CN108977840A - The method that anodic oxidation prepares N- arylamine group formylphosphonic acid ester - Google Patents
The method that anodic oxidation prepares N- arylamine group formylphosphonic acid ester Download PDFInfo
- Publication number
- CN108977840A CN108977840A CN201810795647.6A CN201810795647A CN108977840A CN 108977840 A CN108977840 A CN 108977840A CN 201810795647 A CN201810795647 A CN 201810795647A CN 108977840 A CN108977840 A CN 108977840A
- Authority
- CN
- China
- Prior art keywords
- formamide
- phosphorus
- anodic oxidation
- acid ester
- arylamine group
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention provides a kind of methods that anodic oxidation prepares N- arylamine group formylphosphonic acid ester; it is for formamide using N- aryl phosphorus as raw material, alcohol is solvent and cathode reactant, and tetrabutylammonium iodide is as catalyst; lithium perchlorate carries out anodic oxidation reactions as electrode and obtains as electrolyte, platinized platinum.The present invention is catalyst, I when anodic oxidation using tetrabutylammonium iodide‑Anion in-situ preparation I2It participates in activation N- aryl phosphorus and reacts generation product, I with alcohol for formamide2It is reduced to I‑Anion, I‑Anion realizes under the conditions of electro-redox by I‑Anion is to I2Regeneration and recycling, avoid excessive I2Requirement, simple process, reaction condition is mild, at low cost, and yield is high；It is both reactant with cheap alcohol, also does as solvent, is not only that reaction provides medium, and to react cathode reactant, reduces the pollution to environment.
Description
Technical field
The present invention relates to a kind of preparation method of N- arylamine group formylphosphonic acid ester more particularly to a kind of anodic oxidation sun
Pole aoxidizes the method for preparing N- arylamine group formylphosphonic acid ester, belongs to synthetic organic chemical art.
Background technique
Organic phosphorus compound is closely related with human lives, it is in nucleic acid, coenzyme, organic phosphorus 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.Organophosphonate and its derivative are a kind of chemical combination important in various fields
Object, especially pharmaceutical chemistry, materials chemistry, the fields such as agriculture chemistry and catalysis.For example, phosphonate ester and carbamylphosphonate are
Matrix metalloproteinase (MMP) inhibitor, anti-transfer agent and antitumor agent.
The chemical name of phosphonate ester is N- arylamine group formylphosphonic acid ester, and structural formula is as follows:
Wherein, R1 = H、Br、Cl、CH3、OCH3,R2 =OCH3、OC2H5、OC3H8、OCH(CH3)2。
In recent years, Robinson and Goicoechea is reported and this research group successively realizes PCO and amine addition
Reaction, be prepared for N- alkyl/aryl substituted 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; Eur. J. Org. Chem. 2017, 5546).2018, Quan Zhengjun et al. was reported under excessive elemental iodine promotion
N- aryl replaces phosphorus to react method (the Adv. Syn. Catal. for synthesizing N- arylamine group formylphosphonic acid ester with alcohol for formamide
2017,360,2382).However, the shortcoming of this method is to need using excessive elemental iodine, catalytic amount iodine rush cannot achieve
Into reaction.
Summary of the invention
The purpose of the present invention is aiming at the problems existing in the prior art, provide a kind of anodic oxidation preparation N- arylamine group
The method of formylphosphonic acid ester.
The method that the present invention prepares N- arylamine group formylphosphonic acid ester is for formamide using N- aryl phosphorus as raw material, alcohol
For solvent and cathode reactant, tetrabutylammonium iodide is carried out as electrolyte, platinized platinum as electrode as catalyst, lithium perchlorate
Anodic oxidation reactions and obtain.
Reaction raw materials N- aryl phosphorus is for formamide are as follows: N- (4- methoxyl group-phenyl) phosphorus is for formamide, N- (3,4- dimethoxy
Base-phenyl) phosphorus for formamide, N- phenyl phosphorus for formamide, N- (the chloro- phenyl of 4-) phosphorus for formamide, N- (the bromo- phenyl of 4-) phosphorus generation
Formamide, N- (2- methylphenyl) phosphorus are for formamide or N- (4- methylphenyl) phosphorus for formamide.
Solvent alcohol are as follows: methanol, ethyl alcohol, normal propyl alcohol, isopropanol.
The dosage of catalyst tetrabutylammonium iodide is reaction raw materials N- aryl phosphorus for 0.1 ~ 0.6 times of formamide mole.
Content of the electrolyte lithium perchlorate in alcoholic solvent is 0.1 ~ 0.5 mmol/mL.
The anodic oxidation reactions are that 2 ~ 3h is reacted at 10 DEG C ~ 45 DEG C under the constant current of I=10mA.
Synthetic product of the present invention is detected through means such as infrared, nuclear-magnetism, single crystal diffractions, is N- arylamine group formylphosphonic acid ester
Sterling.
The present invention has the advantage that compared with the prior art
1, using N- aryl phosphorus for formamide and alcohol as raw material, tetrabutylammonium iodide is catalyst, is realized under the conditions of electroxidation
By I-Anion is to I2Regeneration and recycling, avoid excessive I2Requirement；
2, using alcohol as solvent, medium is provided for reaction, while being also cathodic reduction substance, so that system is simpler, behaviour
Facilitate；Alcohol itself is cheap and easy to get, and restores and generate hydrogen, green, environmental protection；
3, preparation process is simple, and reaction condition is mild, at low cost, and yield is high.
Specific embodiment
It is done furtherly below by preparation method of the specific embodiment to N- arylamine group formylphosphonic acid ester of the present invention
It is bright.
The preparation of embodiment 1, dimethyl (p-methylphenyl amido formacyl) phosphonate ester
In three-neck flask, 10 mL methanol are sequentially added, 0.3 mmol lithium perchlorate, 10 mol% tetrabutylammonium iodides, 0.2
Mmol N- phenyl phosphorus is for formamide, and under stirring at room temperature, platinized platinum is as electrode, 2 h of constant-current electrolysis or so at the mA of I=10
(becoming faint yellow to reaction solution from colourless)；It is detected through TCL, after reaction, the quenching reaction of 2 mL saturated ammonium chlorides is added, uses
The ethyl acetate Rapid Extraction of excessive (3 × 15 mL), anhydrous magnesium sulfate is dry, column chromatography for separation (eluant, eluent is ethyl acetate:
Petroleum ether=1:2), obtain the product of sterling --- dimethyl (p-methylphenyl amido formacyl) phosphonate ester.Yield 92%.It is synthesized
Formula is as follows:
1H NMR (600 MHz, CDCl3) δ=8.87 (s, 1H), 7.63 (d, J = 8.4Hz, 2H), 7.35(t,J =7.8Hz,, 2H), 7.19 (t, J = 7.2Hz, 1H), 3.93 (s, 3H), 3.92 (s, 3H).13C NMR
(150MHz,CDCl3) δ = 163.20 (d, J = 226.4 Hz), 136.34 (d, J = 13.2 Hz), 129.16
, 125.74 , 120.09 , 54.76 , 54.72 .31P NMR (162 MHz, CDCl3) δ =1.67。
Embodiment 2: the preparation of diethyl ((4- methoxyphenyl) amido formacyl) phosphonate ester
In three-neck flask, 10 mL ethyl alcohol are sequentially added, 0.3 mmol lithium perchlorate, 10 mol% tetrabutylammonium iodides, 0.2
Phosphorus is for formamide by mmol N- (4- methoxyphenyl), under stirring at room temperature, using platinized platinum as electrode, the permanent electricity at the mA of I=10
2 h of galvanic electricity solution or so (becomes faint yellow to reaction solution from colourless)；It is detected through TCL, after reaction, 2 mL is added and are saturated chlorination
Ammonium quenching reaction, with the ethyl acetate Rapid Extraction of excess (3 × 15 mL), anhydrous magnesium sulfate is dry, column chromatography for separation (elution
Agent is ethyl acetate: petroleum ether=1:2), obtain the product of sterling --- diethyl ((4- methoxyphenyl) amido formacyl) phosphine
Acid esters.Yield 85%.It is as follows that it synthesizes formula:
1H NMR (600 MHz, CDCl3) δ=8.90 (s, 1H), 7.55 (d, J = 1.2Hz, 2H), 6.86 (d,J = 0.6 Hz, 2H), 4.33 – 4.21 (m, 4H), 3.78 (s, 3H), 1.38 (t, J = 7.2 Hz, 6H)
.13C NMR (150 MHz, CDCl3) δ=163.58 (d, J = 225.3 Hz), 157.17 , 129.77 (d, J =
13.7 Hz), 121.71 , 114.17 , 64.61 , 64.57 , 55.43 , 16.25 , 16.21 .31P NMR
(162 MHz, CDCl3) δ= -0.27。
Embodiment 3: the preparation of diisopropyl (o-tolyl amido formacyl) phosphonate ester
In three-neck flask, 10 mL isopropanols are sequentially added, 0.3 mmol lithium perchlorate, 10 mol% tetrabutylammonium iodides, 0.2
Phosphorus is for formamide by mmol N- (2- methylphenyl), under stirring at room temperature, using platinized platinum as electrode, the constant current at I=10mA
It is electrolysed 2 h or so (becoming faint yellow to reaction solution from colourless)；It is detected through TCL, after reaction, 2mL saturated ammonium chloride is added
Quenching reaction, with the ethyl acetate Rapid Extraction of excess (3 × 15mL), anhydrous magnesium sulfate is dry, and (eluant, eluent is column chromatography for separation
Ethyl acetate: petroleum ether=1:2), obtain the product of sterling --- diisopropyl (o-tolyl amido formacyl) phosphonate ester.It produces
Rate 80%.It is as follows that it synthesizes formula:
1H NMR (600 MHz, CDCl3) δ= 8.64 (s, 1H), 7.94 (d, J = 7.8Hz, 1H), 7.23 –
7.20(m, 2H), 7.11 (t, J = 7.8 Hz, 1H), 4.88 – 4.80 (m, 2H), 2.30 (s, 3H),
1.39 (dd, J = 10.8, 6.6 Hz, 12H).13C NMR (151 MHz, CDCl3) δ=164.96 (d, J =
225.8 Hz), 134.45 (d, J = 12.5 Hz), 130.63 , 126.85 , 125.97 , 122.15 , 73.89
, 73.85 , 23.91 , 23.89 , 23.78 , 23.75 , 17.55 .31P NMR (162 MHz, CDCl3) δ= -
2.07。
Embodiment 4: the preparation of diisopropyl ((4- chlorphenyl) amido formacyl) phosphonate ester
In three-neck flask, 10 mL isopropanols are sequentially added, 0.3 mmol lithium perchlorate, 10 mol% tetrabutylammonium iodides, 0.2
Phosphorus is for formamide by mmol N- (the chloro- phenyl of 4-), under stirring at room temperature, using platinized platinum as electrode, the constant current at the mA of I=10
It is electrolysed 2 h or so (becoming faint yellow to reaction solution from colourless)；It is detected through TCL, after reaction, 2 mL saturated ammonium chlorides is added
Quenching reaction, with the ethyl acetate Rapid Extraction of excess (3 × 15mL), anhydrous magnesium sulfate is dry, and (eluant, eluent is column chromatography for separation
Ethyl acetate: petroleum ether=1:2), obtain the product of sterling --- diisopropyl ((4- chlorphenyl) amido formacyl) phosphonate ester.
Yield 75%.It is as follows that it synthesizes formula:
1H NMR (600 MHz, CDCl3) δ=8.82 (s, 1H), 7.58 (d, J = 9.0 Hz, 2H), 7.31
(d, J = 9.0 Hz, 2H), 4.85-4.78(m, 2H), 1.39 (dd, J = 14.4, 6.0 Hz, 12H).13C
NMR (150 MHz, CDCl3) δ=165.09 (d, J = 226.5 Hz), 135.08(d, J = 12.6 Hz),
130.59 , 129.18 , 121.19 , 74.08 , 23.88 , 23.85 , 23.76 , 23.73 .31P NMR (162
MHz,CDCl3) δ=-2.67。
Embodiment 5: the preparation of dimethyl ((4- bromophenyl) amido formacyl) phosphonate ester
In three-neck flask, 10 mL methanol are sequentially added, 0.3 mmol lithium perchlorate, 10 mol% tetrabutylammonium iodides, 0.2
Phosphorus is for formamide by mmol N- (the bromo- phenyl of 4-), under stirring at room temperature, using platinized platinum as electrode, the constant current at the mA of I=10
It is electrolysed 2 h or so (becoming faint yellow to reaction solution from colourless)；It is detected through TCL, after reaction, 2 mL saturated ammonium chlorides is added
Quenching reaction, with the ethyl acetate Rapid Extraction of excess (3 × 15 mL), anhydrous magnesium sulfate is dry, column chromatography for separation (eluant, eluent
For ethyl acetate: petroleum ether=1:2), obtain the product of sterling --- dimethyl ((4- bromophenyl) amido formacyl) phosphonate ester.
Yield 87%.It is as follows that it synthesizes formula:
1H NMR (600 MHz, CDCl3) δ 9.83 (s, 1H), 7.63 (d, J= 8.8 Hz, 2H), 7.43 (d,J= 8.8 Hz,2H), 3.90 (s, 3H), 3.88 (s, 3H).13C NMR (150MHz, CDCl3) δ =164.09
(s), 162.57 (s), 135.98 (d, J= 14.1 Hz), 131.92 (s), 122.10 (s), 118.29 (s),
54.85 (d, J= 6.6 Hz).31P NMR (162 MHz, CDCl3)δ =0.85。
Embodiment 6: the preparation of dipropyl (p-methylphenyl amido formacyl) phosphonate ester
In three-neck flask, 10 mL normal propyl alcohols are sequentially added, 0.3 mmol lithium perchlorate, 10 mol% tetrabutylammonium iodides, 0.2
Phosphorus is for formamide by mmol N- (4- methylphenyl), under stirring at room temperature, using platinized platinum as electrode, the constant current at the mA of I=10
It is electrolysed 2 h or so (becoming faint yellow to reaction solution from colourless)；It is detected through TCL, after reaction, 2mL saturated ammonium chloride is added
Quenching reaction, with the ethyl acetate Rapid Extraction of excess (3 × 15 mL), anhydrous magnesium sulfate is dry, column chromatography for separation (eluant, eluent
For ethyl acetate: petroleum ether=1:2), obtain the product of sterling --- dipropyl (p-methylphenyl amido formacyl) phosphonate ester.It produces
Rate 84%.It is as follows that it synthesizes formula:
1H NMR (600 MHz, CDCl3) δ= 8.92 (s, 1H), 7.51 (d, J = 8.4 Hz, 2H), 7.13
(d, J = 7.8 Hz, 2H), 4.20 – 4.10 (m, 4H), 2.31 (s, 3H), 1.77-1.71 (m, 4H),
0.96 (t, J = 7.2 Hz, 6H).13C NMR (150 MHz, CDCl3) δ= 163.81 (d, J = 225.3 Hz),
135.30 , 134.06 (d, J = 13.4 Hz), 129.55 , 120.05 , 69.99 , 69.95 , 23.72 ,
23.68 , 20.92 , 9.89 .31P NMR (162 MHz,CDCl3) δ= -0.27。
Embodiment 7: the preparation of diethyl ((3,4- Dimethoxyphenyl) amido formacyl) phosphonate ester
In three-neck flask, 10 mL ethyl alcohol are sequentially added, 0.3 mmol lithium perchlorate, 10 mol% tetrabutylammonium iodides, 0.3
Phosphorus is for formamide by mmol N- (3,4- Dimethoxyphenyl), under stirring at room temperature, using platinized platinum as electrode, at I=10mA
2 h of constant-current electrolysis or so (becomes faint yellow to reaction solution from colourless)；It is detected through TCL, after reaction, 2 mL saturation is added
Ammonium chloride quenching reaction, with the ethyl acetate Rapid Extraction of excess (3 × 15 mL), anhydrous magnesium sulfate is dry, column chromatography for separation
(eluant, eluent is ethyl acetate: petroleum ether=1:2), obtains the product of sterling --- diethyl ((3,4- Dimethoxyphenyl) amido
Formoxyl) phosphonate ester.Yield 85%.It is as follows that it synthesizes formula:
1H NMR (600 MHz, CDCl3) δ =9.09 (s, 1H), 7.42 (d, J= 2.0 Hz, 1H), 7.12
(dd, J= 8.6, 2.2 Hz, 1H), 6.80 (d, J= 8.7 Hz, 1H), 4.33 –4.20 (m, 4H), 3.86
(s, 3H), 3.85 (s, 3H), 1.37 (t, J= 7.1 Hz,6H).13C NMR (150MHz, CDCl3) δ 164.40
(s), 162.90 (s), 148.97 (s), 146.65 (s), 130.36 (d, J= 13.8 Hz), 112.20 (s),
111.19 (s), 104.72 (s), 64.63 (d, J= 6.6 Hz), 56.04 (s), 55.87 (s), 16.22 (d,J= 5.9 Hz).31P NMR (162 MHz, CDCl3) δ= -5.27。
In the various embodiments described above, phosphorus is synthesized for formamide according to the method that document provides: Yong-Hui Wu, Zhi-
Feng Li, Wen-Peng Wang, Xi-Cun Wang and Zheng-Jun Quan, Eur. J. Org. Chem.
2017, 5546–5553。
Claims (6)
1. the method that anodic oxidation prepares N- arylamine group formylphosphonic acid ester is for formamide using N- aryl phosphorus as raw material, alcohol
For solvent and cathode reactant, tetrabutylammonium iodide is carried out as electrolyte, platinized platinum as electrode as catalyst, lithium perchlorate
Anodic oxidation reactions and obtain.
2. the method that anodic oxidation as described in claim 1 prepares N- arylamine group formylphosphonic acid ester, it is characterised in that: reaction
Raw material N- aryl phosphorus is for formamide are as follows: N- (4- methoxyl group-phenyl) phosphorus is for formamide, N- (3,4- dimethoxy-phenylf) phosphorus generation
Formamide, N- phenyl phosphorus are for formamide, N- (the chloro- phenyl of 4-) phosphorus for formamide, N- (the bromo- phenyl of 4-) phosphorus for formamide, N- (2-
Methylphenyl) phosphorus for formamide or N- (4- methylphenyl) phosphorus for formamide.
3. the method that anodic oxidation as described in claim 1 prepares N- arylamine group formylphosphonic acid ester, it is characterised in that: solvent
Alcohol is methanol, ethyl alcohol, normal propyl alcohol or isopropanol.
4. the method that anodic oxidation as described in claim 1 prepares N- arylamine group formylphosphonic acid ester, it is characterised in that: catalysis
The dosage of agent tetrabutylammonium iodide is reaction raw materials N- aryl phosphorus for 0.1 ~ 0.6 times of formamide mole.
5. the method that anodic oxidation as described in claim 1 prepares N- arylamine group formylphosphonic acid ester, it is characterised in that: electrolysis
Content of the matter lithium perchlorate in alcoholic solvent is 0.1 ~ 0.5 mmol/mL.
6. the method that anodic oxidation as described in claim 1 prepares N- arylamine group formylphosphonic acid ester, it is characterised in that: described
Anodic oxidation reactions are that 2 ~ 3h is reacted at 10 DEG C ~ 45 DEG C under the constant current of I=10mA.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810795647.6A CN108977840A (en) | 2018-07-19 | 2018-07-19 | The method that anodic oxidation prepares N- arylamine group formylphosphonic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810795647.6A CN108977840A (en) | 2018-07-19 | 2018-07-19 | The method that anodic oxidation prepares N- arylamine group formylphosphonic acid ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108977840A true CN108977840A (en) | 2018-12-11 |
Family
ID=64549754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810795647.6A Pending CN108977840A (en) | 2018-07-19 | 2018-07-19 | The method that anodic oxidation prepares N- arylamine group formylphosphonic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108977840A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111286748A (en) * | 2020-02-12 | 2020-06-16 | 齐鲁工业大学 | Method for electrochemically synthesizing carbazole compounds |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090221842A1 (en) * | 2004-04-21 | 2009-09-03 | Wacker Chemie Ag | Method for the production of organosilicon compounds comprising carboxy radicals |
| CN102153470A (en) * | 2011-02-25 | 2011-08-17 | 苏州大学 | Method for preparing perester compound |
| CN105483749A (en) * | 2015-11-27 | 2016-04-13 | 北京工业大学 | Method for electro-synthesizing 3-amido-2-thio-cyano-alpha, beta-unsaturated carbonyl compound in pairs |
| CN106567104A (en) * | 2016-10-31 | 2017-04-19 | 华南理工大学 | Electrochemical synthesis method of 1,1'-diindolylmethane derivatives |
| CN107829105A (en) * | 2017-11-16 | 2018-03-23 | 南阳师范学院 | A kind of method of electrochemistry formated α acyloxy ketone |
-
2018
- 2018-07-19 CN CN201810795647.6A patent/CN108977840A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090221842A1 (en) * | 2004-04-21 | 2009-09-03 | Wacker Chemie Ag | Method for the production of organosilicon compounds comprising carboxy radicals |
| CN102153470A (en) * | 2011-02-25 | 2011-08-17 | 苏州大学 | Method for preparing perester compound |
| CN105483749A (en) * | 2015-11-27 | 2016-04-13 | 北京工业大学 | Method for electro-synthesizing 3-amido-2-thio-cyano-alpha, beta-unsaturated carbonyl compound in pairs |
| CN106567104A (en) * | 2016-10-31 | 2017-04-19 | 华南理工大学 | Electrochemical synthesis method of 1,1'-diindolylmethane derivatives |
| CN107829105A (en) * | 2017-11-16 | 2018-03-23 | 南阳师范学院 | A kind of method of electrochemistry formated α acyloxy ketone |
Non-Patent Citations (1)
| Title |
|---|
| YONG-HUI WU等: ""Iodine-promoted rapid construction of carbamoylphosphonates from phosphinecarboxamides"", 《ADVANCED SYNTHESIS & CATALYSIS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111286748A (en) * | 2020-02-12 | 2020-06-16 | 齐鲁工业大学 | Method for electrochemically synthesizing carbazole compounds |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhu et al. | Merging electrolysis and nickel catalysis in redox neutral cross-coupling reactions: experiment and computation for electrochemically induced C–P and C–Se bonds formation | |
| US10422047B2 (en) | Electrochemical process for coupling of phenol to aniline | |
| CN106544692B (en) | A kind of electrochemical preparation method of 3- selenium (hetero) aryl indole class compound | |
| US9006491B2 (en) | Structure and method for synthesizing and using dialkyl(2,4,6- or 2,6-alkoxyphenyl)phosphine and its tetrafluoroborate | |
| Bolshan et al. | Copper-catalyzed cross-coupling of amides and potassium alkenyltrifluoroborate salts: a general approach to the synthesis of enamides | |
| Budnikova et al. | Nickel-catalysed electrochemical coupling between mono-or di-chlorophenylphosphines and aryl or heteroaryl halides | |
| CN103992225B (en) | A kind of salicylaldehyde derivatives and preparation method thereof | |
| CN102584795B (en) | Preparing method of crizotinib | |
| CN106045969A (en) | Synthesis method of cobimetinib | |
| Kumar et al. | Bio-catalysts and catalysts based on ruthenium (II) polypyridyl complexes imparting diphenyl-(2-pyridyl)-phosphine as a co-ligand | |
| US20110065961A1 (en) | Process for production of phosphine derivative from phosphine oxide derivative | |
| CN108977840A (en) | The method that anodic oxidation prepares N- arylamine group formylphosphonic acid ester | |
| US5527967A (en) | Process for preparing tertiary diarylalkylphosphines | |
| US5756727A (en) | Chiral manganese triazononane complexes | |
| CN113957461B (en) | Electrochemical synthesis method of 1,1' -binaphthyl compound | |
| Zhu et al. | Practical and highly stereoselective method for the preparation of several chiral arylsulfinamides and arylsulfinates based on the spontaneous crystallization of diastereomerically pure N-benzyl-N-(1-phenylethyl)-arylsulfinamides | |
| CN103804432B (en) | Double-functionalized amine-thiourea organic catalyst based on ferrocene and preparation method and application thereof | |
| Islami et al. | Chemoselective synthesis of stable phosphorus ylides containing a β-amino group | |
| CN106749396B (en) | Method for preparing organic phosphonate compound by efficiently esterifying compound containing P (O) -OH and alcohol | |
| CN104689849A (en) | Phosphamide-(di) secondary amine dual-functional catalyst and synthesis method thereof | |
| KR20150124995A (en) | Electrochemical coupling of a phenol to a naphthol | |
| Du et al. | Reduction of 1-(2-Chloroethyl)-2-nitrobenzene and 1-(2-Bromoethyl)-2-nitrobenzene at Carbon Cathodes: Electrosynthetic Routes to 1-Nitro-2-vinylbenzene and 1H-Indole | |
| EP1394168B1 (en) | Process for the preparation of phosphites and complexes with transition metals | |
| Vasconcelos et al. | New homochiral amino-phosphine ligands: application in asymmetric palladium catalyzed allylic alkylation | |
| CN104151342B (en) | A kind of method synthesizing connection boric acid pinacol ester |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181211 |