-N 0.000 claims description 4
- GHUURDQYRGVEHX-UHFFFAOYSA-N prop-1-ynylbenzene Chemical compound CC#CC1=CC=CC=C1 GHUURDQYRGVEHX-UHFFFAOYSA-N 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- IOPDYTCCKSYLJG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ynylbenzene Chemical group FC(F)(F)C#CC1=CC=CC=C1 IOPDYTCCKSYLJG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 238000004587 chromatography analysis Methods 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 6
- 230000035484 reaction time Effects 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 44
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 44
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 43
- 239000002994 raw material Substances 0.000 description 27
- 238000005160 1H NMR spectroscopy Methods 0.000 description 22
- 238000004458 analytical method Methods 0.000 description 22
- 239000003208 petroleum Substances 0.000 description 22
- 230000015572 biosynthetic process Effects 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 16
- 229910052760 oxygen Inorganic materials 0.000 description 8
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N tert-butyl alcohol Substances CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 3
- DTMHTVJOHYTUHE-UHFFFAOYSA-N thiocyanogen Chemical compound N#CSSC#N DTMHTVJOHYTUHE-UHFFFAOYSA-N 0.000 description 3
- OOZKONVIIMFOKW-UHFFFAOYSA-N 1-ethynyl-2-(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC=CC=C1C#C OOZKONVIIMFOKW-UHFFFAOYSA-N 0.000 description 2
- UFOVULIWACVAAC-UHFFFAOYSA-N 1-ethynyl-2-methoxybenzene Chemical group COC1=CC=CC=C1C#C UFOVULIWACVAAC-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- MERJTCXDDLWWSK-UHFFFAOYSA-N 1-methylpyrrole pyrrolidin-2-one Chemical compound CN1C=CC=C1.N1C(CCC1)=O MERJTCXDDLWWSK-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000004446 heteroarylalkyl group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- GWLJTAJEHRYMCA-UHFFFAOYSA-N phospholane Chemical compound C1CCPC1 GWLJTAJEHRYMCA-UHFFFAOYSA-N 0.000 description 1
- 150000004857 phospholes Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
Classifications
-
- 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
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
- C07F9/65685—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a phosphine oxide or thioxide
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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)
Abstract
The invention discloses a kind of benzo phospha naphthalene derivatives and preparation method thereof, comprising the following steps: alkynes, phosphorus reagent, copper catalyst and organic peroxide are dissolved in solvent, reacted at 50 ~ 100 DEG C, benzo phospha naphthalene derivatives are obtained；Alkynes can be alkyl alkynes, aryl alkynes, quinary heteroaryl alkynes, six membered heteroaryl alkynes.Method disclosed by the invention, reaction condition is mild, and the reaction time is short, the high income of target product, and operation and last handling process are simple.
Description
Technical field
The invention belongs to the preparation technical fields of organic compound, and in particular to a kind of preparation of benzo phospha naphthalene derivatives
Method and application.
Background technique
Phosphorus hetercyclic compound can be used for being catalyzed reaction, such as phospholane, Phospholes, benzo phospha indoles etc.
It can effectively catalyze organic reaction.In addition, phosphorus hetercyclic compound has fire retardation, can be applied in fire proofing.But
It is in the synthetic route of published phosphorus hetercyclic compound, raw material is difficult to obtain, and severe reaction conditions are cumbersome, yield
It is lower.Therefore it is extremely important to develop the synthetic method that a kind of reaction condition is mild, reaction step is succinct, raw material are simple and easy to get.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of benzo phospha naphthalene derivatives, simple with raw material sources,
The advantages that reaction condition is mild, post-processing is simple, yield is high.
To achieve the above object of the invention, the technical solution adopted by the present invention is that:
A kind of preparation method of benzo phospha naphthalene derivatives, comprising the following steps: by alkynes, phosphorus reagent, copper catalyst and
Organic peroxide is dissolved in solvent, is reacted at 50 ~ 100 DEG C, and benzo phospha naphthalene derivatives are obtained.
The invention also discloses in the presence of copper catalyst, organic peroxide, solvent, alkynes, phosphorus reagent are as raw material
Preparing the application in benzo phospha naphthalene derivatives.
In the present invention, the alkyl is selected from ethyl, butyl, heptyl；The aralkyl is in phenethyl or benzene butyl
It is a kind of；
The aryl is as shown in following general formula of the chemical structure:
Wherein R1It is selected from: one of alkoxy, halogen, nitro, trifluoromethyl, ester group；
The heteroaryl is as shown in following general formula of the chemical structure:
Wherein X is selected from: one of O, S or N；Y is selected from: one of O, S, N.
The alkynes is as shown in following general formula of the chemical structure:
Wherein R is selected from one of hydrogen, alkyl, aralkyl, aryl, heteroarylalkyl, heteroaryl；
The phosphorus reagent is as shown in having structure general formula:
Wherein A is selected from aryl or naphthalene.
In the present invention, alkynes can be alkyl alkynes, aryl alkynes, quinary heteroaryl alkynes, six membered heteroaryl alkynes；Institute
Alkyl alkynes is stated as shown in following general formula of the chemical structure:
Wherein R5Selected from one of hydrogen, ethyl, butyl, amyl, heptyl, phenethyl or benzene butyl；
It is described from shown in the following column general formula of the chemical structure of aryl alkynes:
Wherein R1It is selected from: one of alkyl, alkoxy, halogen, nitro, trifluoromethyl, ester group；
The quinary heteroaryl alkynes is as shown in following general formula of the chemical structure:
Wherein X is selected from: one of O, S or N；
The six membered heteroaryl alkynes is as shown in following general formula of the chemical structure:
Wherein Y is selected from: one of O, S, N.
The organic peroxide is as shown in following general formula of the chemical structure:
Wherein R2It is selected from: one of methyl or phenyl；R3It is selected from: one of hydrogen, tert-butyl or benzoyl；
The chemical formula of the copper catalyst is CuXn, and wherein X is one of Cl, Br, I, SCN；N is 1 or 2.
The solvent is selected from: methanol, ethyl alcohol, acetonitrile, acetone, ethyl acetate, water, 1,2- dichloroethanes, toluene, N, N- bis-
One of methylformamide or N-Methyl pyrrolidone.
The benzo phospha naphthalene derivatives are as shown in following general formula of the chemical structure:
Preferably, the alkyl alkynes derivative is selected from: in acetylene, butine, hexin, 4- phenyl -1- butine or heptyne
It is a kind of；(miscellaneous) the arylalkyne hydrocarbon derivative is selected from: phenylacetylene, 4- methyl phenylacetylene, 4- Methoxy-phenylacetylene, 4- fluorophenethyl
Alkynes, 4- chlorobenzene acetylene, 4- bromobenzene acetylene, 4-(trifluoromethyl) phenylacetylene, 4- nitrobenzene acetylene, 4- methoxycarbonyl phenylacetylene,
3- methyl phenylacetylene, 3- chlorobenzene acetylene, 3- Methoxy-phenylacetylene, 2- methyl phenylacetylene, 2- fluorobenzene acetylene, 2- chlorobenzene acetylene, 2-
One in (trifluoromethyl) phenylacetylene, 1- phenyl -1- propine, 4- phenyl -1- butine, 2- thiophene acetylene or 2- ethynyl pyridine
Kind.
In above-mentioned technical proposal, using thin-layer chromatography chromatography (TLC) tracking reaction until being fully completed.
In above-mentioned technical proposal, in molar ratio, alkynes: phosphorus reagent: copper catalyst: organic peroxide 1: 2: 0.2: (2
~ 6).
In above-mentioned technical proposal, column chromatography for separation purification processes are carried out to product after reaction.
The reaction process of above-mentioned technical proposal can be expressed as follows:
Due to the application of the above technical scheme, compared with the prior art, the invention has the following advantages:
1, the present invention is starting material using alkynes, and raw material is easy to get, type is more.
2, method disclosed by the invention, reaction condition is mild, and the reaction time is short, the high income of target product, operation
It is simple with last handling process.
Specific embodiment
The present invention will be further described below with reference to examples:
One: 1-(naphthalene -1- base of embodiment) -3- phenyl benzo [de] phospha naphthalene -1- oxide synthesis
Using phenylacetylene, dinaphthyl phosphine oxide as raw material, reaction step is as follows:
Phenylacetylene (0.051 gram, 0.5 mmol) is added in reaction flask, dinaphthyl oxygen phosphorus (0.30 gram, 1 mmol),
CuI2(0.032g, 0.1 mmol), propyloxy phenyl base hydrogen peroxide (0.23 g, 1.5 mmol) and ethyl acetate (2 mL),
60oC reaction；
TLC tracking reaction is until be fully completed；
The crude by column chromatography separation (ethyl acetate: petroleum ether=1:1) obtained after reaction, obtains target
Product (yield 96%).Based on E44 epoxy resin and dicyandiamide system, the flame retardant property of above-mentioned product is studied according to national standard,
E44/ dicyandiamide, E44/ dicyandiamide/product (addition 12wt%) oxygen index (OI) be respectively 24,27.The analysis data of product are as follows:1H NMR (400 MHz, CDCl3): δ 8.69 (m, 1H), 8.35 (m, 1H), 8.07 (m, 4H), 7.86 (d,J = 8.0 Hz, 2H), 7.59 (m, 3H), 7.41 (m, 5H), 7.26 – 7.19 (m, 2H), 6.56 (m,
1H)。
Two: 1-(naphthalene -1- base of embodiment) -3-(4- tolyl) benzo [de] phospha naphthalene -1- oxide synthesis
Using 4- methyl phenylacetylene, dinaphthyl oxygen phosphorus as raw material, reaction step is as follows:
4- methyl phenylacetylene (0.053 gram, 0.5 mmol) is added in reaction flask, and dinaphthyl oxygen phosphorus (0.30 gram, 1
Mmol), CuI (0.019 g, 0.1 mmol), propyloxy phenyl base hydrogen peroxide (0.46 g, 3 mmol) and water (2 mL),
100oC reaction；
TLC tracking reaction is until be fully completed；
The crude by column chromatography separation (ethyl acetate: petroleum ether=1:1) obtained after reaction, obtains target
Product (yield 85%).The analysis data of product are as follows: 1H NMR (400 MHz, CDCl3): δ8.51 (m, 1H), 8.35
(m, 1H), 8.17 (d, J = 8.3 Hz, 1H), 8.11 (m, 1H), 8.04 (d, J = 7.7 Hz, 2H),
7.89 (d, J = 8.3 Hz, 1H), 7.72 (d, J = 7.4 Hz, 1H), 7.68 – 7.54 (m, 4H), 7.51
– 7.30 (m, 3H), 7.05 (m, 2H), 6.58 (d, J = 9.8 Hz, 1H), 2.44 (s, 3H)。
Three: 1-(naphthalene -1- base of embodiment) -3-(4- methoxyphenyl) benzo [de] phospha naphthalene -1- oxide synthesis
Using 4- Methoxy-phenylacetylene, dinaphthyl oxygen phosphorus as raw material, reaction step is as follows:
4- Methoxy-phenylacetylene (0.066 gram, 0.5 mmol) is added in reaction flask, and dinaphthyl oxygen phosphorus (0.30 gram, 1
Mmol), Cu (SCN)2 (0.0179 gram, 0.1 mmol), tertbutanol peroxide (0.45 mL, 3 mmol) and 1,2- dichloroethanes
(2 mL), 80oC reaction；
TLC tracking reaction is until be fully completed；
The crude by column chromatography separation (ethyl acetate: petroleum ether=1:1) obtained after reaction, obtains target
Product (yield 79%).The analysis data of product are as follows:1H NMR (400 MHz, CDCl3): δ8.31 (m, 1H), 8.21
– 8.05 (m, 2H), 8.02 (d, J = 8.3 Hz, 2H), 7.86 (d, J = 8.1 Hz, 1H), 7.72 (d,J = 7.4 Hz, 1H), 7.60 (m, 3H), 7.46 – 7.32 (m, 3H), 7.24 (m, 2H), 6.96 (d, J
= 8.5 Hz, 2H), 6.56 (d, J = 10.4 Hz, 1H), 3.85 (s, 3H)。
Example IV: 1-(naphthalene -1- base) -3-(4- fluorophenyl) benzo [de] phospha naphthalene -1- oxide synthesis
Using 4- fluorobenzene acetylene, dinaphthyl oxygen phosphorus as raw material, reaction step is as follows:
4- fluorobenzene acetylene (0.060 gram, 0.5 mmol) is added in reaction flask, and dinaphthyl oxygen phosphorus (0.30 gram, 1
Mmol), CuSCN (0.012 gram, 0.1 mmol), tertbutanol peroxide (0.45 mL, 3 mmol) and toluene (2 mL), 90oC
Reaction；
TLC tracking reaction is until be fully completed；
The crude by column chromatography separation (ethyl acetate: petroleum ether=1:1) obtained after reaction, obtains target
Product (yield 82%).The analysis data of product are as follows:1H NMR (400 MHz, CDCl3): δ8.33 (m, 1H), 7.97
(m, 4H), 7.72 (d, J = 7.4 Hz, 1H), 7.50 (m, 7H), 7.11 (m, 4H), 6.55 (s, 1H)。
Five: 1-(naphthalene -1- base of embodiment) -3-(4- chlorphenyl) benzo [de] phospha naphthalene -1- oxide synthesis
Using 4- chlorobenzene acetylene, dinaphthyl oxygen phosphorus as raw material, reaction step is as follows:
4- chlorobenzene acetylene (0.068 gram, 0.5 mmol) is added in reaction flask, and dinaphthyl oxygen phosphorus (0.30 gram, 1
Mmol), CuCl2 (0.014 g, 0.1 mmol), peroxidized t-butyl perbenzoate (0.29 g, 3 mmol) and N, N- dimethyl
Formamide (2 mL), 100oC reaction；
TLC tracking reaction is until be fully completed；
The crude by column chromatography separation (ethyl acetate: petroleum ether=1:1) obtained after reaction, obtains target
Product (yield 85%).The oxygen index (OI) of E44/ dicyandiamide/product (addition 12wt%) is 28；The analysis data of product are as follows:1H
NMR (400 MHz, CDCl3): δ8.31 (m, 1H), 8.07 (m, 5H), 7.87 (d, J = 8.0 Hz, 1H),
7.76 (d, J = 7.4 Hz, 1H), 7.66 – 7.51 (m, 4H), 7.40 (m, 4H), 7.19 (m, 1H),
6.56 (m, 1H)。
Six: 1-(naphthalene -1- base of embodiment) -3-(4- bromophenyl) benzo [de] phospha naphthalene -1- oxide synthesis
Using 4- bromobenzene acetylene, dinaphthyl oxygen phosphorus as raw material, reaction step is as follows:
4- bromobenzene acetylene (0.088 gram, 0.5 mmol) is added in reaction flask, and dinaphthyl oxygen phosphorus (0.30 gram, 1
Mmol), CuCl (0.01 g, 0.1 mmol), peroxidized t-butyl perbenzoate (0.15 g, 1.5 mmol) and N- methylpyrrole
Alkanone (2 mL), 70oC reaction；
TLC tracking reaction is until be fully completed；
The crude by column chromatography separation (ethyl acetate: petroleum ether=1:1) obtained after reaction, obtains target
Product (yield 81%).The analysis data of product are as follows:1H NMR (400 MHz, CDCl3): δ8.31 (m, 1H), 8.06
(m, 4H), 7.88 (d, J = 8.1 Hz, 1H), 7.66 – 7.51 (m, 6H), 7.49 – 7.27 (m, 4H),
7.26 (m, 1H), 6.56 (m, 1H)。
Seven: 1-(naphthalene -1- base of embodiment) -3-(4- nitrobenzophenone) benzo [de] phospha naphthalene -1- oxide synthesis
Using 4- nitrobenzene acetylene, dinaphthyl oxygen phosphorus as raw material, reaction step is as follows:
4- nitrobenzene acetylene (0.077 gram, 0.5 mmol) is added in reaction flask, and dinaphthyl oxygen phosphorus (0.30 gram, 1
Mmol), CuBr2 (0.022 g, 0.1 mmol), di-tert-butyl peroxide (0.45 g, 3 mmol) and acetone (2 mL),
50oC reaction；
TLC tracking reaction is until be fully completed；
The crude by column chromatography separation (ethyl acetate: petroleum ether=1:1) obtained after reaction, obtains target
Product (yield 65%).The analysis data of product are as follows:1H NMR (400 MHz, CDCl3): δ8.35 – 8.25 (m,
3H), 8.21 (d, J = 8.1 Hz, 1H), 8.18 – 8.11 (m, 1H), 8.07 (m, 2H), 7.98 (d, J
= 8.6 Hz, 1H), 7.90 (d, J = 8.2 Hz, 1H), 7.74 – 7.52 (m, 5H), 7.52 – 7.39 (m,
2H), 7.28 (m, 1H), 6.61 (d, J = 9.4 Hz, 1H)。
Eight: 1-(naphthalene -1- base of embodiment) -3-(4- methoxycarbonyl-phenyl) benzo [de] phospha naphthalene -1- oxide conjunction
At
Using 4- methoxycarbonyl phenylacetylene, dinaphthyl oxygen phosphorus as raw material, reaction step is as follows:
4- methoxycarbonyl phenylacetylene (0.080 gram, 0.5 mmol) is added in reaction flask, dinaphthyl oxygen phosphorus (0.30
Gram, 1 mmol), CuBr (0.014 g, 0.1 mmol), di-tert-butyl peroxide (0.30 g, 2 mmol) and water (2
ML), 80oC reaction；
TLC tracking reaction is until be fully completed；
The crude by column chromatography separation (ethyl acetate: petroleum ether=1:1) obtained after reaction, obtains target
Product (yield 75%).The analysis data of product are as follows: 1H NMR (400 MHz, CDCl3): δ8.30 (m, 1H), 8.20
– 8.15 (m, 1H), 8.11 (m, 3H), 8.02 (m, 2H), 7.89 (t, J = 7.9 Hz, 2H), 7.67 –
7.58 (m, 2H), 7.56 (d, J = 4.8 Hz, 2H), 7.50 – 7.39 (m, 3H), 7.30 – 7.20 (m,
1H), 6.58 (d, J = 8.8 Hz, 1H), 3.94 (s, 3H)。
Nine: 1-(naphthalene -1- base of embodiment) -3-(4- trifluoromethyl) benzo [de] phospha naphthalene -1- oxide synthesis
Using 4- trifluoromethyl phenylacetylene, dinaphthyl oxygen phosphorus as raw material, reaction step is as follows:
4- trifluoromethyl phenylacetylene (0.085 gram, 0.5 mmol) is added in reaction flask, dinaphthyl oxygen phosphorus (0.30 gram,
1 mmol), CuI2 (0.032 g, 0.1 mmol), propyloxy phenyl base hydrogen peroxide (0.46 g, 3 mmol) and N, N- diformazan
Base formamide (2 mL), 70oC reaction；
TLC tracking reaction is until be fully completed；
The crude by column chromatography separation (ethyl acetate: petroleum ether=1:1) obtained after reaction, obtains target
Product (yield 82%).The analysis data of product are as follows:1H NMR (400 MHz, CDCl3): δ8.68 (m, 1H), 8.75–
8.69 (m, 1H), 8.56 – 8.29 (m, 1H), 8.18 – 7.90 (m, 2H), 7.88 – 7.80 (m, 2H),
7.65 – 7.63 (m, 4H), 7.60– 7.58 (m, 4H), 7.40 – 7.35 (m, 1H), 7.25 (m, 2H),
6.38 (m, 1H)。
Ten: 1-(naphthalene of embodiment) -3-(3- tolyl)-benzo [de] phospha naphthalene -1- oxide synthesis
Using 3- methyl phenylacetylene, dinaphthyl oxygen phosphorus as raw material, reaction step is as follows:
3- methyl phenylacetylene (0.058 gram, 0.5 mmol) is added in reaction flask, and dinaphthyl oxygen phosphorus (0.30 gram, 1
Mmol), CuI (0.019 g, 0.1 mmol), propyloxy phenyl base hydrogen peroxide (0.23 g, 1.5 mmol) and ethyl alcohol (2
ML), 70oC reaction；
TLC tracking reaction is until be fully completed；
The crude by column chromatography separation (ethyl acetate: petroleum ether=1:1) obtained after reaction, obtains target
Product (yield 84%).The analysis data of product are as follows:1H NMR (400 MHz, CDCl3): δ 8.54 (m, 1H), 8.46
– 8.29 (m, 1H), 8.30 – 8.10 (m, 1H), 8.10 – 7.97 (m, 2H), 7.94 – 7.85 (m,
2H), 7.79 – 7.67 (m, 2H), 7.62 – 7.51 (m, 4H), 7.48 – 7.32 (m, 2H), 7.20 (m,
2H), 6.57 (m, 1H), 2.44 (s, 3H)。
11: 1-(naphthalene -1- base of embodiment) -3-(3- methoxyphenyl) benzo [de] phospha naphthalene -1- oxide synthesis
Using 3- Methoxy-phenylacetylene, dinaphthyl oxygen phosphorus as raw material, reaction step is as follows:
3- Methoxy-phenylacetylene (0.066 gram, 0.5 mmol) is added in reaction flask, and dinaphthyl oxygen phosphorus (0.30 gram, 1
Mmol), Cu (SCN)2 (0.0179 gram, 0.1 mmol), tertbutanol peroxide (0.45 mL, 3 mmol) and acetonitrile (2 mL),
60oC reaction；
TLC tracking reaction is until be fully completed；
The crude by column chromatography separation (ethyl acetate: petroleum ether=1:1) obtained after reaction, obtains target
Product (yield 73%).The analysis data of product are as follows:1H NMR (400 MHz, CDCl3): δ8.33 (m, 1H), 8.20
– 7.97 (m, 5H), 7.86 (d, J = 8.2 Hz, 1H), 7.76 – 7.65 (m, 1H), 7.58 (m, 3H),
7.37 (m, 1H), 7.26 – 7.16 (m, 3H), 6.95 (m, 2H), 6.59 (d, J = 9.9 Hz, 1H),
3.81 (s, 1H)。
12: 1-(naphthalene of embodiment) -3-(3- chlorphenyl)-benzo [de] phospha naphthalene -1- oxide synthesis
Using 3- chlorobenzene acetylene, dinaphthyl oxygen phosphorus as raw material, reaction step is as follows:
3- chlorobenzene acetylene (0.068 gram, 0.5 mmol) is added in reaction flask, and dinaphthyl oxygen phosphorus (0.30 gram, 1
Mmol), CuSCN (0.012 gram, 0.1 mmol), tertbutanol peroxide (0.45 mL, 3 mmol) and water (2 mL), 80oC is anti-
It answers；
TLC tracking reaction is until be fully completed；
The crude by column chromatography separation (ethyl acetate: petroleum ether=1:1) obtained after reaction, obtains target
Product (yield 77%).The analysis data of product are as follows:1H NMR (400 MHz, CDCl3): δ8.30 (m, 1H), 8.08
(m, 4H), 7.87 (d, J = 8.1 Hz, 1H), 7.66 – 7.51 (m, 3H), 7.28 (m, 6H), 7.26
(m, 2H), 6.56 (m, 1H)。
13: 1-(naphthalene of embodiment) -3-(2- aminomethyl phenyl)-benzo [de] phospha naphthalene -1- oxide synthesis
Using 2- methyl phenylacetylene, dinaphthyl oxygen phosphorus as raw material, reaction step is as follows:
2- methyl phenylacetylene (0.058 gram, 0.5 mmol) is added in reaction flask, and dinaphthyl oxygen phosphorus (0.30 gram, 1
Mmol), CuCl2 (0.014 g, 0.1 mmol), peroxidized t-butyl perbenzoate (0.15 g, 1.5 mmol) and N- methyl pyrrole
Pyrrolidone (2 mL), 60oC reaction；
TLC tracking reaction is until be fully completed；
The crude by column chromatography separation (ethyl acetate: petroleum ether=1:1) obtained after reaction, obtains target
Product (yield 72%).The analysis data of product are as follows:1H NMR (400 MHz, CDCl3): δ8.54 (m, 1H), 8.46
– 8.29 (m, 1H), 8.30 – 8.10 (m, 4H), 8.10 – 7.97 (m, 2H), 7.94 – 7.85 (m,
2H), 7.79 – 7.67 (m, 4H), 7.62 – 7.51 (m, 4H), 7.48 – 7.32 (m, 1H), 7.20 (m,
2H), 6.57 (m, 1H), 2.38 (s, 3H)。
14: 1-(naphthalene -1- base of embodiment) -3-(2- methoxyphenyl) benzo [de] phospha naphthalene -1- oxide synthesis
Using 2- Methoxy-phenylacetylene, dinaphthyl oxygen phosphorus as raw material, reaction step is as follows:
2- Methoxy-phenylacetylene (0.066 gram, 0.5 mmol) is added in reaction flask, and dinaphthyl oxygen phosphorus (0.30 gram, 1
Mmol), CuCl (0.01 g, 0.1 mmol), di-tert-butyl peroxide (0.45 g, 3 mmol) and N- crassitude
Ketone (2 mL), 70oC reaction；
TLC tracking reaction is until be fully completed；
The crude by column chromatography separation (ethyl acetate: petroleum ether=1:1) obtained after reaction, obtains target
Product (yield 73%).The analysis data of product are as follows:1H NMR (400 MHz, CDCl3): δ8.63 (m, 1H), 8.12
– 7.96 (m, 4H), 7.92 – 7.82 (m, 2H), 7.59 – 7.47 (m, 3H), 7.42 (m, 2H), 7.23
(m, 1H), 7.16 – 7.05 (m, 3H), 6.55 (m, 1H), 3.66 (s, 3H)。
15: 1-(naphthalene -1- base of embodiment) -3-(2- chlorphenyl) benzo [de] phospha naphthalene -1- oxide synthesis
Using 2- chlorobenzene acetylene, dinaphthyl oxygen phosphorus as raw material, reaction step is as follows:
2- chlorobenzene acetylene (0.068 gram, 0.5 mmol) is added in reaction flask, and dinaphthyl oxygen phosphorus (0.30 gram, 1
Mmol), CuBr2 (0.022 g, 0.1 mmol), di-tert-butyl peroxide (0.30 g, 2 mmol) and ethyl alcohol (2 mL),
80oC reaction；
TLC tracking reaction is until be fully completed；
The crude by column chromatography separation (ethyl acetate: petroleum ether=1:1) obtained after reaction, obtains target
Product (yield 74%).The analysis data of product are as follows:1H NMR (400 MHz, CDCl3): δ8.30 (m, 1H), 8.08
(m, 4H), 7.86 (d, J = 8.1 Hz, 1H), 7.66 – 7.51 (m, 4H), 7.28 (m, 6H), 7.23
(m, 1H), 6.50 (m, 1H)。
16: 1-(naphthalene of embodiment) -3-(2- fluorophenyl)-benzo [de] phospha naphthalene -1- oxide synthesis
Using 2- fluorobenzene acetylene, dinaphthyl oxygen phosphorus as raw material, reaction step is as follows:
2- fluorobenzene acetylene (0.060 gram, 0.5 mmol) is added in reaction flask, and dinaphthyl oxygen phosphorus (0.30 gram, 1
Mmol), CuBr (0.014 g, 0.1 mmol), propyloxy phenyl base hydrogen peroxide (0.46 g, 3 mmol) and ethyl alcohol (2
ML), 70oC reaction；
TLC tracking reaction is until be fully completed；
The crude by column chromatography separation (ethyl acetate: petroleum ether=1:1) obtained after reaction, obtains target
Product (yield 78%).The analysis data of product are as follows:1H NMR (400 MHz, CDCl3): δ8.30 (m, 1H), 7.91
(m, 6H), 7.50 (m, 8H), 7.08 (m, 2H), 6.53 (m, 1H)。
17: 1-(naphthalene -1- base of embodiment) -3-(2- trifluoromethyl) benzo [de] phospha naphthalene -1- oxide conjunction
At
Using 2- trifluoromethyl phenylacetylene, dinaphthyl oxygen phosphorus as raw material, reaction step is as follows:
2- trifluoromethyl phenylacetylene (0.085 gram, 0.5 mmol) is added in reaction flask, dinaphthyl oxygen phosphorus (0.30 gram,
1 mmol), CuI2 (0.032 g, 0.1 mmol), tertbutanol peroxide (0.45 mL, 3 mmol) and ethyl alcohol (2 mL),
60oC reaction；
TLC tracking reaction is until be fully completed；
The crude by column chromatography separation (ethyl acetate: petroleum ether=1:1) obtained after reaction, obtains target
Product (yield 77%).The analysis data of product are as follows:1H NMR (400 MHz, CDCl3): δ8.68 (m, 1H), 8.5 –
8.26 (m, 4H), 8.12 – 7.90 (m, 2H), 7.85 – 7.60 (m, 3H), 7.42 (m, 2H), 7.23
(m, 1H), 7.16 – 7.05 (m, 3H), 7.08 (m, 1H), 6.7 (m, 1H)。
18: 1-(naphthalene -1- base of embodiment) -2- methyl -3- phenyl benzo [de] phospha naphthalene -1- oxide synthesis
Using 1- phenyl propyne, dinaphthyl oxygen phosphorus as raw material, reaction step is as follows:
1- phenyl propyne (0.058 gram, 0.5 mmol) is added in reaction flask, and dinaphthyl oxygen phosphorus (0.30 gram, 1
Mmol), CuI (0.019 g, 0.1 mmol), propyloxy phenyl base hydrogen peroxide (0.31 g, 2 mmol) and acetonitrile (2 mL),
50oC reaction；
TLC tracking reaction is until be fully completed；
The crude by column chromatography separation (ethyl acetate: petroleum ether=1:1) obtained after reaction, obtains target
Product (yield 91%).The analysis data of product are as follows: 1H NMR (400 MHz, CDCl3): δ8.65 (m, 1H), 8.11
– 7.94 (m, 3H), 7.88 – 7.78 (m, 2H), 7.65 (m, 1H), 7.56 – 7.46 (m, 2H), 7.46
– 7.34 (m, 6H), 7.29 – 7.21 (m, 1H), 7.21 – 7.09 (m, 2H), 1.71 (s, 3H)。
19: 1-(naphthalene -1- base of embodiment) -3- phenethyl benzo [de] phospha naphthalene -1- oxide synthesis
Using 4- phenyl butine, dinaphthyl oxygen phosphorus as raw material, reaction step is as follows:
4- phenyl butine (0.065 gram, 0.5 mmol) is added in reaction flask, and dinaphthyl oxygen phosphorus (0.30 gram, 1
Mmol), Cu (SCN)2 (0.0179 gram, 0.1 mmol), tertbutanol peroxide (0.30 mL, 2 mmol) and water (2 mL), 60oC
Reaction；
TLC tracking reaction is until be fully completed；
The crude by column chromatography separation (ethyl acetate: petroleum ether=1:1) obtained after reaction, obtains target
Product (yield 85%).The analysis data of product are as follows:1H NMR (400 MHz, CDCl3): δ8.18 – 8.10 (m,
3H), 8.02 (m, 3H), 7.88 (d, J = 8.1 Hz, 1H), 7.68 (m, 1H), 7.64 – 7.52 (m,
2H), 7.44 (m, 1H), 7.25 – 7.13 (m, 6H), 6.61 (d, J = 7.5 Hz, 1H), 3.33 – 3.15
(m, 2H), 3.05 (m, 2H)。
20: 1-(naphthalene -1- base of embodiment) -3-(thiophene -2- base) benzo [de] phospha naphthalene -1- oxide synthesis
Using 2- thiophene acetylene, dinaphthyl oxygen phosphorus as raw material, reaction step is as follows:
2- thiophene acetylene (0.054 gram, 0.5 mmol) is added in reaction flask, and dinaphthyl oxygen phosphorus (0.30 gram, 1
Mmol), CuSCN (0.012 gram, 0.1 mmol), propyloxy phenyl base hydrogen peroxide (0.23 g, 1.5 mmol) and water (2
ML), 70oC reaction；
TLC tracking reaction is until be fully completed；
The crude by column chromatography separation (ethyl acetate: petroleum ether=1:1) obtained after reaction, obtains target
Product (yield 68%).The analysis data of product are as follows:1H NMR (400 MHz, CDCl3): δ8.67 (m, 1H), 8.43
(m, 2H), 8.32 – 8.17 (m, 3H), 8.05 (d, J = 50.4 Hz, 1H), 7.84 (m, 5H), 7.59
(m, 1H), 7.28 (m, 1H), 7.20 – 6.81 (m, 2H), 6.66 (m, 1H)。
21: 1-(naphthalene -1- base of embodiment) -3-(pyridine -2- base) benzo [de] phospha naphthalene -1- oxide synthesis
Using 2- ethynyl pyridine, dinaphthyl oxygen phosphorus as raw material, reaction step is as follows:
2- ethynyl pyridine (0.052 gram, 0.5 mmol) is added in reaction flask, and dinaphthyl oxygen phosphorus (0.30 gram, 1
Mmol), CuI (0.019 g, 0.1 mmol), di-tert-butyl peroxide (0.30 g, 2 mmol) and acetone (2 mL),
50oC reaction；
TLC tracking reaction is until be fully completed；
The crude by column chromatography separation (ethyl acetate: petroleum ether=1:1) obtained after reaction, obtains target
Product (yield 63%).The oxygen index (OI) of E44/ dicyandiamide/product (addition 12wt%) is 27；The analysis data of product are as follows:1H
NMR (400 MHz, CDCl3): δ8.62 (m, 1H), 8.34 (m, 1H), 8.21 (d, J = 8.1 Hz, 1H),
8.18 – 8.02 (m, 4H), 7.92 (d, J = 8.1 Hz, 1H), 7.65 (m, 3H), 7.51 – 7.42 (m,
2H), 7.26 (m, 2H), 7.16 (m, 1H), 6.98 (m, 1H), 6.82 (d, J = 9.7 Hz, 1H)。
22: 1-(naphthalene -1- base of embodiment) -3- amyl benzo [de] phospha naphthalene -1- oxide synthesis
Using heptyne, dinaphthyl oxygen phosphorus as raw material, reaction step is as follows:
Heptyne (0.048 gram, 0.5 mmol) is added in reaction flask, dinaphthyl oxygen phosphorus (0.30 gram, 1 mmol),
CuCl2 (0.014 g, 0.1 mmol), propyloxy phenyl base hydrogen peroxide (0.31 g, 2 mmol) and acetonitrile (2 mL), 50oC is anti-
It answers；
TLC tracking reaction is until be fully completed；
The crude by column chromatography separation (ethyl acetate: petroleum ether=1:1) obtained after reaction, obtains target
Product (yield 75%).The oxygen index (OI) of E44/ dicyandiamide/product (addition 12wt%) is 27；The analysis data of product are as follows: 1H
NMR (400 MHz, CDCl3): δ8.62 (m, 1H), 8.34 (m, 1H), 8.21 (d, J = 8.1 Hz, 1H),
8.18 – 8.02 (m, 4H), 7.92 (d, J = 8.1 Hz, 1H), 7.65 (m, 3H), 7.51 – 7.42 (m,
2H), 6.82 (d, J = 9.7 Hz, 1H), 2.12 (m, 2H), 1.58 (m, 6H), 0.98 (m, 3H)。
Claims (3)
1. a kind of preparation method of benzo phospha naphthalene derivatives, comprising the following steps: by alkynes, phosphorus reagent, copper catalyst and have
Machine peroxide is dissolved in solvent, is reacted at 50 ~ 100 DEG C, and benzo phospha naphthalene derivatives are obtained；The alkynes is selected from: second
Alkynes, butine, hexin, 4- phenyl -1- butine, heptyne, phenylacetylene, 4- methyl phenylacetylene, 4- Methoxy-phenylacetylene, 4- fluorophenethyl
Alkynes, 4- chlorobenzene acetylene, 4- bromobenzene acetylene, 4-(trifluoromethyl) phenylacetylene, 4- nitrobenzene acetylene, 4- methoxycarbonyl phenylacetylene,
3- methyl phenylacetylene, 3- chlorobenzene acetylene, 3- Methoxy-phenylacetylene, 2- methyl phenylacetylene, 2- fluorobenzene acetylene, 2- chlorobenzene acetylene, 2-
One in (trifluoromethyl) phenylacetylene, 1- phenyl -1- propine, 4- phenyl -1- butine, 2- thiophene acetylene or 2- ethynyl pyridine
Kind；
The phosphorus reagent is as shown in having structure general formula:
Wherein A is selected from aryl or naphthalene；
The aryl is as shown in following general formula of the chemical structure:
Wherein R1It is selected from: one of alkoxy, halogen, nitro, trifluoromethyl, ester group；
The organic peroxide is as shown in following general formula of the chemical structure:
Wherein R2It is selected from: one of methyl or phenyl；R3It is selected from: one of hydrogen, tert-butyl or benzoyl；
The chemical formula of the copper catalyst is CuXn, and wherein X is one of Cl, Br, I, SCN；N is 1 or 2；
The solvent is selected from: methanol, ethyl alcohol, acetonitrile, acetone, ethyl acetate, water, 1,2- dichloroethanes, toluene, N, N- dimethyl
One of formamide or N-Methyl pyrrolidone.
The benzo phospha naphthalene derivatives are as shown in following general formula of the chemical structure:
R comes from alkynes.
2. the preparation method of benzo phospha naphthalene derivatives according to claim 1, which is characterized in that utilize thin-layer chromatography chromatography
Tracking reaction is until be fully completed；Column chromatography for separation purification processes are carried out to product after reaction.
3. the preparation method of benzo phospha naphthalene derivatives according to claim 1, which is characterized in that in molar ratio, alkynes: phosphorus
Reagent: copper catalyst: organic peroxide 1: 2: 0.2: (2 ~ 6).
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| CN110256496B (en) * | 2017-09-08 | 2021-08-17 | 江苏强盛功能化学股份有限公司 | Beta-thioindolone derivative and preparation method thereof |
| CN108329347B (en) * | 2018-01-15 | 2020-05-01 | 苏州大学 | Method for preparing β -chloroalkenylphosphono derivatives |
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