CN108484668A - Organic phosphine compound and its preparation method and application with sulfonyl function - Google Patents
Organic phosphine compound and its preparation method and application with sulfonyl function Download PDFInfo
- Publication number
- CN108484668A CN108484668A CN201810379226.5A CN201810379226A CN108484668A CN 108484668 A CN108484668 A CN 108484668A CN 201810379226 A CN201810379226 A CN 201810379226A CN 108484668 A CN108484668 A CN 108484668A
- Authority
- CN
- China
- Prior art keywords
- group
- phosphine compound
- sulfonyl
- compound
- organic phosphine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 55
- -1 phosphine compound Chemical class 0.000 title claims abstract description 46
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 43
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 12
- 125000000524 functional group Chemical group 0.000 claims abstract description 9
- 230000000269 nucleophilic effect Effects 0.000 claims abstract description 6
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims abstract description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 5
- DIGGWMOTBUMCTG-UHFFFAOYSA-N P.[C] Chemical compound P.[C] DIGGWMOTBUMCTG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006073 displacement reaction Methods 0.000 claims abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 239000011737 fluorine Substances 0.000 claims abstract description 5
- 238000005859 coupling reaction Methods 0.000 claims abstract description 4
- 229940124530 sulfonamide Drugs 0.000 claims description 13
- 150000003456 sulfonamides Chemical class 0.000 claims description 13
- 125000000623 heterocyclic group Chemical group 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000005842 heteroatom Chemical group 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 239000012038 nucleophile Substances 0.000 claims description 4
- 125000004171 alkoxy aryl group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000008064 anhydrides Chemical group 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000002883 imidazolyl group Chemical group 0.000 claims description 3
- 125000000468 ketone group Chemical group 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 239000003446 ligand Substances 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000005457 optimization Methods 0.000 abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000004293 19F NMR spectroscopy Methods 0.000 description 2
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 description 2
- 238000004679 31P NMR spectroscopy Methods 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- IUYHWZFSGMZEOG-UHFFFAOYSA-M magnesium;propane;chloride Chemical compound [Mg+2].[Cl-].C[CH-]C IUYHWZFSGMZEOG-UHFFFAOYSA-M 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RQEUFEKYXDPUSK-UHFFFAOYSA-N 1-phenylethylamine Chemical class CC(N)C1=CC=CC=C1 RQEUFEKYXDPUSK-UHFFFAOYSA-N 0.000 description 1
- FCSKOFQQCWLGMV-UHFFFAOYSA-N 5-{5-[2-chloro-4-(4,5-dihydro-1,3-oxazol-2-yl)phenoxy]pentyl}-3-methylisoxazole Chemical compound O1N=C(C)C=C1CCCCCOC1=CC=C(C=2OCCN=2)C=C1Cl FCSKOFQQCWLGMV-UHFFFAOYSA-N 0.000 description 1
- DRSHXJFUUPIBHX-UHFFFAOYSA-N COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 Chemical compound COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 DRSHXJFUUPIBHX-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XYOGBCBYMIAUAB-UHFFFAOYSA-L trifluoromethanesulfonate;triphenyl(triphenylphosphaniumyloxy)phosphanium Chemical compound [O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)O[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 XYOGBCBYMIAUAB-UHFFFAOYSA-L 0.000 description 1
- 238000005406 washing Methods 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
- C07F9/28—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
- C07F9/5054—Preparation; Separation; Purification; Stabilisation by a process in which the phosphorus atom is not involved
-
- 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
- C07F9/5068—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-Hal
Landscapes
- 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 kind of organic phosphine compound and its preparation method and application with sulfonyl function has sulfonyl group and contains phosphine groups, further includes the functional group that can be left away by nucleophilic displacement of fluorine.When preparation, sulfonic acid chloride is reacted with the reagent with leaving group, introduces the functional group that can be left away by nucleophilic displacement of fluorine；Then carbon phosphine key is built by nucleophilic substitution or coupling reaction, introduces and contains phosphine groups.The organic phosphine compound with sulfonyl function of the present invention; it can be by the way that necleophilic reaction occurs with nucleopilic reagent; quick structure ligand library; good technology is provided for the design and synthesis of ligand; the discovery and optimization for accelerating reaction can be applied to carry out nucleophilic substitution structure containing phosphine compound with nucleopilic reagent.
Description
Technical field
The present invention relates to organic synthesis field, especially a kind of organic phosphine compound with sulfonyl function.
Background technology
Organic phosphine compound with sulfonyl function shows outstanding catalytic performance in many reactions
(Chem.Eur.J.2015,21,2062-2075).In transition metal-catalyzed, organic phosphine compound is a kind of important ligand.
The activity and selectivity of reaction are closely related with the structure and property of Phosphine ligands.The phosphine for efficiently succinctly synthesizing various structure-rich is matched
Body is that the optimization of reaction creates favorable conditions.
Containing phosphine compound route of the preparation method structure with sulfonamide reported on document at present is as follows:1. sulfonic acid chloride with
Sulfonamide is obtained by the reaction in amine；2. capturing the hydrogen atom on aromatic ring by n-BuLi builds carbon phosphine key.This method is cumbersome, walks
Rapid length, combined coefficient are low, and are limited to the high activity of n-BuLi, it is difficult to obtain the abundant compound of functional group, functional group
Compatibility is bad, limits catalyst source.
Invention content
The object of the present invention is to provide a kind of organic phosphine compounds with sulfonyl function, can pass through nitrogenous class parent
Core reagent is directly reacted with sulfonyl function, and structure sulfonamides contains phosphine compound.
It is a further object to provide the preparation methods of above-mentioned organic phosphine compound.
A further object of the invention is that above-mentioned organic phosphine compound is applied to structure sulfonamides to contain phosphine compound, is carried
For a kind of convenient, economic synthesis thinking.
The object of the present invention is achieved like this：A kind of organic phosphine compound with sulfonyl function has sulphonyl
Group and contain phosphine groups, compound formula is：
Wherein：R1Selected from the functional group that can be left away by nucleophilic displacement of fluorine；R2Can be identical or different, independently selected from hydrogen, halogen
Element, hydroxyl, cyano, carbonyl, substituted carbonyl, ketone group, alkyl, alkoxy, alkoxy aryl, aryloxy group, aryl, saturation or part
The heterocycle of saturation；X is selected from the heterocycle of saturated or unsaturated carbochain or carbochain containing hetero atom, aryl, saturation or fractional saturation
The assembly of base or aforementioned forms.
The R1Selected from halogen group, anhydride group, imidazole group, phenolic group group, 2- thiazole sulfur quinoline groups, heterocycle function
Group or following structures
Wherein X is selected from the heterocycle of saturated or unsaturated carbochain or carbochain containing hetero atom, aryl, saturation or fractional saturation
The assembly of base or aforementioned forms.
The preparation method of the above-mentioned organic phosphine compound with sulfonyl function, includes the following steps：Including following step
Suddenly：A) sulfonic acid chloride is reacted with the reagent with leaving group, introduces R1Functional group；B) pass through nucleophilic substitution or coupling reaction structure
Carbon phosphine key is built, introduces and contains phosphine groups.
The above-mentioned organic phosphine compound with sulfonyl function is applied to carry out nucleophilic substitution structure with nucleopilic reagent
It builds and contains phosphine compound.
The above-mentioned organic phosphine compound with sulfonyl function is applied to prepare sulfonamides containing phosphine compound.
The organic phosphine compound with sulfonyl function of the present invention, can be anti-by the way that nucleophilic occurs with nucleopilic reagent
It answers, it is quick to build ligand library, good technology is provided for the design and synthesis of ligand, accelerates the discovery and optimization of reaction.
Specific implementation mode
The present invention is a kind of organic phosphine compound with sulfonyl function, has sulfonyl group and contains phosphine groups, and
And two group linked together by various chemical species.
Compound formula is：
Wherein：R1Selected from the functional group that can be left away by nucleophilic displacement of fluorine；R2Can be identical or different, independently selected from hydrogen, halogen
Element, hydroxyl, cyano, carbonyl, substituted carbonyl, ketone group, alkyl, alkoxy, alkoxy aryl, aryloxy group, aryl, saturation or part
The heterocycle of saturation；X is selected from the heterocycle of saturated or unsaturated carbochain or carbochain containing hetero atom, aryl, saturation or fractional saturation
The assembly of base or aforementioned forms.
The R1Selected from halogen group, anhydride group, imidazole group, phenolic group group, 2- thiazole sulfur quinoline groups, heterocycle function
Group and subordinate's structure
The preparation method of the above-mentioned organic phosphine compound with sulfonyl function, includes the following steps：A) sulfonic acid chloride with
Reagent reaction with leaving group, introduces R1Functional group；B) carbon phosphine key is built by nucleophilic substitution or coupling reaction, introduced
Containing phosphine groups.
The above-mentioned organic phosphine compound with sulfonyl function can be applied to prepare sulfonamides containing phosphine compound.Pass through
N-Containing Nucleophiles are directly reacted with sulfonyl function, can build sulfonamides (as follows) containing phosphine compound.The route is anti-
Mild condition is answered, there is good functional group compatibility, quick approach is provided for structure ligand library, is significantly better than existing skill
Art, obtained sulfonamides can be used for catalyst containing phosphine compound.Preferably, the N-Containing Nucleophiles are to contain-NH
Or-NH2The nucleopilic reagent of group.
Be explained further the present invention with reference to embodiments, but specific embodiment the present invention is not done it is any type of
It limits.
1 benzene sulfonyl chloride of embodiment is Material synthesis compound III
1. the iodo- 5- toluenesulfonic acids phenyl-pentafluoride phenolic esters (II) (R=I) of 2-
Pentafluorophenol and the dichloromethane (~0.13-1M) of drying are added into reaction bulb, and three second are added dropwise toward the solution
Amine (2-3 equivalents).After being stirred at room temperature 30-120 minutes, (1-2 works as the dichloromethane solution of past mixture dropwise addition compound III
Amount, 0.5M).After being added dropwise, reaction continues stirring 12-48 hours at room temperature.Then dichloromethane dilution is added, and successively
With 1N aq HCl, 2N aq.NaOH and salt water washing organic phase.After gained organic phase is dried over anhydrous sodium sulfate, solvent is removed
Obtain the target product II, yield 85-90% of white.Testing result is：1H NMR(400MHz,CDCl3)δ:2.41(s,3H),
7.20 (d, J=8Hz, 1H), 7.87 (s, 1H), 7.76 (t, J=8Hz, 1H)；13C NMR(100MHz,CDCl3)δ:20.91,
88.44,132.26,136.54,138.50,139.12,139.33,141.02,141.67,143.16,143.61；19F NMR
(282MHz,CDCl3)δ:- 160.98 (t, J=19.8Hz, 2F), -155.09 (t, J=21.8Hz, 1F), -149.99 (d, J=
17.8Hz,2F).
2- 2. (diphenylphosphine) -5- toluenesulfonic acid phenyl-pentafluoride phenolic esters (III)
Compound II and anhydrous tetrahydro furan (0.5-1M) are added into reaction bulb, and the solution is cooled to zero degree.So
Isopropylmagnesium chloride solution (1.5-2 equivalents, 1M tetrahydrofuran solutions) is added toward the solution under stiring afterwards.Gained reaction mixing
Object continues stirring 2-10 hours in zero degree.It is subsequently added into diphenyl phosphine chloride (1.2-3 equivalents).Following reaction continues to stir in room temperature
It mixes 12-48 hours.It is eventually adding saturated aqueous ammonium chloride and reaction is quenched.
Organic phase is detached, ethyl acetate is used in combination to be catalyzed water phase.Merge organic phase, is used in combination saturated brine to wash, anhydrous slufuric acid
Sodium is dried.After removing drier and solvent, purify to obtain the target product of white powder, yield 60-70% through column chromatography.
Testing result is：1H NMR(400MHz,CDCl3)δ:2.45 (s, 3H), 7.18 (d, J=8Hz, 1H), 7.43-
7.26(m,11H),7.92(s,1H)；19F NMR(282MHz,CDCl3)δ:- 161.38 (m, 2F), -155.79 (t, J=
21.9Hz, 1F), -149.94 (dd, J=18.1,8.6Hz, 2F)；31P NMR(162MHz,CDCl3)δ:-8.84.
2 compound IV application build sulfonamides V containing phosphine compound of embodiment
The synthesis of compound IV compound III during the preparation method is the same as that of Example 1, only the methyl wherein on phenyl ring replace
At methoxyl group.
Triethylamine (2-4 equivalent) ﹑ 1- phenyl ethylamines (1-2 equivalents) and 4- dimethylaminos is added in acetonitrile solution (1-2M) toward IV
Pyridine (0.1-0.5 equivalents), then the mixture in stirring 12-24 hours, reaction temperature is that room temperature extremely flows back.Reaction terminates
Afterwards, acetonitrile is removed, gained residue purifies to obtain the target product V of white powder through column chromatography.
Testing result is：1H NMR(400MHz,CDCl3)δ:1.57 (d, J=6.9Hz, 3H), 3.86 (s, 3H), 4.52
(p, J=6.8Hz, 1H), 6.94-7.35 (m, 16H), 7.60 (t, J=3.0Hz, 1H)；13C NMR(101MHz,CDCl3)δ:
160.00,146.99,146.73,141.97,137.76,136.25,136.19,135.75,135.69,133.61,133.43,
133.24,128.86,128.82,128.64,128.54,128.49,128.46,128.43,127.60,126.34,125.48,
125.29,118.02,114.70,114.65,55.69,54.41,23.78.；31P NMR(162MHz,CDCl3)δ:-14.15.
3 compound VII synthesis of embodiment
The dichloromethane solution (0.2-0.5M) of VI is cooled to zero degree and Pentafluorophenol (1-2 equivalents) is added, gained is mixed
Object is closed to react 1-2 hours in zero degree.Then Hendrickson's Reagent (2-3 equivalents) are added dropwise toward the mixture.It drips
Bi Hou, reaction continue stirring 12-48 hours at room temperature.After reaction, white solid is filtered off, and removes the dichloro in filtrate
Methane obtains crude product.It further purifies to obtain the VII of white through column chromatography, yield is in 75-85%.
4 compound VIII synthesis of embodiment
Cesium fluoride (2-4 equivalents) is added in acetonitrile solution (1-2M) toward IV, and then the mixture is stirred 12-24 hours,
Reaction temperature is that room temperature extremely flows back.After reaction, it removes insoluble matter and solvent, gained residue purifies to obtain white through column chromatography
Color powdered target product VII, yield 70-90%.
Claims (8)
1. a kind of organic phosphine compound with sulfonyl function has sulfonyl group and contains phosphine groups, compound formula is：
Wherein：R1Selected from the functional group that can be left away by nucleophilic displacement of fluorine；R2Can be identical or different, independently selected from hydrogen, halogen,
Hydroxyl, cyano, carbonyl, substituted carbonyl, ketone group, alkyl, alkoxy, alkoxy aryl, aryloxy group, aryl, saturation or part are full
The heterocycle of sum；X is selected from the heterocycle of saturated or unsaturated carbochain or carbochain containing hetero atom, aryl, saturation or fractional saturation,
Or the assembly of aforementioned forms.
2. the organic phosphine compound according to claim 1 with sulfonyl function, it is characterised in that：The R1Choosing
From halogen group, anhydride group, imidazole group, phenolic group group, 2- thiazole sulfur quinoline groups, heterocycle functional group or following structures
Wherein X is selected from the heterocycle of saturated or unsaturated carbochain or carbochain containing hetero atom, aryl, saturation or fractional saturation, or
It is the assembly of aforementioned forms.
3. the organic phosphine compound according to claim 1 with sulfonyl function, it is characterised in that：The compound
Atom in general formula is selected from isotope form.
4. the preparation method of the organic phosphine compound as claimed in claim 1,2 or 3 with sulfonyl function, including following step
Suddenly：A) sulfonic acid chloride is reacted with the reagent with leaving group, introduces R1Functional group；B) pass through nucleophilic substitution or coupling reaction structure
Carbon phosphine key is built, introduces and contains phosphine groups.
5. the organic phosphine compound with sulfonyl function of claim 1,2 or 3 is applied to carry out parent with nucleopilic reagent
Core substitution reaction structure contains phosphine compound.
6. the organic phosphine compound with sulfonyl function of claim 1,2 or 3 is applied to prepare sulfonamides containing phosphine
Compound.
7. the organic phosphine compound with sulfonyl function is applied to prepare sulfonamides containing phosphine according to claim 6
Close object, it is characterised in that：It is directly reacted with the sulfonyl function of the organic phosphine compound by N-Containing Nucleophiles, structure
It builds sulfonamides and contains phosphine compound.
8. the organic phosphine compound with sulfonyl function is applied to prepare sulfonamides containing phosphine according to claim 7
Close object, it is characterised in that：The N-Containing Nucleophiles are to contain-NH or-NH2The nucleopilic reagent of group.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810379226.5A CN108484668A (en) | 2018-04-25 | 2018-04-25 | Organic phosphine compound and its preparation method and application with sulfonyl function |
| PCT/CN2019/084017 WO2019206166A1 (en) | 2018-04-25 | 2019-04-24 | Organic phosphine compound having sulfonyl functional group as well as preparation method therefor and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810379226.5A CN108484668A (en) | 2018-04-25 | 2018-04-25 | Organic phosphine compound and its preparation method and application with sulfonyl function |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108484668A true CN108484668A (en) | 2018-09-04 |
Family
ID=63314041
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810379226.5A Pending CN108484668A (en) | 2018-04-25 | 2018-04-25 | Organic phosphine compound and its preparation method and application with sulfonyl function |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108484668A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111574567A (en) * | 2020-05-09 | 2020-08-25 | 中山大学 | Rigid heterocyclic compound, preparation method and application thereof, phosphine-containing sulfonamide compound and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051312A (en) * | 1986-07-21 | 1991-05-15 | 联合碳化化学品及塑料有限公司 | Produce the catalyst for oligomerization of alpha-olefin |
| CN1243518A (en) * | 1997-01-14 | 2000-02-02 | 纳幕尔杜邦公司 | Polymerization of ethylene |
| CN1320601A (en) * | 2000-02-18 | 2001-11-07 | 阿迪尔公司 | 6-amino or 6-hydrazino-sulfonyl-3-quinolyl phosphonic acid compound, preparing process thereof and pharmaceutical composition contg. same |
| JP2007332086A (en) * | 2006-06-16 | 2007-12-27 | Kuraray Co Ltd | Metal compound, catalytic composition for polymerizing vinylic monomer by using the same, and use of the composition for polymerization of vinylic monomer |
| CN102105485A (en) * | 2008-05-21 | 2011-06-22 | 新世界实验室公司 | Selective caspase inhibitors and uses thereof |
| JP2012201673A (en) * | 2011-03-28 | 2012-10-22 | Japan Polyethylene Corp | New triaryl phosphine or triaryl arsine compound, olefinic polymerization catalyst using the same, and method for producing olefinic copolymer |
| JP2012229190A (en) * | 2011-04-27 | 2012-11-22 | Japan Polyethylene Corp | Novel triarylphosphine or triarylarsine compound, olefin polymerization catalyst obtained by using the same, and manufacturing method of olefin copolymer |
| JP2012236824A (en) * | 2011-04-27 | 2012-12-06 | Japan Polyethylene Corp | New triarylphosphine or triarylarsine compound and olefin-based polymerization catalyst thereby and method for producing olefin-based copolymer |
| CN103875117A (en) * | 2011-10-21 | 2014-06-18 | 三井化学株式会社 | Nonaqueous electrolyte solution containing phosphonosulfonic acid compound, and lithium secondary battery |
-
2018
- 2018-04-25 CN CN201810379226.5A patent/CN108484668A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051312A (en) * | 1986-07-21 | 1991-05-15 | 联合碳化化学品及塑料有限公司 | Produce the catalyst for oligomerization of alpha-olefin |
| CN1243518A (en) * | 1997-01-14 | 2000-02-02 | 纳幕尔杜邦公司 | Polymerization of ethylene |
| CN1320601A (en) * | 2000-02-18 | 2001-11-07 | 阿迪尔公司 | 6-amino or 6-hydrazino-sulfonyl-3-quinolyl phosphonic acid compound, preparing process thereof and pharmaceutical composition contg. same |
| JP2007332086A (en) * | 2006-06-16 | 2007-12-27 | Kuraray Co Ltd | Metal compound, catalytic composition for polymerizing vinylic monomer by using the same, and use of the composition for polymerization of vinylic monomer |
| CN102105485A (en) * | 2008-05-21 | 2011-06-22 | 新世界实验室公司 | Selective caspase inhibitors and uses thereof |
| JP2012201673A (en) * | 2011-03-28 | 2012-10-22 | Japan Polyethylene Corp | New triaryl phosphine or triaryl arsine compound, olefinic polymerization catalyst using the same, and method for producing olefinic copolymer |
| JP2012229190A (en) * | 2011-04-27 | 2012-11-22 | Japan Polyethylene Corp | Novel triarylphosphine or triarylarsine compound, olefin polymerization catalyst obtained by using the same, and manufacturing method of olefin copolymer |
| JP2012236824A (en) * | 2011-04-27 | 2012-12-06 | Japan Polyethylene Corp | New triarylphosphine or triarylarsine compound and olefin-based polymerization catalyst thereby and method for producing olefin-based copolymer |
| CN103875117A (en) * | 2011-10-21 | 2014-06-18 | 三井化学株式会社 | Nonaqueous electrolyte solution containing phosphonosulfonic acid compound, and lithium secondary battery |
Non-Patent Citations (8)
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111574567A (en) * | 2020-05-09 | 2020-08-25 | 中山大学 | Rigid heterocyclic compound, preparation method and application thereof, phosphine-containing sulfonamide compound and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103080118B (en) | Ruthenium-diamine complexe and the method for producing optically active compound | |
| Shaikh et al. | Secondary phosphine oxides: Versatile ligands in transition metal-catalyzed cross-coupling reactions | |
| Wen et al. | Enantioselective organocatalytic phospha-Michael reaction of α, β-unsaturated ketones | |
| CN103087105B (en) | Chiral phosphine ligand and comprise the metal catalyst of this part and their application | |
| CN102947000B (en) | Carboxylation catalysts | |
| CN107880079B (en) | Cyclic N-heterocyclic bis-carbene-palladium complex and preparation method and application thereof | |
| CN105348321B (en) | One kind synthesis α, the method for α difluoro methylene alkenyl phosphonates | |
| CN109718851A (en) | A kind of hand quaternary phosphine phase transfer catalyst and its preparation method and application | |
| Morimoto et al. | A new chiral 2-sulfonylamino-2′-phosphino-1, 1′-binaphthyl ligand for highly enantioselective copper-catalyzed conjugate addition of diethylzinc to benzylideneacetones | |
| US7485744B2 (en) | Iron-catalyzed allylic alkylation | |
| CN108484668A (en) | Organic phosphine compound and its preparation method and application with sulfonyl function | |
| WO2001000581A1 (en) | Ligands based on chiral 2-amino-2'-hydroxy-1,1'-binaphthyl and related frameworks for asymmetric catalysis | |
| Gavrilov et al. | Development of P∗-monodentate diamidophosphites with a C1-symmetric 1, 2-diamine backbone: the effects of substituents in the 1, 3, 2-diazaphospholidine cycle on Pd-catalyzed asymmetric allylations | |
| CN109503670B (en) | Chiral monophosphine ligand WJ-Phos of ferrocene skeleton, preparation method and application | |
| Li et al. | Copper-catalyzed C–P cross-coupling of secondary phosphines with (hetero) aromatic bromide | |
| Liang et al. | Syntheses and resolutions of new chiral biphenyl backbones: 2-amino-2′-hydroxy-6, 6′-dimethyl-1, 1′-biphenyl and 2-amino-2′-hydroxy-4, 4′, 6, 6′-tetramethyl-1, 1′-biphenyl | |
| CN108467408B (en) | Diaryl phosphorus compound with hydroxyphenyl functional group and preparation method thereof | |
| CN109593085B (en) | Pyridine-amide-oxazoline ligand, synthetic method thereof, metal complex thereof and application thereof | |
| CN105669743B (en) | Method for preparing phosphinic acid/phosphonous acid/phosphate from P (O) -OH compound and arylboronic acid | |
| CN113735752B (en) | Method for preparing isothiourea compound based on substituted iodobenzene | |
| JP5208939B2 (en) | 2,2 ', 6,6'-tetrasubstituted aminophosphine ligand and method for synthesis thereof | |
| CN108467409A (en) | Pentavalent phosphine compound with sulfonyl function and its preparation method and application | |
| CN109666044B (en) | Organophosphorus compound based on [2.2] p-cyclophane alkyl skeleton and intermediate, preparation method and application thereof | |
| CN104744514A (en) | Chiral phosphorus alkene ligand, synthesis method and application thereof in asymmetric reaction | |
| CN1938280A (en) | Thiourea compositions and uses thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180904 |
|
| RJ01 | Rejection of invention patent application after publication |