CN106008601B - A kind of preparation method of N- aryl phosphorus for formamide - Google Patents
A kind of preparation method of N- aryl phosphorus for formamide Download PDFInfo
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- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000011574 phosphorus Substances 0.000 title claims abstract description 51
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 52
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- ZVCDLGYNFYZZOK-UHFFFAOYSA-M sodium cyanate Chemical compound [Na]OC#N ZVCDLGYNFYZZOK-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 239000000284 extract Substances 0.000 claims abstract description 3
- 229960000583 acetic acid Drugs 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- JBIJLHTVPXGSAM-UHFFFAOYSA-N 2-naphthylamine Chemical compound C1=CC=CC2=CC(N)=CC=C21 JBIJLHTVPXGSAM-UHFFFAOYSA-N 0.000 claims description 4
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical class NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 claims description 4
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical class CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 claims description 4
- LGDHZCLREKIGKJ-UHFFFAOYSA-N 3,4-dimethoxyaniline Chemical class COC1=CC=C(N)C=C1OC LGDHZCLREKIGKJ-UHFFFAOYSA-N 0.000 claims description 3
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical class NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 claims description 3
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical group COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 239000003205 fragrance Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- -1 aryl phosphorus Chemical compound 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000003125 aqueous solvent Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract description 2
- 230000005311 nuclear magnetism Effects 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 42
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- 239000012153 distilled water Substances 0.000 description 15
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 8
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 238000004679 31P NMR spectroscopy Methods 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 7
- 238000004440 column chromatography Methods 0.000 description 7
- 238000000605 extraction Methods 0.000 description 7
- 235000011167 hydrochloric acid Nutrition 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004799 bromophenyl group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000000068 chlorophenyl group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- DAYXECLOGLTQIG-UHFFFAOYSA-N N#CO.[P] Chemical compound N#CO.[P] DAYXECLOGLTQIG-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000005515 coenzyme Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XXUJMEYKYHETBZ-UHFFFAOYSA-N ethyl 4-nitrophenyl ethylphosphonate Chemical compound CCOP(=O)(CC)OC1=CC=C([N+]([O-])=O)C=C1 XXUJMEYKYHETBZ-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003958 nerve gas Substances 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- JKANAVGODYYCQF-UHFFFAOYSA-N prop-2-yn-1-amine Chemical compound NCC#C JKANAVGODYYCQF-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 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
- C07F9/5036—Phosphines containing the structure -C(=X)-P or NC-P
-
- 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
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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of N aryl phosphorus for the preparation method of formamide, belongs to technical field of organic synthetic chemistry.The method of the present invention is that in an ar atmosphere, in acetic acid aqueous solvent, phosphorus Zassol reacts 3 ~ 24 h with aromatic amine at 10 DEG C ~ 45 DEG C；After reaction, it extracts, separation obtains N aryl phosphorus for formamide.Synthetic product through the means such as infrared, nuclear-magnetism, single crystal diffraction detect, be N aryl phosphorus for formamide sterling, yield is 40% or more.The present invention is not required to, through any pretreatment, without by preparing the salt compounds of aniline come pre-activate aniline, directly react with phosphorus Zassol and target compound is made, simple for process, reaction condition is mild, at low cost, and yield is higher using aromatic amine as raw material；Using the aqueous solution of acetic acid as solvent, it is not only that reaction provides medium, and provides proton for reaction system, is conducive to improve reaction rate and efficiency, while reducing the pollution to environment.
Description
Technical field
The invention belongs to synthetic organic chemical art, it is related to a kind of preparation method of N- aryl phosphorus for formamide.
Background technology
Organic phosphorus compound is closely related with human lives, it is in nucleic acid, coenzyme, organophosphor nerve gas, organophosphorus insecticidal
Worm agent, organophosphorus herbicide, chemotherapeutant, plasticizer, antioxidant, surfactant, complexing agent, organophosphorous extractant,
Flotation agent and fire retardant etc. are widely used.For phosphamide as organic phosphorus compound, purposes is very extensive, in agricultural, doctor
Medicine, the fields such as industry suffer from important purposes.The chemical name of phosphamide be N- aryl phosphorus for formamide, structural formula is as follows：
。
2015, Robinson and Goicoechea reported PCO with propargyl amine or Armeen and secondary amine in acid
Property under the conditions of reaction, be prepared for N- alkyl replace phosphorus for formamide (Robinson, T. P.; Goicoechea, J. M.Chem. Eur. J. 2015, 21, 5727; Jupp, A. R.; Trott, G.; Payen de la Garanderie,
E.; Holl, J. D.; Carmichael, D.; Goicoechea, J. M. Chem. Eur. J. 2015, 21,
8015.).However, what is used in this method is the aliphatic amine of high activity entirely, and need previously prepared its esters compound（Example
Such as hydrochloride, fluoroform sulphonate）, preparation process is complicated, of high cost, low yield.In addition, these methods are using organic molten
Agent THF or pyridine are reaction medium, and aftertreatment technology is complicated, and is unfavorable for environment.
Invention content
The purpose of the present invention is being directed to problems of the prior art, provide a kind of simple process and low cost, yield compared with
High prepares method of the N- aryl phosphorus for formamide.
The present invention prepares method of the N- aryl phosphorus for formamide, is aromatic amine and phosphorus cyanic acid using acetic acid aqueous solution as solvent
Sodium is directly reacted and is obtained.Its concrete technology is：In an ar atmosphere, phosphorus Zassol（PCONa）With aromatic amine in acetic acid aqueous solvent,
3 ~ 24 h are reacted at 10 DEG C ~ 45 DEG C；After reaction, it extracts, separation obtains N- aryl phosphorus for formamide.
Aromatic amine be 4- aminoanisoles, 3,4- dimethoxyanilines, aniline, 4- chloroanilines, 4- bromanilines, beta-naphthylamine,
4- methylanilines.The molar ratio of aromatic amine and phosphorus Zassol is 1:0.25~1:4.
In acetic acid aqueous solution, the volume ratio of distilled water and glacial acetic acid is 1:1~1:4.
Reaction formula is as follows：
Synthetic product through the means such as infrared, nuclear-magnetism, single crystal diffraction detect, be N- aryl phosphorus for formamide sterling, yield can
Up to 65%.
The present invention has the following advantages compared with the prior art：
1, the present invention is not required to through any pretreatment, using aromatic amine as raw material without the salt chemical combination by preparing aniline
Object carrys out pre-activate aniline, is directly reacted with phosphorus Zassol and target compound is made, simple for process, reaction condition is mild, cost
Low, yield is higher；
2, the present invention is using the aqueous solution of acetic acid as solvent, and only reaction does not provide medium, and is reaction system
Proton is provided, is conducive to improve reaction rate and efficiency, while reducing the pollution to environment；
3, raw material and various reagents needed for the present invention are inexpensively easy, reduce production cost, are that the industrially scalable of product is given birth to
Production and commercialization create good condition.
Specific implementation mode
N- aryl phosphorus of the present invention is described further for the preparation method of formamide below by specific embodiment.
Embodiment 1：Preparation of the N- phenyl phosphorus for formamide
In Schlenk pipes, 3 mL acetic acid, 4 mL distilled water are sequentially added, 4 mmol aniline delay under stirring at room temperature
The slow aqueous solution that phosphorus Zassol is added（6mmol phosphorus Zassols are dissolved in 2 mL distilled water）, the reaction was continued 10 h after being added dropwise
Left and right（It is clarified to reaction solution）；After reaction, with the ethyl acetate Rapid Extraction of 3 × 15 mL, anhydrous magnesium sulfate drying adds
Enter 0.5 mL concentrated hydrochloric acids with unreacted aniline of going out（Its hydrochloride does not dissolve in ethyl acetate Precipitation）, column chromatography for separation obtains
To the product of sterling --- N- phenyl phosphorus is for formamide.Yield 65%.It is as follows that it synthesizes formula：
1H NMR (400 MHz, CDCl3) δ 7.52 (s, 1H), 7.39 (d, J = 7.2 Hz, 2H), 7.25
(t, J = 7.1 Hz, 2H), 7.06 (s, 1H), 4.04 (s, 1H) ppm, 3.52 (s, 1H). 13C NMR
(150 MHz, CDCl3) δ 171.8, 171.6, 129.1, 124.9, 119.9 ppm. 31P NMR (162 MHz,
CDCl3) δ -123.6 ppm。
Embodiment 2：N-（4- methoxyphenyls）Preparation of the phosphorus for formamide
In Schlenk pipes, 2 mL acetic acid, 3 mL distilled water, 1 mmol 4- aminoanisoles, in room temperature are sequentially added
The aqueous solution of phosphorus Zassol is slowly added under stirring（1.5 mmol phosphorus Zassols are dissolved in 1 mL distilled water）, it is added dropwise subsequent
10 h of continuous reaction or so（It is clarified to reaction solution）；After reaction, with the ethyl acetate Rapid Extraction of 3 × 15 mL, anhydrous slufuric acid
Magnesium is dried, and 0.1 mL concentrated hydrochloric acids are added to remove unreacted 4- aminoanisoles（Its hydrochloride is precipitated insoluble in ethyl acetate
It is precipitated）, column chromatography for separation obtains the product of sterling --- N-（4- methoxyphenyls）Phosphorus is for formamide, yield 56%.It synthesizes formula
It is as follows：
1H NMR (400 MHz, CDCl3) δ 7.73 (s, 1H), 7.37 (d, J = 8.5 Hz, 2H), 6.84
(d, J = 8.6 Hz, 2H), 4.08 (s, 1H), 3.78 (s, 3H), 3.56 (s, 1H) ppm. 13C NMR
(100 MHz, CDCl3) δ 171.6, 171.5, 156.8, 130.7, 122.0, 114.1, 55.4 ppm. 31P NMR
(162 MHz, CDCl3 δ -123.9 ppm。
Embodiment 3：N-（3,4- dimethoxy-phenylfs）Preparation of the phosphorus for formamide
In Schlenk pipes, 2 mL acetic acid are sequentially added, 3 mL distilled water, 1 mmol 3,4- dimethoxyanilines,
The aqueous solution for being slowly added to phosphorus Zassol is stirred at room temperature down（1.5 mmol phosphorus Zassols are dissolved in 1 mL distilled water）, it is added dropwise
The reaction was continued afterwards 10 h or so（It is clarified to reaction solution）；After reaction, anhydrous with the ethyl acetate Rapid Extraction of 3 × 15 mL
Magnesium sulfate is dried, and 0.1 mL concentrated hydrochloric acids are added with unreacted anil of going out（Its hydrochloride is heavy insoluble in ethyl acetate
Precipitation goes out）, column chromatography for separation obtains the product of sterling --- N-（3,4- dimethoxy-phenylfs）Phosphamide, yield 59%.It is closed
An accepted way of doing sth is as follows：
1H NMR (400 MHz, CDCl3) δ 7.66 (s, 1H), 7.24 (d, J = 2.5 Hz, 1H), 6.88
(dd, J = 8.7, 2.5 Hz, 1H), 6.79 (d, J = 8.6 Hz, 1H), 4.08 (s, 1H), 3.85 (s,
6H), 3.56 (s, 1H) ppm. 13C NMR (100 MHz, CDCl3) δ 146.9, 144.3, 129.1, 110.1,
109.2, 103.1, 54.0 ppm. 31P NMR (162 MHz, CDCl3) δ -123.7 ppm.
Embodiment 4：N-（The chloro- phenyl of 4-）Preparation of the phosphorus for formamide
In Schlenk pipes, 2 mL acetic acid, 3 mL distilled water are sequentially added, 1 mmol 4- chloroanilines are stirred at room temperature
Under be slowly added to the aqueous solution of phosphorus Zassol（1.5 mmol phosphorus Zassols are dissolved in 1 mL distilled water）, continue after being added dropwise anti-
Answer 10 h or so（It is clarified to reaction solution）；After reaction, with the ethyl acetate Rapid Extraction of 3 × 15 mL, anhydrous magnesium sulfate is dry
It is dry, 0.1 mL concentrated hydrochloric acids are added with unreacted 4- chloroanilines of going out（Its hydrochloride does not dissolve in ethyl acetate Precipitation）, column
Chromatography obtains the product of sterling --- N-（The chloro- phenyl of 4-）Phosphorus is for formamide, yield 43%.It is as follows that it synthesizes formula：
1H NMR (600 MHz, CDCl3) δ 7.59 (s, 1H), 7.41 (d, J = 8.0 Hz, 2H), 7.28
(d, J = 8.3 Hz, 2H), 4.01 (s, 1H), 3.66 (s, 1H) ppm. 13C NMR (150 MHz, CDCl3)
δ 171.7, 135.9, 129.9, 129.1, 121.2 ppm. 31P NMR (162 MHz, CDCl3) δ -123.9
ppm。
Embodiment 5：N-（The bromo- phenyl of 4-）Preparation of the phosphorus for formamide
In Schlenk pipes, 2 mL acetic acid, 3 mL distilled water are sequentially added, 1 mmol 4- bromanilines are stirred at room temperature
Under be slowly added to the aqueous solution of phosphorus Zassol（1.5 mmol phosphorus Zassols are dissolved in 1 mL distilled water）, continue after being added dropwise anti-
Answer 10 h or so（It is clarified to reaction solution）；After reaction, with the ethyl acetate Rapid Extraction of 3 × 15 mL, anhydrous magnesium sulfate is dry
It is dry, 0.1 mL concentrated hydrochloric acids are added with unreacted 4- chloro-bromobenzenes amine of going out（Its hydrochloride does not dissolve in ethyl acetate Precipitation）,
Column chromatography for separation obtains the product of sterling --- N-（The bromo- phenyl of 4-）Phosphorus is for formamide.Yield 40%.It is as follows that it synthesizes formula：
1H NMR (600 MHz, DMSO-d6) δ 10.50 (s, 1H), 7.50 (d, J = 8.8 Hz, 2H),
7.47 - 7.43 (m, 2H), 3.96 (s, 1H), 3.60 (s, 1H) ppm. 13C NMR (150 MHz, DMSO-
d6) δ 172.5, 138.4 (d, J = 2.7 Hz), 132.0, 121.7, 115.8 ppm. 31P NMR (162 MHz,
DMSO) δ -125.0 ppm。
Embodiment 6：N-（4- methylphenyls）Preparation of the phosphorus for formamide
In Schlenk pipes, 2 mL acetic acid, 3 mL distilled water are sequentially added, 1 mmol 4- methylanilines are stirred in room temperature
Mix down the aqueous solution for being slowly added to phosphorus Zassol（1.5 mmol phosphorus Zassols are dissolved in 1 mL distilled water）, continue after being added dropwise
React 10 h or so（It is clarified to reaction solution）；After reaction, with the ethyl acetate Rapid Extraction of 3 × 15 mL, anhydrous magnesium sulfate
It is dry, 0.1 mL concentrated hydrochloric acids are added with unreacted 4- methylanilines of going out（Its hydrochloride is insoluble in ethyl acetate precipitation analysis
Go out）, column chromatography for separation obtains the product of sterling --- N-（4- methylphenyls）Phosphorus is for formamide.Yield 58%.It synthesizes formula such as
Under：
1H NMR (600 MHz, CDCl3) δ 8.11 (s, 1H), 7.34 (d, J = 7.9 Hz, 2H), 7.07
(d, J = 8.0 Hz, 2H), 3.97 (s, 1H), 3.62 (s, 1H), 2.29 (s, 3H) ppm. 13C NMR
(150 MHz, CDCl3) δ 171.3, 135.2, 134.5, 129.5, 120.3, 20.9. 31P NMR (162 MHz,
CDCl3) δ -124.02 ppm。
Embodiment 7：N-（Betanaphthyl）Preparation of the phosphorus for formamide
In Schlenk pipes, 2 mL acetic acid are sequentially added, 3 mL distilled water, 1 mmol beta-naphthylamines, under stirring at room temperature
It is slowly added to the aqueous solution of phosphorus Zassol（1.5 mmol phosphorus Zassols are dissolved in 1 mL distilled water）, the reaction was continued after being added dropwise
10 h or so（It is clarified to reaction solution）；After reaction, with the ethyl acetate Rapid Extraction of excessive 3 × 15 mL, anhydrous magnesium sulfate
It is dry, 0.1 mL concentrated hydrochloric acids are added with unreacted beta-naphthylamine of going out（Its hydrochloride does not dissolve in ethyl acetate Precipitation）, column
Chromatography obtains the product of sterling --- N-（Betanaphthyl）Preparation of the phosphorus for formamide.Yield 44%.It is as follows that it synthesizes formula：
1H NMR (600 MHz, DMSO-d6) δ 10.59 (s, 1H), 8.21 (s, 1H), 7.86-7.78 (m,
3H), 7.54 (dd, J = 8.8, 1.7 Hz, 1H), 7.46 (dd, J = 11.0, 4.0 Hz, 1H), 7.40
(dd, J = 10.9, 3.9 Hz, 1H), 4.03 (s, 1H), 3.67 (s, 1H) ppm. 13C NMR (151 MHz,
DMSO-d6) δ 172.4, 136.7, 133.7, 130.4, 128.9, 127.9, 126.9, 125.3, 120.3,
116.1 ppm. 31P NMR (162 MHz, DMSO-d6) δ -124.98 ppm。
In the various embodiments described above, phosphorus Zassol is synthesized according to the method that document provides: D. Heift, Z. Benkő
and H. Grützmacher, Dalton Trans., 2014, 43, 831。
Claims (3)
1. a kind of N- aryl phosphorus is for the preparation method of formamide, it is characterised in that：Be using acetic acid aqueous solution as solvent, aromatic amine with
Phosphorus Zassol is directly reacted and is obtained；Specifically preparation process is：In an ar atmosphere, phosphorus Zassol and aromatic amine are in acetic acid aqueous solution
In, 3 ~ 24 h are reacted at 10 DEG C ~ 45 DEG C；After reaction, it extracts, separation obtains N- aryl phosphorus for formamide；The fragrance
Amine is 4- aminoanisoles, 3,4- dimethoxyanilines, aniline, 4- chloroanilines, 4- bromanilines, beta-naphthylamine or 4- methylanilines.
2. N- aryl phosphorus as described in claim 1 is for the preparation method of formamide, it is characterised in that：Aromatic amine and phosphorus Zassol
Molar ratio is 1:0.25~1:4.
3. N- aryl phosphorus as described in claim 1 is for the preparation method of formamide, it is characterised in that：In acetic acid aqueous solution, distillation
The volume ratio of water and glacial acetic acid is 1:1~1:4.
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| "磷氰酸根负离子的合成及其在含磷有机(杂环)化合物合成中的应用研究进展";权正军 等;《有机化学》;20150708;第35卷;第2301-2312页 * |
| AndrewR.Jupp,et al.."Exploiting the Brønsted Acidity of Phosphinecarboxamides for the Synthesis of New Phosphides and Phosphines".《Chem. Eur.J.》.2015,第21卷第8015-8018页. * |
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