CN113773346B - Process for preparing cyanoarylphosphines - Google Patents
Process for preparing cyanoarylphosphines Download PDFInfo
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- CN113773346B CN113773346B CN202110972377.3A CN202110972377A CN113773346B CN 113773346 B CN113773346 B CN 113773346B CN 202110972377 A CN202110972377 A CN 202110972377A CN 113773346 B CN113773346 B CN 113773346B
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- phosphine
- alkyl
- aryl
- substituted
- cyanoarylphosphine
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- 238000004519 manufacturing process Methods 0.000 title claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 34
- -1 cyano-aryl phosphine Chemical compound 0.000 claims abstract description 27
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 125000001424 substituent group Chemical group 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 9
- LELOWRISYMNNSU-UHFFFAOYSA-N Hydrocyanic acid Natural products N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 230000009471 action Effects 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 125000003118 aryl group Chemical group 0.000 claims description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 claims description 7
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims description 3
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 125000005561 phenanthryl group Chemical group 0.000 claims description 3
- 125000001725 pyrenyl group Chemical group 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 claims description 2
- IUBQJLUDMLPAGT-UHFFFAOYSA-N potassium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([K])[Si](C)(C)C IUBQJLUDMLPAGT-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- WRIKHQLVHPKCJU-UHFFFAOYSA-N sodium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([Na])[Si](C)(C)C WRIKHQLVHPKCJU-UHFFFAOYSA-N 0.000 claims description 2
- 150000003003 phosphines Chemical class 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000013459 approach Methods 0.000 abstract description 2
- 238000001228 spectrum Methods 0.000 description 42
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 16
- 229910052698 phosphorus Inorganic materials 0.000 description 16
- 239000011574 phosphorus Substances 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- YBVAFSDMWYZZSK-UHFFFAOYSA-N C1(=CC=CC=C1)C1(CCPCC1)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)C1(CCPCC1)C1=CC=CC=C1 YBVAFSDMWYZZSK-UHFFFAOYSA-N 0.000 description 9
- 238000004440 column chromatography Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000003446 ligand Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 150000002903 organophosphorus compounds Chemical class 0.000 description 5
- DXTLCLWOCYLDHL-UHFFFAOYSA-N 2-ethoxybenzonitrile Chemical compound CCOC1=CC=CC=C1C#N DXTLCLWOCYLDHL-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- CTPPICLRNCIVJB-UHFFFAOYSA-N 2-ethoxynaphthalene-1-carbonitrile Chemical compound C1=CC=CC2=C(C#N)C(OCC)=CC=C21 CTPPICLRNCIVJB-UHFFFAOYSA-N 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- POVDSBNOIOOBPF-UHFFFAOYSA-N 1-ethoxy-5,6,7,8-tetrahydronaphthalene-2-carbonitrile Chemical compound CCOC(C(CCCC1)=C1C=C1)=C1C#N POVDSBNOIOOBPF-UHFFFAOYSA-N 0.000 description 1
- POWKFDSPJRDQBI-UHFFFAOYSA-N 2-ethoxy-3,6-dimethylbenzonitrile Chemical compound CCOC1=C(C)C=CC(C)=C1C#N POWKFDSPJRDQBI-UHFFFAOYSA-N 0.000 description 1
- PJRLUGQMEZZDIY-UHFFFAOYSA-N 4-ethoxybenzonitrile Chemical compound CCOC1=CC=C(C#N)C=C1 PJRLUGQMEZZDIY-UHFFFAOYSA-N 0.000 description 1
- OEIUREBSSMWLGP-UHFFFAOYSA-N 5-(diethylamino)-2-ethoxybenzonitrile Chemical compound CCN(CC)C(C=C1)=CC(C#N)=C1OCC OEIUREBSSMWLGP-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical compound C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012011 nucleophilic catalyst Substances 0.000 description 1
- 229910000064 phosphane Inorganic materials 0.000 description 1
- 150000003002 phosphanes Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- FEMRXDWBWXQOGV-UHFFFAOYSA-N potassium amide Chemical compound [NH2-].[K+] FEMRXDWBWXQOGV-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
- C07F9/5063—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds
- C07F9/5072—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds from starting materials having the structure P-H
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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)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of cyano-aryl phosphine, which takes ethoxy aryl nitrile and disubstituted phosphine alkane as raw materials to react under the action of alkali and organic solvent under protective atmosphere to prepare the cyano-aryl phosphine. According to the invention, the ethoxy aryl carbonitrile and the disubstituted phosphine are used as raw materials, a metal catalyst is not needed, the preparation of the cyanoaryl phosphine with different substituents is realized under the action of alkali, the operation is simple, and a novel and rapid approach is provided for the preparation of the cyanoaryl phosphine with different substituents.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and relates to a preparation method of cyano aryl phosphine with different substituents, in particular to a preparation method of corresponding cyano aryl phosphine by using ethoxy aryl carbonitrile, disubstituted phosphine and alkali as raw materials.
Background
Organophosphorus compounds are not only useful building blocks in organic synthesis, but also widely exist and are applied to life chemistry, pharmaceutical chemistry and catalytic ligands. For example, in organic synthesis, wittig reagent has become an indispensable reagent for constructing carbon-carbon double bonds; the wide application of phosphorus-containing ligands (such as BINAP) in the reactions of transition metal-catalyzed coupling, asymmetric reduction and the like promotes the revolutionary development of metal organic chemistry, medical industry and functional materials; phosphorus-containing heterocycles are also of significant research value in life sciences. In addition, the organic phosphine compound can be used as a nucleophilic catalyst, and can also form coordinate bonds with the vacant orbitals of transition metals through the lone-pair electrons of phosphorus to construct different types of transition metal catalysts. Organophosphine ligand (PR) 3 ) The chemical and physical properties of the transition metal catalyst can be influenced by the electron donating capability and the space size of the organic phosphine ligand, and the electron donating capability and the space size of the organic phosphine ligand can be regulated and controlled by changing the electrical property and the steric hindrance of the R group, so that the performance of the transition metal catalyst can be further regulated and controlled by changing the R group. If a chiral environment is introduced into the organic phosphine compound, the synthesis of the chiral catalyst and the application of the chiral catalyst in asymmetric catalysis can be realized. It follows that the position of organophosphinic compounds in organic synthesis is very important.
At present, the main synthesis method of the organic phosphorus compound is to construct pentavalent phosphine through transition metal catalysis, and then prepare trivalent organic phosphorus compound through reduction; in addition, the new trivalent organic phosphorus compound can be prepared by taking trivalent phosphine protected by borane as a raw material and carrying out chemical modification and reduction. These synthetic methods all require more than two steps to achieve the synthesis of trivalent organophosphorus compounds, require transition metal catalysis, and require the use of highly toxic boranes. In addition, cyano groups as an effective functional group can be used to prepare the corresponding amines, aldehydes, amides and carboxylic acids by reduction and hydrolysis. Taking triarylphosphine as an example, introducing a cyano group on an aromatic ring can give cyanoarylphosphine, which can be further converted to prepare chiral phosphine ligands.
Disclosure of Invention
Aiming at the defects of the existing synthesis of different substituent cyanoaryl phosphines, the invention aims to provide a preparation method of different substituent cyanoaryl phosphines. The method is simple and convenient to operate, has no metal catalysis, uses non-toxic reaction reagents, is green and environment-friendly, and provides a novel and quick way for preparing the cyano aryl phosphine with different substituents.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
the preparation method of the cyano-aryl phosphine comprises the step of reacting ethoxy aryl carbonitrile and disubstituted phosphine serving as raw materials under the action of alkali and an organic solvent in a protective atmosphere to prepare the cyano-aryl phosphine.
Preferably, the aryl in the ethoxyarylcarbonitrile is a substituted phenyl group or a fused ring aryl group.
More preferably, the substituted phenyl is phenyl substituted by at least one substituent selected from the group consisting of C1 to C5 alkyl, alkoxy, alkenyl, and diethylamino;
the condensed ring aryl is naphthyl, anthryl, phenanthryl or pyrenyl.
Preferably, the disubstituted phosphine is a diaryl substituted phosphine or a dialkyl substituted phosphine.
More preferably, the diaryl substituted phosphine alkane is C1-C5 alkyl, alkoxy or trifluoromethyl substituted phenyl phosphine alkane, and is the same polysubstitution;
the dialkyl substituted phosphine alkyl comprises alkyl of C1-C5, cyclohexyl or adamantyl substituent, and is the same polysubstitution.
The term "identical polysubstituted" means that, in the diaryl substituted phosphine, two aryl groups are identical substituents; or dialkyl substituted phosphanes in which both alkyl groups are the same substituent.
Preferably, the mole ratio of the ethoxy aryl nitrile, the disubstituted phosphine alkane and the alkali is 1:1.0 to 1.5:1.5 to 2.0.
Preferably, the base is at least one selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, lithium bistrimethylsilyl amide, sodium bistrimethylsilyl amide and potassium bistrimethylsilyl amide; more preferably at least one of lithium tert-butoxide, sodium tert-butoxide, and potassium tert-butoxide.
Preferably, the organic solvent is at least one selected from the group consisting of toluene, cyclohexane, 1, 4-dioxane, N-dimethylformamide, and tetrahydrofuran.
Preferably, the reaction temperature is 20-100 ℃; more preferably 60 to 80 ℃.
Preferably, the reaction time is 15 to 20 hours.
The invention has the beneficial effects that:
according to the invention, the ethoxy aryl carbonitrile and the disubstituted phosphine are used as raw materials, a metal catalyst is not needed, the preparation of the cyanoaryl phosphine with different substituents is realized under the action of alkali, the operation is simple, and a novel and rapid approach is provided for the preparation of the cyanoaryl phosphine with different substituents. The cyanoaryl phosphine compounds prepared by the method can be further subjected to cyano functional group conversion to synthesize different chiral phosphine ligands.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a sample prepared in example 1 of the present invention;
FIG. 2 is a nuclear magnetic carbon spectrum of a sample obtained in example 1 of the present invention;
FIG. 3 is a nuclear magnetic phosphorus spectrum of a sample obtained in example 1 of the present invention;
FIG. 4 is a nuclear magnetic hydrogen spectrum of a sample prepared in example 2 of the present invention;
FIG. 5 is a nuclear magnetic carbon spectrum of a sample prepared in example 2 of the present invention;
FIG. 6 is a nuclear magnetic phosphorus spectrum of a sample prepared in example 2 of the present invention;
FIG. 7 is a nuclear magnetic hydrogen spectrum of a sample obtained in example 3 of the present invention;
FIG. 8 is a nuclear magnetic carbon spectrum of a sample obtained in example 3 of the present invention;
FIG. 9 is a nuclear magnetic phosphorus spectrum of a sample prepared in example 3 of the present invention;
FIG. 10 is a nuclear magnetic hydrogen spectrum of a sample obtained in example 4 of the present invention;
FIG. 11 is a nuclear magnetic carbon spectrum of a sample obtained in example 4 of the present invention;
FIG. 12 is a nuclear magnetic phosphorus spectrum of a sample obtained in example 4 of the present invention;
FIG. 13 is a nuclear magnetic hydrogen spectrum of a sample obtained in example 5 of the present invention;
FIG. 14 is a nuclear magnetic carbon spectrum of a sample obtained in example 5 of the present invention;
FIG. 15 is a nuclear magnetic phosphorus spectrum of a sample prepared in example 5 of the present invention;
FIG. 16 is a nuclear magnetic hydrogen spectrum of a sample obtained in example 6 of the present invention;
FIG. 17 is a nuclear magnetic carbon spectrum of a sample obtained in example 6 of the present invention;
FIG. 18 is a nuclear magnetic phosphorous spectrum of a sample prepared in example 6 of the present invention;
FIG. 19 is a nuclear magnetic hydrogen spectrum of a sample obtained in example 7 of the present invention;
FIG. 20 is a nuclear magnetic carbon spectrum of a sample obtained in example 7 of the present invention;
FIG. 21 is a nuclear magnetic phosphorus spectrum of a sample obtained in example 7 of the present invention.
Detailed Description
The invention is further illustrated with reference to specific examples. It should be noted that these examples are only for illustrating the present invention and do not limit the present invention in any way. However, the actual application of the invention will still be within the scope of the present invention as modified and modified by those skilled in the art. The reaction equations are shown in formula (1):
in the formula (1), NC-Ar-OEt is ethoxy aryl formonitrile,
is disubstituted phosphine alkane.
Wherein Ar is substituted phenyl or condensed ring aryl;
further, the substituted phenyl is phenyl with at least one substituent of C1-C5 alkyl, alkoxy, alkenyl and diethylamino;
the condensed ring aryl is naphthyl, anthryl, phenanthryl or pyrenyl.
The disubstituted phosphine is diaryl substituted phosphine or dialkyl substituted phosphine.
Further, the diaryl substituted phosphine alkyl is C1-C5 alkyl, alkoxy or trifluoromethyl substituted phenyl phosphine alkyl, and is the same polysubstitution;
the dialkyl substituted phosphine alkyl comprises alkyl of C1-C5, cyclohexyl or adamantyl substituent, and is the same polysubstitution.
It should be noted that the substitution positions of CN-and-OEt on the benzene ring may be ortho-, meta-or para-positions.
Example 1
5-diethylamino-2-ethoxybenzonitrile (1.09g, 5.0mmol,1.0 equiv.), diphenylphosphinane (1.02g, 5.5mmol,1.1 equiv.), potassium tert-butoxide (842mg, 7.5mmol,1.5 equiv.) and cyclohexane (10 mL) were added to a reaction flask under a nitrogen atmosphere. The mixed system is reacted for 15h at 80 ℃. After the reaction was completed, the reaction system was cooled to room temperature, diluted with dichloromethane, filtered, and subjected to spin-drying of the solvent for column chromatography to obtain the objective product (1.61 g, yield 90%).
The hydrogen spectrum data, the carbon spectrum data and the phosphorus spectrum data are respectively as follows:
1 H NMR(400MHz,CDCl 3 )δ7.49(s,1H),7.36(d,J＝7.4Hz,10H),6.55(d,J＝8.5Hz,1H),6.05(s,1H),3.15(q,J＝7.2Hz,4H),0.96(t,J＝7.1Hz,6H).
13 C NMR(100MHz,CDCl 3 )δ149.7,143.3(d,J＝17.6Hz),135.4(d,J＝10.8Hz),135.1(d,J＝5.8Hz),134.0(d,J＝20.1Hz),129.2,128.7(d,J＝7.1Hz),119.6(d,J＝3.9Hz),116.2,110.7,101.7(d,J＝31.2Hz),44.6,12.2.
31 P NMR(162MHz,CDCl 3 )δ-7.5.
example 2
Under a nitrogen atmosphere, 4-ethoxybenzonitrile (736mg, 5.0mmol,1.0 equiv.), diphenylphosphinane (1.02g, 5.5mmol,1.1 equiv.), potassium tert-butoxide (842mg, 7.5mmol,1.5 equiv.) and cyclohexane (10 mL) were charged into a reaction flask. The mixed system is reacted for 15h at 80 ℃. After the reaction was completed, the reaction system was cooled to room temperature, diluted with dichloromethane, filtered, and subjected to spin-drying of the solvent for column chromatography to obtain the objective product (0.7 g, yield 49%).
The hydrogen spectrum data, the carbon spectrum data and the phosphorus spectrum data are respectively as follows:
1 H NMR(400MHz,CDCl 3 )δ7.58(d,J＝7.8Hz,2H),7.47–7.29(m,12H).
13 C NMR(100MHz,CDCl 3 )δ145.2(d,J＝16.7Hz),135.5(d,J＝10.5Hz),134.1(d,J＝20.2Hz),133.6(d,J＝18.5Hz),131.8(d,J＝6.1Hz),129.6,128.9(d,J＝7.5Hz),118.8,112.0.
31 P NMR(162MHz,CDCl 3 )δ-4.3.
example 3
Under a nitrogen atmosphere, 3, 6-dimethyl-2-ethoxybenzonitrile (876 mg,5.0mmol,1.0 equivalent), diphenylphosphinane (1.02g, 5.5mmol,1.1 equivalent), potassium tert-butoxide (842mg, 7.5mmol,1.5 equivalent) and cyclohexane (10 mL) were charged into a reaction flask. The mixed system is reacted for 15h at 80 ℃. After the reaction was completed, the reaction system was cooled to room temperature, diluted with dichloromethane, filtered, and subjected to column chromatography to obtain the objective product (1.31 g, yield 83%).
The hydrogen spectrum data, the carbon spectrum data and the phosphorus spectrum data are respectively as follows:
1 H NMR(400MHz,CDCl 3 )δ7.41–7.33(m,10H),7.31–7.29(m,2H),2.53(s,3H),2.20(s,3H).
13 C NMR(100MHz,CDCl 3 )δ143.2(d,J＝13.2Hz),142.0(d,J＝4.8Hz),137.6(d,J＝24.0Hz),134.9(d,J＝3.1Hz),134.4(d,J＝12.3Hz),132.5(d,J＝19.1Hz),131.6,128.73,128.65(d,J＝3.3Hz),120.7(d,J＝23.8Hz),117.04(d,J＝4.0Hz),22.5(d,J＝15.2Hz),21.1.
31 P NMR(162MHz,CDCl 3 )δ-7.2.
example 4
1-ethoxy-5, 6,7, 8-tetrahydronaphthalene-2-carbonitrile (1.01g, 5.0mmol,1.0 equivalent), diphenylphosphinane (1.02g, 5.5mmol,1.1 equivalent), potassium tert-butoxide (842mg, 7.5mmol,1.5 equivalent) and cyclohexane (10 mL) were added to a reaction flask under a nitrogen atmosphere. The mixed system is reacted for 15h at 80 ℃. After the reaction was completed, the reaction system was cooled to room temperature, diluted with dichloromethane, filtered, and subjected to spin-drying of the solvent for column chromatography to obtain the objective product (1.43 g, yield 84%).
The hydrogen spectrum data, the carbon spectrum data and the phosphorus spectrum data are respectively as follows:
1 H NMR(400MHz,CDCl 3 )δ7.47(d,J＝8.0Hz,1H),7.42–7.28(m,10H),7.19(d,J＝8.0Hz,1H),2.88–2.75(m,4H),1.75–1.63(m,4H).
13 C NMR(100MHz,CDCl 3 )δ145.1(d,J＝18.3Hz),143.2(d,J＝4.3Hz),138.0(d,J＝24.5Hz),134.4(d,J＝11.7Hz),132.92(d,J＝19.4Hz),132.86(d,J＝2.8Hz),131.3,128.8,128.7(d,J＝6.4Hz),118.3(d,J＝2.7Hz),116.8(d,J＝12.9Hz),30.6,29.5(d,J＝23.9Hz),22.9(d,J＝3.6Hz),22.0.
31 P NMR(162MHz,CDCl 3 )δ-11.6.
example 5
Under a nitrogen atmosphere, 2-ethoxy-1-naphthonitrile (986 mg,5.0mmol,1.0 equivalent), diphenylphosphinane (1.02g, 5.5mmol,1.1 equivalent), potassium tert-butoxide (842mg, 7.5mmol,1.5 equivalent) and cyclohexane (10 mL) were charged into a reaction flask. The mixed system is reacted for 15h at 20 ℃. After the reaction was completed, the reaction system was cooled to room temperature, diluted with dichloromethane, filtered, and subjected to column chromatography to obtain the objective product (1.62 g, 96% yield).
The hydrogen spectrum data, the carbon spectrum data and the phosphorus spectrum data are respectively as follows:
1 H NMR(400MHz,CDCl 3 )δ8.31(d,J＝8.4Hz,1H),7.94(d,J＝8.3Hz,1H),7.89(d,J＝8.3Hz,1H),7.70(t,J＝7.8Hz,1H),7.62(t,J＝7.6Hz,1H),7.43–7.34(m,10H),7.21–7.16(m,1H).
13 C NMR(100MHz,CDCl 3 )δ143.5(d,J＝20.8Hz),135.2(d,J＝10.7Hz),134.0(d,J＝20.2Hz),133.3(d,J＝6.3Hz),132.7,132.5,129.5,128.99,128.97,128.90,128.6,128.1,125.4(d,J＝1.7Hz),116.7(d,J＝19.9Hz),116.5(d,J＝10.8Hz).
31 P NMR(162MHz,CDCl 3 )δ-7.1.
example 6
2-ethoxy-1-naphthonitrile (394mg, 2.0mmol,1.0 equivalent), diamantalkylphosphine (0.665g, 2.2mmol,1.1 equivalent), potassium bistrimethylsilyl amino (3.0mmol, 1.5 equivalent), and cyclohexane (10 mL) were added to a reaction flask under a nitrogen atmosphere. The mixed system is reacted for 15h at 80 ℃. After the reaction, the reaction system was cooled to room temperature, diluted with dichloromethane, filtered, and the solvent was dried by spinning to obtain the objective product (0.48 g, 53% yield).
The hydrogen spectrum data, the carbon spectrum data and the phosphorus spectrum data are respectively as follows:
1 H NMR(400MHz,CDCl 3 )δ8.36(d,J＝8.3Hz,1H),7.98(s,2H),7.93(d,J＝8.2Hz,1H),7.72–7.60(m,2H),2.12–2.02(m,6H),2.00–1.88(m,12H),1.71–1.62(m,12H).
13 C NMR(100MHz,CDCl 3 )δ141.7(d,J＝32.1Hz),133.4(d,J＝9.2Hz),132.8,131.6(d,J＝2.6Hz),129.9,128.5,128.3,128.0,126.1,121.6(d,J＝42.0Hz),117.7(d,J＝5.0Hz),41.8(d,J＝12.4Hz),37.8(d,J＝23.8Hz),36.9,28.9(d,J＝8.7Hz).
31 P NMR(162MHz,CDCl 3 )δ-34.0.
example 7
Under a nitrogen atmosphere, 2-ethoxybenzonitrile (0.74g, 5.0mmol,1.0 equiv), diphenylphosphinane (1.02g, 5.5mmol,1.1 equiv), potassium tert-butoxide (842mg, 7.5mmol,1.5 equiv) and cyclohexane (10 mL) were added to a reaction flask. The mixed system is reacted for 15h at 80 ℃. After the reaction was completed, the reaction system was cooled to room temperature, diluted with dichloromethane, filtered, and subjected to spin-drying of the solvent for column chromatography to obtain the objective product (1.28 g, yield 89%).
The hydrogen spectrum data, the carbon spectrum data and the phosphorus spectrum data are respectively as follows:
1 H NMR(400MHz,CDCl 3 )δ7.71(d,J＝6.5Hz,1H),7.48(t,J＝7.6Hz,1H),7.45–7.27(m,11H),7.05(dd,J＝7.8,3.3Hz,1H).
13 C NMR(100MHz,CDCl 3 )δ143.1(d,J＝19.6Hz),134.7(d,J＝10.2Hz),134.1(d,J＝20.4Hz),133.8(d,J＝4.8Hz),133.5,132.5,129.5,129.0,128.9(d,J＝7.3Hz),117.9(d,J＝32.8Hz),117.7(d,J＝3.7Hz).
31 P NMR(162MHz,CDCl 3 )δ-8.6.
example 8
2-ethoxybenzonitrile (0.74g, 5.0mmol,1.0 equiv.), diphenylphosphinane (1.02g, 5.5mmol,1.1 equiv.), potassium hydroxide (420mg, 7.5mmol,1.5 equiv.) and cyclohexane (10 mL) were charged into a reaction flask under a nitrogen atmosphere. The mixed system is reacted for 15h at 80 ℃. After the reaction was completed, the reaction system was cooled to room temperature, diluted with dichloromethane, filtered, and the solvent was dried by spinning to perform column chromatography to obtain the objective product (0.57 g, yield 20%).
Example 9
2-ethoxybenzonitrile (0.74g, 5.0mmol,1.0 equiv.), diphenylphosphinane (1.02g, 5.5mmol,1.1 equiv.), bistrimethylsilyl amino potassium (7.5mmol, 1.5 equiv.) and cyclohexane (10 mL) were charged into a reaction flask under a nitrogen atmosphere. The mixed system is reacted for 15h at 80 ℃. After the reaction, the reaction system was cooled to room temperature, diluted with dichloromethane, filtered, and the solvent was dried by spinning to obtain the objective product (0.14 g, 5% yield).
Example 10
Under a nitrogen atmosphere, 2-ethoxybenzonitrile (0.74g, 5.0mmol,1.0 equiv), diphenylphosphinane (1.02g, 5.5mmol,1.1 equiv), potassium tert-butoxide (842mg, 7.5mmol,1.5 equiv) and tetrahydrofuran (10 mL) were added to a reaction flask. The mixed system is reacted for 15h at 80 ℃. After the reaction was completed, the reaction system was cooled to room temperature, diluted with dichloromethane, filtered, and subjected to spin-drying of the solvent for column chromatography to obtain the objective product (1.18 g, yield 82%).
Claims (5)
1. A process for the preparation of a cyanoarylphosphine, characterized in that: under protective atmosphere, taking ethoxy aryl nitrile and disubstituted phosphine alkane as raw materials, and reacting under the action of alkali and an organic solvent to prepare cyano aryl phosphine;
the aryl in the ethoxy aryl carbonitrile is phenyl, substituted phenyl or fused ring aryl;
the substituted phenyl is phenyl of at least one substituent group of C1-C5 alkyl, C1-C5 alkoxy, alkenyl and diethylamino;
the condensed ring aryl is naphthyl, anthryl, phenanthryl or pyrenyl;
the disubstituted phosphine alkyl is diaryl substituted phosphine alkyl or dialkyl substituted phosphine alkyl;
the diaryl substituted phosphine alkyl is C1-C5 alkyl, C1-C5 alkoxy or trifluoromethyl substituted phenyl phosphine alkyl, and is the same polysubstitution;
the dialkyl substituted phosphine alkyl comprises C1-C5 alkyl, cyclohexyl or adamantyl substituted alkyl phosphine alkyl, and is the same polysubstitution;
the alkali is selected from at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, lithium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide and potassium bis (trimethylsilyl) amide.
2. A process for the preparation of a cyanoarylphosphine according to claim 1, wherein: the mole ratio of the ethoxy aryl formonitrile, the disubstituted phosphine alkane and the alkali is 1:1.0 to 1.5:1.5 to 2.0.
3. The method for producing a cyanoarylphosphine according to claim 1, wherein: the organic solvent is at least one selected from toluene, cyclohexane, 1, 4-dioxane, N, N-dimethylformamide and tetrahydrofuran.
4. A process for the preparation of a cyanoarylphosphine according to claim 1, wherein: the reaction temperature is 20 to 100 ℃.
5. The method for producing a cyanoarylphosphine according to claim 1, wherein: the reaction time is 15 to 20 hours.
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