CN111377963B - Method for preparing thiophosphine compound through visible light-promoted dehydrogenation coupling reaction - Google Patents

Method for preparing thiophosphine compound through visible light-promoted dehydrogenation coupling reaction Download PDF

Info

Publication number
CN111377963B
CN111377963B CN202010263678.4A CN202010263678A CN111377963B CN 111377963 B CN111377963 B CN 111377963B CN 202010263678 A CN202010263678 A CN 202010263678A CN 111377963 B CN111377963 B CN 111377963B
Authority
CN
China
Prior art keywords
compound
mmol
visible light
thiophosphine
preparing
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.)
Active
Application number
CN202010263678.4A
Other languages
Chinese (zh)
Other versions
CN111377963A (en
Inventor
吴立朋
王显亚
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lanzhou Institute of Chemical Physics LICP of CAS
Original Assignee
Lanzhou Institute of Chemical Physics LICP of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Lanzhou Institute of Chemical Physics LICP of CAS filed Critical Lanzhou Institute of Chemical Physics LICP of CAS
Priority to CN202010263678.4A priority Critical patent/CN111377963B/en
Publication of CN111377963A publication Critical patent/CN111377963A/en
Application granted granted Critical
Publication of CN111377963B publication Critical patent/CN111377963B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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

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)

Abstract

The invention relates to a method for preparing a thiophosphine compound by a dehydrogenation coupling reaction promoted by visible light, which comprises the following steps: dissolving an organic phosphine compound and a visible light photosensitizer into a solvent, then adding a thiophenol compound and an oxidant, reacting for 12 hours at normal temperature under the irradiation of LED white light in a protective atmosphere, and then separating to obtain the thiophosphine compound. The method has the advantages of simple and convenient operation, mild conditions and low energy consumption, and is suitable for large-batch laboratory preparation.

Description

Method for preparing thiophosphine compound through visible light-promoted dehydrogenation coupling reaction
Technical Field
The invention relates to the technical field of organic synthesis, main group elements and visible light catalysis, in particular to a method for preparing a thiophosphine compound by a dehydrogenation coupling reaction promoted by visible light.
Background
There are relatively few examples of using a catalytic oxidative dehydrogenation coupling process to form E-E' bonds between main group element compounds (where E is a main group element other than carbon). In this respect, methods for synthesizing thiophosphine compounds are more rare. Both systems have been reported to be carried out at temperatures above 110 ℃ without extending the applicability to the substrate. The thiophosphine compound has wide application potential in the aspects of pharmacy and pesticide chemistry, so the development of the method for synthesizing the thiophosphine by directly oxidizing, dehydrogenating and coupling the organic phosphine and the thiophenol under mild conditions has important application value and research significance.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing a thiophosphine compound by a visible light-promoted dehydrogenation coupling reaction, which is simple and convenient to operate and mild in condition.
In order to solve the above problems, the method for preparing a thiophosphine compound by a visible light-promoted dehydrocoupling reaction according to the present invention is characterized in that: dissolving an organic phosphine compound and a visible light photosensitizer into a solvent, then adding a thiophenol compound and a weak oxidant, reacting for 12 hours at normal temperature under the irradiation of LED white light in a protective atmosphere, and then separating to obtain a thiophosphine compound; the feeding molar ratio of the organic phosphine compound to the visible light photosensitizer is 1: 0.01; the feeding molar ratio of the organic phosphine compound to the thiophenol compound is 1: 1 or 1: 3.
the reaction equation in the synthesis method is as follows:
Figure DEST_PATH_IMAGE001
the organophosphine compound is aryl-substituted primary and secondary phosphonous compounds, and the structural formula of the organophosphine compound is as follows: r1R2PH, wherein R2 = H or R1，R1Is an aryl substituent.
The visible light photosensitizer is tris (2-phenylpyridine) iridium (Ir (ppy)3) Tris (2, 2' -bipyridine) ruthenium (II) chloride hexahydrate ([ Ru (bpy))3]Cl2·6H2O), Eosin Y (Eosin-Y), Eosin B (Eosin-B), Bengal (Rose Bengal).
The solvent is one of acetonitrile, absolute ethyl alcohol, tetrahydrofuran, 1, 4-dioxane, toluene, dichloromethane and dimethyl sulfoxide.
The thiophenol compound is aryl thiophenol with a structural formula
Figure 100002_DEST_PATH_IMAGE002
Wherein R is3Is one of methoxy, methyl, ethyl, isopropyl and fluorine and chlorine substituent, the substituent is mono-substituted or di-substituted, and the position of the substituent is any position on a benzene ring.
The weak oxidizing agent (HA) is an unsaturated compound containing double bonds.
The oxidant is one of benzophenone, imine, styrene, azobenzene and benzaldehyde.
The protective atmosphere refers to nitrogen or argon.
Compared with the prior art, the invention has the following advantages:
1. the invention uses visible light as an energy source, so that the reaction can be carried out at room temperature, and the requirements of green chemistry are met.
2. The invention avoids the oxidation of the reaction substrate organic phosphine under the condition of other oxidants by using unsaturated compounds as weak oxidants.
3. The invention has simple operation and low energy consumption, and is suitable for large-scale laboratory preparation.
Detailed Description
Example 1 a method for preparing thiophosphine compounds by a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE003
diphenylphosphine (0.2 mmol, 37.2 mg), p-methoxythiophenol (0.2 mmol, 28 mg), azobenzene (0.2 mmol, 36.4 mg), Eosin Y (0.002 mmol, 1.4 mg), acetonitrile (1 mL) were added to the reaction tube in this order under a nitrogen (1 atm) atmosphere, and irradiated under an LED white light lamp for 12 hours under a nitrogen (1 atm) atmosphere. The yield of the product 3a is 35% by nuclear magnetic phosphine spectroscopy.
Example 2 a method for preparing a thiophosphine compound by a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE004
diphenylphosphine (0.2 mmol, 37.2 mg), p-methoxythiophenol (0.2 mmol, 28 mg), azobenzene (0.2 mmol, 36.4 mg), Eosin B (0.002 mmol, 1.2 mg), acetonitrile (1 mL) were added to the reaction tube in this order under a nitrogen (1 atm) atmosphere, and irradiated under an LED white light lamp for 12 hours under a nitrogen (1 atm) atmosphere. The yield of the product 3a is 39% by nuclear magnetic phosphine spectrum detection.
Example 3a method for preparing a thiophosphine compound using a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE005
diphenylphosphine (0.2 mmol, 37.2 mg), p-methoxyphenylphenol (0.2 mmol, 28 mg), azobenzene (0.2 mmol, 36.4 mg), [ Ru (bpy) ], were sequentially added to the reaction tube under a nitrogen atmosphere (1 atm)3]Cl2·6H2O (0.002 mmol, 1.5 mg), acetonitrile (1 mL) under nitrogen (1 atm) at LAnd an ED white light lamp irradiates for 12 h. The yield of the product 3a is 56% by nuclear magnetic phosphine spectroscopy.
Example 4a method for preparing a thiophosphine compound using a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE006
diphenylphosphine (0.2 mmol, 37.2 mg), p-methoxyphenylthiophenol (0.2 mmol, 28 mg), azobenzene (0.2 mmol, 36.4 mg), Rose Bengal (0.002 mmol, 1.9 mg), acetonitrile (1 mL) were added to the reaction tube in this order under a nitrogen (1 atm) atmosphere, and the mixture was irradiated under a LED white light for 12 hours under a nitrogen (1 atm) atmosphere. The yield of the product 3a is 35% by nuclear magnetic phosphine spectroscopy.
Example 5 a method for preparing a thiophosphine compound using a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE007
diphenylphosphine (0.2 mmol, 37.2 mg), p-methoxyphenylphenol (0.2 mmol, 28 mg), azobenzene (0.2 mmol, 36.4 mg), Ir (ppy) were added successively to the reaction tube under a nitrogen (1 atm) atmosphere3(0.002 mmol, 1.3 mg), acetonitrile (1 mL) under nitrogen (1 atm) for 12h in an LED white light. The yield of the product 3a is 65% by nuclear magnetic phosphine spectroscopy.
Example 6 a method for preparing a thiophosphine compound using a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE008
diphenylphosphine (0.2 mmol, 37.2 mg), p-methoxythiophenol (0.2 mmol, 28 mg), benzophenone (0.2 mmol, 36.4 mg), Ir (ppy) were added successively to the reaction tube under a nitrogen (1 atm) atmosphere3(0.002 mmol, 1.3 mg), acetonitrile (1 mL) in a nitrogen (1 atm) atmosphere in a LED white lightThe lamp irradiates for 12 h. The yield of the product 3a is 29% by nuclear magnetic phosphine spectroscopy.
Example 7 a method for preparing a thiophosphine compound using a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE009
diphenylphosphine (0.2 mmol, 37.2 mg), p-methoxythiophenol (0.2 mmol, 28 mg), imine (0.2 mmol, 36.2 mg), Ir (ppy)3(0.002 mmol, 1.3 mg), acetonitrile (1 mL) under nitrogen (1 atm) for 12h in an LED white light. The yield of the product 3a is 32% by nuclear magnetic phosphine spectroscopy.
Example 8 a method for preparing a thiophosphine compound using a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE010
diphenylphosphine (0.2 mmol, 37.2 mg), p-methoxythiophenol (0.2 mmol, 28 mg), styrene (0.2 mmol, 20.8 mg), Ir (ppy)3(0.002 mmol, 1.3 mg), acetonitrile (1 mL) under nitrogen (1 atm) for 12h in an LED white light. The yield of the product 3a is trace by nuclear magnetic phosphine spectrum detection.
Example 9 a method for preparing a thiophosphine compound using a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE011
diphenylphosphine (0.2 mmol, 37.2 mg), p-methoxythiophenol (0.2 mmol, 28 mg), benzaldehyde (0.2 mmol, 21.2 mg), Ir (ppy) were sequentially added to the reaction tube under a nitrogen (1 atm) atmosphere3(0.002 mmol, 1.3 mg), acetonitrile (1 mL) in a LED white lamp under a nitrogen (1 atm) atmosphereThe irradiation was carried out for 12 hours. The yield of the product 3a is 96% by nuclear magnetic phosphine spectroscopy.
Example 10 a method for preparing a thiophosphine compound by a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE012
diphenylphosphine (0.2 mmol, 37.2 mg), p-methoxythiophenol (0.2 mmol, 28 mg), benzaldehyde (0.2 mmol, 21.2 mg), Ir (ppy) were sequentially added to the reaction tube under a nitrogen (1 atm) atmosphere3(0.002 mmol, 1.3 mg), absolute ethanol (1 mL), under nitrogen (1 atm) atmosphere, was irradiated for 12h with an LED white light. The yield of the product 3a is 20% by nuclear magnetic phosphine spectroscopy.
Example 11 a method for preparing a thiophosphine compound using a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE013
diphenylphosphine (0.2 mmol, 37.2 mg), p-methoxythiophenol (0.2 mmol, 28 mg), benzaldehyde (0.2 mmol, 21.2 mg), Ir (ppy) were sequentially added to the reaction tube under a nitrogen (1 atm) atmosphere3(0.002 mmol, 1.3 mg), methylene chloride (1 mL) was irradiated under nitrogen (1 atm) for 12h in an LED white light. The yield of the product 3a is 78% by nuclear magnetic phosphine spectroscopy.
Example 12 a method for preparing a thiophosphine compound using a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE014
diphenylphosphine (0.2 mmol, 37.2 mg), p-methoxythiophenol (0.2 mmol, 28 mg), benzaldehyde (0.2 mmol, 21.2 mg), Ir (ppy) were sequentially added to the reaction tube under a nitrogen (1 atm) atmosphere3(0.002 mmol, 1.3 mg), tetrahydrofuran (1 mL) in a nitrogen (1 atm) atmosphereAnd irradiating for 12h by using an LED white light lamp. The yield of the product 3a is 88 percent by nuclear magnetic phosphine spectrum detection.
Example 13 a method for preparing a thiophosphine compound using a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE015
diphenylphosphine (0.2 mmol, 37.2 mg), p-methoxythiophenol (0.2 mmol, 28 mg), benzaldehyde (0.2 mmol, 21.2 mg), Ir (ppy) were sequentially added to the reaction tube under a nitrogen (1 atm) atmosphere3(0.002 mmol, 1.3 mg), dimethyl sulfoxide (1 mL), under nitrogen (1 atm) for 12 h. The yield of the product 3a is 92% by nuclear magnetic phosphine spectroscopy.
Example 14 a method for preparing a thiophosphine compound by a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE016
diphenylphosphine (0.2 mmol, 37.2 mg), p-methoxythiophenol (0.2 mmol, 28 mg), benzaldehyde (0.2 mmol, 21.2 mg), Ir (ppy) were sequentially added to the reaction tube under a nitrogen (1 atm) atmosphere3(0.002 mmol, 1.3 mg), 1, 4-dioxane (1 mL), under nitrogen (1 atm) in an LED white light for 12 h. The yield of the product 3a is 92% by nuclear magnetic phosphine spectroscopy.
Example 15 a method for preparing a thiophosphine compound by a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE017
diphenylphosphine (0.2 mmol, 37.2 mg), p-methoxythiophenol (0.2 mmol, 28 mg), benzaldehyde (0.2 mmol, 21.2 mg), Ir (ppy) were sequentially added to the reaction tube under a nitrogen (1 atm) atmosphere3(0.002 mmol, 1.3 mg), toluene (1 mL) under nitrogenIrradiating for 12h under atmosphere of gas (1 atm) in LED white light lamp. The yield of the product 3a is 76% by nuclear magnetic phosphine spectroscopy.
Example 16 a method for preparing a thiophosphine compound using a visible light-promoted dehydrocoupling reaction:
Figure 359504DEST_PATH_IMAGE011
diphenylphosphine (0.2 mmol, 37.2 mg), p-methoxythiophenol (0.2 mmol, 28 mg), benzaldehyde (0.2 mmol, 21.2 mg), Ir (ppy) were sequentially added to the reaction tube under an argon (1 atm) atmosphere3(0.002 mmol, 1.3 mg), acetonitrile (1 mL) under argon (1 atm) atmosphere for 12h in an LED white light. The yield of the product 3a is 95% by nuclear magnetic phosphine spectroscopy.
Example 17 a method for preparing a thiophosphine compound using a visible light-promoted dehydrocoupling reaction:
Figure 139242DEST_PATH_IMAGE011
diphenylphosphine (0.2 mmol, 37.2 mg), p-methoxythiophenol (0.2 mmol, 28 mg), benzaldehyde (0.2 mmol, 21.2 mg), Ir (ppy) were sequentially added to the reaction tube under a nitrogen (1 atm) atmosphere3(0.002 mmol, 1.3 mg), acetonitrile (1 mL) under nitrogen (1 atm) for 12h in an LED white light. And (3) after the reaction is finished through nuclear magnetic phosphine spectrum detection, performing reduced pressure spin drying on the solvent, purifying the product by using a silica gel column chromatography, and using petroleum ether as an eluent to obtain the colorless oily thiophosphine compound 3a with the yield of 92%.
The characterization data for this compound are as follows:1H NMR (400 MHz, CDCl3) δ 7.61 – 7.55 (m, 4H), 7.39 – 7.33 (m, 8H), 6.78 (d, J = 8.8 Hz, 2H), 3.76 (s, 3H).13C NMR (100 MHz, CDCl3) δ 159.4, 137.9, 134.4, 132.8, 132.6, 129.2, 128.5, 128.5, 125.0, 114.7, 55.33. 31P NMR (162 MHz, CDCl3) δ 36.38. HRMS calcd for C19H18OPS+: 325.0810 [M+H]+, found:325.0828.
example 18 a method for preparing a thiophosphine compound using a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE018
diphenylphosphine (0.2 mmol, 37.2 mg), m-methoxythiophenol (0.2 mmol, 28 mg), benzaldehyde (0.2 mmol, 21.2 mg), Ir (ppy) were sequentially added to the reaction tube under a nitrogen (1 atm) atmosphere3(0.002 mmol, 1.3 mg), acetonitrile (1 mL) under nitrogen (1 atm) for 12h in an LED white light. Adding BH after the reaction of nuclear magnetic phosphine spectrum detection3 .THF (1.0M solution in THF) was stirred for 1h, then the solvent was spin-dried under reduced pressure, and the product was purified by silica gel column chromatography using petroleum ether as an eluent to give the thiophosphine compound 3b as a colorless oil.BH3The yield was 90%.
The characterization data for this compound are as follows:1H NMR (400 MHz, CDCl3) δ 7.76 (dd, J = 12.5, 8.3 Hz, 4H), 7.50 (d, J = 7.5 Hz, 2H), 7.46 – 7.40 (m, 4H), 7.14 – 7.03 (m, 4H), 2.20 (s, 3H).13C NMR (100 MHz, CDCl3) δ 138.8, 137.0, 133.2, 132.8, 131.7, 130.3, 123.0, 129.5, 128.7, 128.6, 126.2, 21.1.31P NMR (162 MHz, CDCl3) δ 54.07 (d, J = 76.8 Hz). 11B NMR (128 MHz, CDCl3) δ -32.47 – -39.80 (m).
example 19 a method for preparing a thiophosphine compound using a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE019
diphenylphosphine (0.2 mmol, 37.2 mg), m-methylphenylthiol (0.2 mmol, 24.8 mg), benzaldehyde (0.2 mmol, 21.2 mg), Ir (ppy) were sequentially added to the reaction tube under a nitrogen (1 atm) atmosphere3(0.002 mmol, 1.3 mg), acetonitrile (1 mL) under nitrogen (1 atm) for 12h in an LED white light. Adding BH after the reaction of nuclear magnetic phosphine spectrum detection3 .THF (1.0M solution in THF) was stirred for 1h, then the solvent was spin-dried under reduced pressure, and the product was purified by silica gel column chromatography using petroleum ether as an eluent to give the thiophosphine compound 3c as a colorless oil.BH3The yield was 94%.
The characterization data for this compound are as follows:1H NMR (400 MHz, CDCl3) δ 7.81 – 7.72 (m, 4H), 7.54 – 7.47 (m, 2H), 7.46 – 7.39 (m, 4H), 7.13 – 7.03 (m, 4H), 2.19 (s, 3H).13C NMR (100 MHz, CDCl3) δ 138.83, 137.00, 133.22, 133.19, 132.84, 132.74, 131.73, 130.33, 129.95, 129.48, 128.74, 128.63, 21.14.31P NMR (162 MHz, CDCl3) δ 54.06 (d, J = 65.2 Hz). 11B NMR (128 MHz, CDCl3) δ -33.10 – -39.93 (m).
example 20 a method for preparing a thiophosphine compound using a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE020
diphenylphosphine (0.2 mmol, 37.2 mg), o-methylthiophenol (0.2 mmol, 24.8 mg), benzaldehyde (0.2 mmol, 21.2 mg), Ir (ppy)3(0.002 mmol, 1.3 mg), acetonitrile (1 mL) under nitrogen (1 atm) for 12h in an LED white light. Adding BH after the reaction of nuclear magnetic phosphine spectrum detection3 .THF (1.0M solution in THF) was stirred for 1h, then the solvent was spin-dried under reduced pressure, and the product was purified by silica gel column chromatography using petroleum ether as an eluent to give the thiophosphine compound 3d as a colorless oil.BH3The yield was 95%.
The characterization data for this compound are as follows:1H NMR (400 MHz, CDCl3) δ 7.80 – 7.73 (m, 4H), 7.55 – 7.48 (m, 2H), 7.47 – 7.40 (m, 4H), 7.25 – 7.15 (m, 3H), 7.02 – 6.94 (m, 1H), 2.27 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 144.0, 137.4, 132.8, 131.7, 130.8, 129.8, 128.7, 126.3, 21.6. 31P NMR (162 MHz, CDCl3) δ 54.56 (d, J = 77.0 Hz). 11B NMR (128 MHz, CDCl3) δ -36.21 – -37.28 (m).
example 21 a method for preparing a thiophosphine compound using a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE021
diphenylphosphine (0.2 mmol, 37.2 mg), p-ethylthiophenol (0.2 mmol, 27.6 mg), benzaldehyde (0.2 mmol, 21.2 mg), Ir (ppy) were sequentially added to the reaction tube under a nitrogen (1 atm) atmosphere3(0.002 mmol, 1.3 mg), acetonitrile (1 mL) under nitrogen (1 atm) for 12h in an LED white light. And (3) after the reaction is finished through nuclear magnetic phosphine spectrum detection, performing reduced pressure spin drying on the solvent, purifying the product by using a silica gel column chromatography, and using petroleum ether as an eluent to obtain the colorless oily thiophosphine compound 3e with the yield of 90%.
Example 22 a method for preparing a thiophosphine compound by a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE022
diphenylphosphine (0.2 mmol, 37.2 mg), p-isopropylthiophenol (0.2 mmol, 30.4 mg), benzaldehyde (0.2 mmol, 21.2 mg), Ir (ppy)3(0.002 mmol, 1.3 mg), acetonitrile (1 mL) under nitrogen (1 atm) for 12h in an LED white light. And (3) after the reaction is finished through nuclear magnetic phosphine spectrum detection, performing reduced pressure spin drying on the solvent, purifying the product by using a silica gel column chromatography, and using petroleum ether as an eluent to obtain the colorless oily thiophosphine compound 3f with the yield of 88%.
Example 23 a method for preparing a thiophosphine compound using a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE023
diphenylphosphine (0.2 mmol, 37.2 mg), m-fluorophenylthiol (0.2 mmol, 25.6 mg), benzaldehyde (0.2 mmol, 21.2 mg), Ir (ppy) were added to the reaction tube in this order under a nitrogen (1 atm) atmosphere3(0.002 mmol, 1.3 mg), acetonitrile (1 mL) under nitrogen (1 atm) for 12h in an LED white light. After the reaction is finished by nuclear magnetic phosphine spectrum detection, the solvent is decompressed and dried, the product is purified by silica gel column chromatography, and petroleum ether is used as an eluent, so that 3g of colorless oily thiophosphine compound is obtained, and the yield is 88%.
The characterization data for this compound are as follows:1H NMR (400 MHz, CDCl3) δ 7.81 – 7.75 (m, 4H), 7.53 (td, J = 7.3, 1.6 Hz, 2H), 7.45 (td, J = 7.3, 2.8 Hz, 4H), 7.21 – 7.10 (m, 2H), 7.05 – 6.97 (m, 2H).13C NMR (100 MHz, CDCl3) δ 162.2 (d, J = 252.1 Hz), 132.7 (d, J = 10.3 Hz), 132.2 – 131.8 (m), 129.3 (d, J = 47.1 Hz), 128.9 (d, J = 10.3 Hz), 123.0 (dd, J = 22.4, 3.1 Hz), 116.8 (dd, J = 21.0, 2.4 Hz).31P NMR (162 MHz, CDCl3) δ 32.00. HRMS calcd for C18H15FPS+: 313.0611 [M+H]+, found: 313.0621.
example 24A method for preparing a thiophosphine compound by a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE024
diphenylphosphine (0.2 mmol, 37.2 mg), o-fluorophenylthiol (0.2 mmol, 25.6 mg), benzaldehyde (0.2 mmol, 21.2 mg), Ir (ppy) were added in this order to a reaction tube under a nitrogen (1 atm) atmosphere3(0.002 mmol, 1.3 mg), acetonitrile (1 mL), under nitrogen (1 atm) gasAnd irradiating for 12h under an atmosphere of an LED white light lamp. And (3) after the reaction is detected by nuclear magnetic phosphine spectrometry, decompressing and spin-drying the solvent, purifying the product by using a silica gel column chromatography, and using petroleum ether as an eluent to obtain the colorless oily thiophosphine compound for 3 hours, wherein the yield is 93 percent.
The characterization data for this compound are as follows:1H NMR (400 MHz, CDCl3) δ 7.81 (dd, J = 12.6, 8.3 Hz, 4H), 7.54 – 7.49 (m, 2H), 7.45 (dd, J = 8.2, 2.1 Hz, 5H), 7.40 – 7.28 (m, 2H), 7.04 – 6.97 (m, 2H).13C NMR (100 MHz, CDCl3) δ 163.6 (dd, J = 249.7, 3.4 Hz), 138.8 (d, J = 3.1 Hz), 132.7 (d, J = 10.3 Hz), 132.0 – 131.9 (m), 131.9 (d, J = 2.6 Hz), 129.6 (d, J = 47.4 Hz), 124.4 (dd, J = 4.0, 2.1 Hz), 116.1 (dd, J = 23.0, 2.1 Hz).31P NMR (162 MHz, CDCl3) δ34.60 HRMS calcd for C18H15FPS+:313.0611 [M+H]+, found:313.0612.
example 25 a method for preparing a thiophosphine compound by a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE025
diphenylphosphine (0.2 mmol, 37.2 mg), p-chlorothiophenol (0.2 mmol, 28.6 mg), benzaldehyde (0.2 mmol, 21.2 mg), Ir (ppy) were added to the reaction tube in this order under a nitrogen (1 atm) atmosphere3(0.002 mmol, 1.3 mg), acetonitrile (1 mL) under nitrogen (1 atm) for 12h in an LED white light. Adding BH after nuclear magnetic phosphine spectrum detection reaction3 .THF (1.0M solution in THF) was stirred for 1h, then the solvent was spin-dried under reduced pressure, and the product was purified by silica gel column chromatography using petroleum ether as an eluent to give the thiophosphine compound 3i as a colorless oil.BH3The yield was 90%.
The characterization data for this compound are as follows:1H NMR (400 MHz, CDCl3) δ 7.81 – 7.73 (m, 4H), 7.55 – 7.50 (m, 2H), 7.46 (dd, J = 8.2, 2.1 Hz, 4H), 7.23 (d, J = 1.6 Hz, 2H), 7.18 (d, J = 8.5 Hz, 2H).13C NMR (100 MHz, CDCl3) δ 137.5, 137.5, 136.2, 136.2, 132.8, 132.7, 131.9, 129.2, 128.9, 128.8.31P NMR (162 MHz, CDCl3) δ 55.09 (d, J = 56.2 Hz).11B NMR (128 MHz, CDCl3) δ -33.96 – -39.34 (m).
example 26 a method for preparing a thiophosphine compound using a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE026
diphenylphosphine (0.2 mmol, 37.2 mg), 2, 6-dimethylthiophenol (0.2 mmol, 27.6 mg), benzaldehyde (0.2 mmol, 21.2 mg), Ir (ppy)3(0.002 mmol, 1.3 mg), acetonitrile (1 mL) under nitrogen (1 atm) for 12h in an LED white light. And (3) after the reaction is detected by nuclear magnetic phosphine spectrometry, decompressing and spin-drying the solvent, purifying the product by using a silica gel column chromatography, and adopting petroleum ether as an eluent to obtain the colorless oily thiophosphine compound 3j with the yield of 94%.
The characterization data for this compound are as follows:1H NMR (400 MHz, CDCl3) δ 7.69 – 7.51 (m, 4H), 7.41 – 7.30 (m, 6H), 7.08 (d, J = 2.6 Hz, 3H), 2.40 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 143.4, 139.1, 138.9, 132.9, 132.7, 132.6, 132.4, 129.2, 128.5, 128.3, 128.18, 128.16, 23.0.31P NMR (162 MHz, CDCl3) δ 34.60. HRMS calcd for C20H20PS+: 323.1018 [M+H]+, found: 323.1016.
example 27 a method for preparing a thiophosphine compound by a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE027
diphenylphosphine (0.2 mmol, 37.2 mg), 3, 4-dichlorothiophenol (0.2 mmol, 27.6 mg), benzaldehyde (0.2 mmol, 21.2 mg), Ir (ppy)3(0.002 mmol, 1.3 mg), acetonitrile (1 mL) under nitrogen (1 atm) for 12h in an LED white light. And (3) after the reaction is detected by nuclear magnetic phosphine spectrometry, decompressing and spin-drying the solvent, purifying the product by silica gel column chromatography, and adopting petroleum ether as an eluent to obtain a colorless oily thiophosphine compound 3k with the yield of 92%.
The characterization data for this compound are as follows:1H NMR (400 MHz, CDCl3) δ 7.56 (td, J = 7.8, 3.2 Hz, 5H), 7.41 – 7.36 (m, 6H), 7.29 (d, J = 1.0 Hz, 2H).13C NMR (100 MHz, CDCl3) δ 136.7, 136.4, 135.4, 135.2, 133.1, 133.0, 132.9, 132.8, 132.7, 131.3, 131.0, 130.9, 130.6, 129.7, 128.8, 128.7.31P NMR (162 MHz, CDCl3) δ 34.27.
example 28 a method for preparing a thiophosphine compound using a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE028
diphenylphosphine (0.2 mmol, 37.2 mg), p-methoxythiophenol (0.6 mmol, 84 mg), benzaldehyde (0.2 mmol, 21.2 mg), Ir (ppy) were sequentially added to the reaction tube under a nitrogen (1 atm) atmosphere3(0.002 mmol, 1.3 mg), acetonitrile (1 mL) under nitrogen (1 atm) for 12h in an LED white light. And (3) after the reaction is detected by nuclear magnetic phosphine spectrometry, decompressing and spin-drying the solvent, purifying the product by silica gel column chromatography, and adopting petroleum ether as an eluent to obtain the colorless oily thiophosphine compound 4a with the yield of 95%.
The characterization data for this compound are as follows:1H NMR (400 MHz, CDCl3) δ 7.70 – 7.62 (m, 2H), 7.40 – 7.36 (m, 3H), 7.33 – 7.28 (m, 4H), 6.80 – 6.74 (m, 4H), 3.78 (s, 6H).13C NMR (100 MHz, CDCl3) δ 159.8, 135.7, 131.7, 129.9, 128.5, 125.3, 123.2, 123.1, 114.6, 55.3.31P NMR (162 MHz, CDCl3) δ 92.08. HRMS calcd for C20H20O2PS2 +: 387.0637 [M+H]+, found: 387.0635.
example 29A method for preparing a thiophosphine compound by a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE029
diphenylphosphine (0.2 mmol, 37.2 mg), p-methylphenylthiol (0.6 mmol, 74.4 mg), benzaldehyde (0.2 mmol, 21.2 mg), Ir (ppy) were sequentially added to the reaction tube under a nitrogen (1 atm) atmosphere3(0.002 mmol, 1.3 mg), acetonitrile (1 mL) under nitrogen (1 atm) for 12h in an LED white light. And (3) after the reaction is detected by nuclear magnetic phosphine spectrometry, decompressing and spin-drying the solvent, purifying the product by silica gel column chromatography, and adopting petroleum ether as an eluent to obtain the colorless oily thiophosphine compound 4b with the yield of 96%.
The characterization data for this compound are as follows:1H NMR (400 MHz, CDCl3) δ 7.75 – 7.68 (m, 2H), 7.39 (dd, J = 4.5, 3.3 Hz, 3H), 7.28 (d, J = 7.7 Hz, 4H), 7.04 (d, J = 8.1 Hz, 4H), 2.31 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 137.9, 137.9, 133.8, 133.7, 131.9, 131.7, 123.0, 129.7, 129.3, 129.2, 128.6, 128.5, 21.1. 31P NMR (162 MHz, CDCl3) δ 90.29. HRMS calcd for C20H20PS2 +: 355.0739 [M+H]+, found: 355.0763.
example 30 a method for preparing a thiophosphine compound by a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE030
diphenylphosphine (0.2 mmol, 37.2 mg), m-methylbenzene were added to the reaction tube in this order under a nitrogen (1 atm) atmosphereThiophenol (0.6 mmol, 74.4 mg), benzaldehyde (0.2 mmol, 21.2 mg), Ir (ppy)3(0.002 mmol, 1.3 mg), acetonitrile (1 mL) under nitrogen (1 atm) for 12h in an LED white light. And (3) after the nuclear magnetic phosphine spectrum detection reaction is finished, performing reduced pressure spin drying on the solvent, purifying the product by using a silica gel column chromatography, and using petroleum ether as an eluent to obtain the colorless oily thiophosphine compound 4c with the yield of 90%.
The characterization data for this compound are as follows:1H NMR (400 MHz, CDCl3) δ 7.74 (td, J = 6.7, 6.2, 3.1 Hz, 2H), 7.44 – 7.38 (m, 3H), 7.23 (d, J = 7.7 Hz, 2H), 7.18 (s, 2H), 7.12 (t, J = 7.6 Hz, 2H), 7.05 (d, J = 7.6 Hz, 2H), 2.25 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 138.8, 134.2, 134.1, 132.8, 132.7, 132.0, 131.8, 130.6, 130.5, 130.1, 128.8, 128.6, 128.6, 21.2. 31P NMR (162 MHz, CDCl3) δ 90.78. HRMS calcd for C20H20PS2 +: 355.0739 [M+H]+, found: 355.0739.
example 31 a method for preparing a thiophosphine compound by a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE031
diphenylphosphine (0.2 mmol, 37.2 mg), o-methylthiophenol (0.6 mmol, 74.4 mg), benzaldehyde (0.2 mmol, 21.2 mg), Ir (ppy)3(0.002 mmol, 1.3 mg), acetonitrile (1 mL) under nitrogen (1 atm) for 12h in an LED white light. And (3) after the reaction is detected by nuclear magnetic phosphine spectrometry, decompressing and spin-drying the solvent, purifying the product by silica gel column chromatography, and adopting petroleum ether as an eluent to obtain the colorless oily thiophosphine compound 4d with the yield of 89%.
The characterization data for this compound are as follows:1H NMR (400 MHz, CDCl3) δ 7.83 – 7.76 (m, 2H), 7.45 – 7.39 (m, 5H), 7.16 (d, J = 3.9 Hz, 4H), 7.09 – 7.02 (m, 2H), 2.35 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 141.2, 134.8, 134.7, 132.0, 131.7, 130.4, 130.1, 128.6, 128.6, 128.1, 126.5, 21.3.31P NMR (162 MHz, CDCl3) δ 86.27.
example 32 a method for preparing a thiophosphine compound using a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE032
diphenylphosphine (0.2 mmol, 37.2 mg), p-ethylthiophenol (0.6 mmol, 82.8 mg), benzaldehyde (0.2 mmol, 21.2 mg), Ir (ppy)3(0.002 mmol, 1.3 mg), acetonitrile (1 mL) under nitrogen (1 atm) for 12h in an LED white light. And (3) after the reaction is detected by nuclear magnetic phosphine spectrometry, decompressing and spin-drying the solvent, purifying the product by silica gel column chromatography, and adopting petroleum ether as an eluent to obtain the colorless oily thiophosphine compound 4e with the yield of 92%.
The characterization data for this compound are as follows:1H NMR (400 MHz, Chloroform-d) δ 7.76 – 7.68 (m, 2H), 7.42 – 7.35 (m, 3H), 7.30 (d, J = 7.6 Hz, 4H), 7.06 (d, J = 8.1 Hz, 4H), 2.60 (q, J = 7.6 Hz, 4H), 1.21 (t, J = 7.6 Hz, 6H).13C NMR (101 MHz, CDCl3) δ 144.2, 133.8, 133.8, 132.0, 131.7, 130.0, 129.6, 129.5, 128.6, 28.5, 15.5.31P NMR (162 MHz, CDCl3) δ 90.87. HRMS calcd for C22H24PS2 +: 383.1052 [M+H]+, found: 383.1052.
example 33 a method for preparing a thiophosphine compound using a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE033
diphenylphosphine (0.2 m) was added to the reaction tube in sequence under nitrogen (1 atm) atmospheremol, 37.2 mg), p-isopropylthiophenol (0.6 mmol, 91.2 mg), benzaldehyde (0.2 mmol, 21.2 mg), Ir (ppy)3(0.002 mmol, 1.3 mg), acetonitrile (1 mL) under nitrogen (1 atm) for 12h in an LED white light. And (3) after the nuclear magnetic phosphine spectrum detection reaction is finished, performing reduced pressure spin drying on the solvent, purifying the product by using a silica gel column chromatography, and using petroleum ether as an eluent to obtain the colorless oily thiophosphine compound 4f with the yield of 88%.
The characterization data for this compound are as follows:1H NMR (400 MHz, CDCl3) δ 7.75 – 7.69 (m, 2H), 7.42 – 7.36 (m, 3H), 7.30 (d, J = 7.7 Hz, 4H), 7.08 (d, J = 8.2 Hz, 4H), 2.86 (p, J = 6.9 Hz, 2H), 1.22 (d, J = 6.9 Hz, 12H).13C NMR (100 MHz, CDCl3) δ 148.8, 133.8, 133.7, 131.9, 131.7, 130.0, 129.8, 129.6, 128.6, 128.5, 127.1, 33.8, 23.9.31P NMR (162 MHz, CDCl3) δ 91.31. HRMS calcd for C24H28PS2 +: 411.1365 [M+H]+, found: 411.1363.
example 34 a method for preparing a thiophosphine compound using a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE034
diphenylphosphine (0.2 mmol, 37.2 mg), p-fluorophenylthiol (0.6 mmol, 76.8 mg), benzaldehyde (0.2 mmol, 21.2 mg), Ir (ppy)3(0.002 mmol, 1.3 mg), acetonitrile (1 mL) under nitrogen (1 atm) for 12h in an LED white light. After the reaction is finished by nuclear magnetic phosphine spectrum detection, the solvent is decompressed and dried, the product is purified by silica gel column chromatography, and petroleum ether is used as an eluent, so that 4g of colorless oily thiophosphine compound is obtained, and the yield is 86%.
Example 35 a method for preparing a thiophosphine compound using a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE035
diphenylphosphine (0.2 mmol, 37.2 mg), m-fluorophenylthiol (0.6 mmol, 76.8 mg), benzaldehyde (0.2 mmol, 21.2 mg), Ir (ppy)3(0.002 mmol, 1.3 mg), acetonitrile (1 mL) under nitrogen (1 atm) for 12h in an LED white light. And (3) after the reaction is detected by nuclear magnetic phosphine spectrometry, decompressing and spin-drying the solvent, purifying the product by using a silica gel column chromatography, and using petroleum ether as an eluent to obtain the colorless oily thiophosphine compound for 4 hours with the yield of 93 percent.
The characterization data for this compound are as follows:1H NMR (400 MHz, CDCl3) δ 7.76 – 7.69 (m, 2H), 7.45 – 7.40 (m, 3H), 7.24 – 7.16 (m, 4H), 7.11 (dd, J = 10.5, 2.6 Hz, 2H), 6.99 – 6.91 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 162.5 (d, J = 249.5 Hz), 131.84 (d, J = 23.2 Hz), 130.6, 130.2 (d, J = 8.4 Hz), 129.0 (dd, J = 5.7, 3.1 Hz), 128.8 (d, J = 6.7 Hz), 120.2 (dd, J = 22.6, 6.0 Hz), 115.2 (d, J = 1.7 Hz), 114.9 (d, J = 1.7 Hz). 31P NMR (162 MHz, CDCl3) δ 90.15.
example 36A method for preparing a thiophosphine compound by a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE036
diphenylphosphine (0.2 mmol, 37.2 mg), o-fluorophenylthiol (0.6 mmol, 76.8 mg), benzaldehyde (0.2 mmol, 21.2 mg), Ir (ppy) were added successively to a reaction tube under a nitrogen (1 atm) atmosphere3(0.002 mmol, 1.3 mg), acetonitrile (1 mL) under nitrogen (1 atm) for 12h in an LED white light. And (3) after the nuclear magnetic phosphine spectrum detection reaction is finished, performing reduced pressure spin drying on the solvent, purifying the product by using a silica gel column chromatography, and using petroleum ether as an eluent to obtain the colorless oily thiophosphine compound 4i with the yield of 90%.
The characterization data for this compound are as follows:1H NMR (400 MHz, CDCl3) δ 7.79 (td, J = 7.2, 3.1 Hz, 2H), 7.50 – 7.44 (m, 2H), 7.42 (dd, J = 4.4, 2.0 Hz, 3H), 7.28 – 7.22 (m, 2H), 7.06 – 6.99 (m, 4H).13C NMR (100 MHz, CDCl3) δ 162.5 (dd, J = 247.4, 2.3 Hz), 136.1 (d, J = 7.1 Hz), 131.8 (d, J = 22.9 Hz), 130.4, 130.2 (dd, J = 7.8, 1.8 Hz), 128.7 (d, J = 6.5 Hz), 124.5 (d, J = 4.0 Hz), 116.0 (d, J = 23.0 Hz).31P NMR (162 MHz, CDCl3) δ 91.20. HRMS calcd for C18H14F2P+: 363.0237 [M+H]+, found: 363.0234.
example 37 a method for preparing a thiophosphine compound using a visible light-promoted dehydrocoupling reaction:
Figure DEST_PATH_IMAGE037
diphenylphosphine (0.2 mmol, 37.2 mg), p-chlorothiophenol (0.6 mmol, 76.8 mg), benzaldehyde (0.2 mmol, 21.2 mg), Ir (ppy)3(0.002 mmol, 1.3 mg), acetonitrile (1 mL) under nitrogen (1 atm) for 12h in an LED white light. And (3) after the nuclear magnetic phosphine spectrum detection reaction is finished, performing reduced pressure spin drying on the solvent, purifying the product by using a silica gel column chromatography, and using petroleum ether as an eluent to obtain a colorless oily thiophosphine compound 4j with the yield of 90%.
The characterization data for this compound are as follows:1H NMR (400 MHz, CDCl3) δ 7.72 – 7.63 (m, 2H), 7.46 – 7.38 (m, 3H), 7.34 – 7.26 (m, 4H), 7.20 (d, J = 8.5 Hz, 4H).13C NMR (100 MHz, CDCl3) δ 134.9, 134.8, 134.4, 134.4, 131.9, 131.7, 131.2, 131.0, 130.5, 129.2, 128.8, 128.7.31P NMR (162 MHz, CDCl3) δ 91.38.
the foregoing embodiments have described the general principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the present invention, and that various changes and modifications may be made without departing from the scope of the principles of the present invention, and the invention is intended to be covered by the appended claims.

Claims (2)

1. A method for preparing a thiophosphine compound by a dehydrogenation coupling reaction promoted by visible light is characterized by comprising the following steps: dissolving an organic phosphine compound and a visible light photosensitizer into a solvent, then adding a thiophenol compound and a weak oxidant, reacting for 12 hours at normal temperature under the irradiation of LED white light in a protective atmosphere, and then separating to obtain the thiophosphine compound, wherein the structural formula of the thiophosphine compound is shown in the specification
Figure 333737DEST_PATH_IMAGE001
(ii) a The feeding molar ratio of the organic phosphine compound to the visible light photosensitizer is 1: 0.01; the feeding molar ratio of the organic phosphine compound to the thiophenol compound is 1: 1 or 1: 3; the organophosphine compound is aryl-substituted primary and secondary phosphonous compounds, and the structural formula of the organophosphine compound is as follows: r1R2PH, wherein R2= H or R1，R1Is an aryl substituent; the visible light photosensitizer is one of tris (2-phenylpyridine) iridium, tris (2, 2' -bipyridine) ruthenium chloride (II) hexahydrate, eosin Y, eosin B and Bengal red; the solvent is one of acetonitrile, absolute ethyl alcohol, tetrahydrofuran, 1, 4-dioxane, toluene, dichloromethane and dimethyl sulfoxide; the thiophenol compound is aryl thiophenol with a structural formula
Figure DEST_PATH_IMAGE002
Wherein R is3Is one of methoxy, methyl, ethyl, isopropyl and fluorine and chlorine substituent groups, the substituent group is mono-substituted or di-substituted, and the position of the substituent group is any position on a benzene ring; the weak oxidant is one of benzophenone, imine, styrene, azobenzene and benzaldehydeAnd (4) seed preparation.
2. The process for preparing a thiophosphine compound through a visible light-promoted dehydrocoupling reaction according to claim 1, wherein: the protective atmosphere refers to nitrogen or argon.
CN202010263678.4A 2020-04-07 2020-04-07 Method for preparing thiophosphine compound through visible light-promoted dehydrogenation coupling reaction Active CN111377963B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010263678.4A CN111377963B (en) 2020-04-07 2020-04-07 Method for preparing thiophosphine compound through visible light-promoted dehydrogenation coupling reaction

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010263678.4A CN111377963B (en) 2020-04-07 2020-04-07 Method for preparing thiophosphine compound through visible light-promoted dehydrogenation coupling reaction

Publications (2)

Publication Number Publication Date
CN111377963A CN111377963A (en) 2020-07-07
CN111377963B true CN111377963B (en) 2021-09-03

Family

ID=71215631

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010263678.4A Active CN111377963B (en) 2020-04-07 2020-04-07 Method for preparing thiophosphine compound through visible light-promoted dehydrogenation coupling reaction

Country Status (1)

Country Link
CN (1) CN111377963B (en)

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108440291B (en) * 2018-03-26 2020-08-28 南京工业大学 Method for dehydrogenation and self-coupling of 1, 3-dicarbonyl compound under catalysis of visible light

Also Published As

Publication number Publication date
CN111377963A (en) 2020-07-07

Similar Documents

Publication Publication Date Title
Wang et al. Multicomponent Self‐Assembly of Metallo‐Supramolecular Macrocycles and Cages through Dynamic Heteroleptic Terpyridine Complexation
KR20170084048A (en) Method for preparing deuterated aromatic compounds
CN108164475B (en) Method for catalytic synthesis of difluoromethyl-substituted linear aryl hetero-ketone
Redon et al. Metal-Free ipso-Selenocyanation of Arylboronic Acids Using Malononitrile and Selenium Dioxide
Block et al. 1, 3-Dithietane
Klein et al. Convenient synthesis of tridentate 2, 6-di (pyrazol-1-yl)-4-carboxypyridine and tetradentate 6, 6′-di (pyrazol-1-yl)-4, 4′-dicarboxy-2, 2′-bipyridine ligands
Luo et al. Synthesis of heteroleptic phosphine–copper (I) complexes: Fluorescence sensing and catalytic properties
Hafedh et al. Synthesis and chiroptical properties of organometallic complexes of helicenic N‐heterocyclic carbenes
CN111377963B (en) Method for preparing thiophosphine compound through visible light-promoted dehydrogenation coupling reaction
Bruce et al. Synthesis of a linear bis-porphyrin with a Ru (phen) 2 2+-complexed 2, 2′-bipyridine spacer
Fleckenstein et al. Redox‐Switchable Phase Tags–Facile Mitsunobu Reactions using Ferrocenyl‐Tagged Triphenylphosphine
Vaheesar et al. Formation of phosphorus heterocycles using a cationic electrophilic phosphinidene complex
CN112778272B (en) 2, 2' -biazaaryl ring bidentate ligand and preparation method and application thereof
CN112898202B (en) Heterocyclyl cyclopropane compound and synthesis method thereof
CN110540553B (en) Phosphorus-containing quinoline compound and preparation method and application thereof
Zavozin et al. Novel di-and tetra (pyrazolyl) bipyridine ligands and their Co (II)-complexes for electrochemical applications
Kerrigan et al. Salen ligands derived from trans-1, 2-dimethyl-1, 2-cyclohexanediamine: preparation and application in oxo-chromium salen mediated asymmetric epoxidation of alkenes
CN110386903B (en) Tetrazine-containing oligomeric phenylene acetylene compound and preparation method thereof
Wang et al. Synthesis of a phosphapyracene via metal-mediated cyclization: structural and reactivity effects of acenaphthene precursors
Tsai et al. Reactions of Ruthenium Complexes Containing Pentatetraenylidene Ligand
Sivaramakrishna et al. Synthesis and structural aspects of M-allyl (M= Ir, Rh) complexes
Vincent et al. Synthesis and redox properties of mono-, di-and tri-metallic platinum-ethynyl complexes based on the trans-Pt (C6H4N {C6H4OCH3-4} 2)(CCR)(PPh3) 2 motif
Deng et al. Unusual C–O bond cleavage of aromatic ethers in ruthenium complexes bearing a 2-alkoxypyridyl fragment
CN116135867A (en) Method for preparing pyridine ferrocene compound
CN118324806A (en) Diaryl alkyl phosphine and preparation method and application 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
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20211210

Address after: 730000 No. 18 Tianshui Middle Road, Chengguan District, Gansu, Lanzhou

Patentee after: Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences

Address before: 730000 No. 18 Tianshui Middle Road, Chengguan District, Gansu, Lanzhou

Patentee before: Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences

Patentee before: Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Suzhou Research Institute

TR01 Transfer of patent right