CN114805436B - Organic phosphine oxide compound and synthesis method thereof - Google Patents
Organic phosphine oxide compound and synthesis method thereof Download PDFInfo
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- CN114805436B CN114805436B CN202210586107.3A CN202210586107A CN114805436B CN 114805436 B CN114805436 B CN 114805436B CN 202210586107 A CN202210586107 A CN 202210586107A CN 114805436 B CN114805436 B CN 114805436B
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- -1 phosphine oxide compound Chemical class 0.000 title claims abstract description 25
- 238000001308 synthesis method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 6
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 3
- 238000010189 synthetic method Methods 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 10
- 239000000654 additive Substances 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 abstract 1
- 229910000024 caesium carbonate Inorganic materials 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 11
- 238000004440 column chromatography Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 8
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- VWBYXJRDIQCSLW-UHFFFAOYSA-N O=[P](c1ccccc1)c1ccccc1 Chemical compound O=[P](c1ccccc1)c1ccccc1 VWBYXJRDIQCSLW-UHFFFAOYSA-N 0.000 description 6
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 3
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PTHGDVCPCZKZKR-UHFFFAOYSA-N (4-chlorophenyl)methanol Chemical compound OCC1=CC=C(Cl)C=C1 PTHGDVCPCZKZKR-UHFFFAOYSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- KMTDMTZBNYGUNX-UHFFFAOYSA-N 4-methylbenzyl alcohol Chemical compound CC1=CC=C(CO)C=C1 KMTDMTZBNYGUNX-UHFFFAOYSA-N 0.000 description 1
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- RREGWFNURZJKNB-UHFFFAOYSA-N bis(4-methoxyphenyl)-oxophosphanium Chemical compound C1=CC(OC)=CC=C1[P+](=O)C1=CC=C(OC)C=C1 RREGWFNURZJKNB-UHFFFAOYSA-N 0.000 description 1
- ZHIPXAFNKGZMSC-UHFFFAOYSA-N bis(4-methylphenyl)-oxophosphanium Chemical compound C1=CC(C)=CC=C1[P+](=O)C1=CC=C(C)C=C1 ZHIPXAFNKGZMSC-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- FVEINXLJOJPHLH-UHFFFAOYSA-N p-tert-Butylbenzyl alcohol Chemical compound CC(C)(C)C1=CC=C(CO)C=C1 FVEINXLJOJPHLH-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5333—Arylalkane phosphine oxides or thioxides
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an organic phosphine oxide compound and a synthesis method thereof, wherein an alcohol compound and a P (O) -H compound are used as reaction raw materials, 5mol percent of ferric acetylacetonate is used as a catalyst, 1 equivalent of cesium carbonate and cyclohexane is used as a solvent, and the organic phosphine oxide compound is obtained by heating to 130 ℃ in a nitrogen atmosphere, and effectively reacting 24 and H in a higher yield. The method has the advantages of high yield, simple operation, less additives, low cost, no pollution and the like, and has certain feasibility for realizing the industrialized production of the method.
Description
[ field of technology ]
The invention belongs to the field of transition metal catalytic organic synthesis, and particularly relates to an organic phosphine oxide compound and a synthesis method thereof.
[ background Art ]
The organic phosphine oxide compound is widely applied to pesticides, flame retardants, surfactants and the like, and the organic phosphine oxide group is an important component in medicine molecules, pesticide molecules and material structural molecules. The organic phosphine oxide compound can be reduced into a trivalent phosphine compound, and can be used as a ligand in reactions such as asymmetric catalysis, transition metal catalysis and the like. Therefore, the synthesis of organic phosphine oxide compounds has been the focus of attention of researchers.
Traditional methods for synthesizing organic phosphine oxides mainly rely on the conversion of organic halides, such as Michaelis-Arbusov reaction, nucleophilic substitution reaction of organolithium reagents or Grignard reagents with P (O) -X compounds, or cross-coupling of transition metal-catalyzed halides with P (O) -H compounds, and the like. However, these chemical reactions are often harsh in terms of reaction conditions, the raw materials are sensitive to water and air, unstable and highly toxic, and produce metered by-products with low atomic utilization and severe pollution.
Alcohol compounds widely exist in nature, are cheap and easy to obtain, have low toxicity, and are widely used as ideal raw materials in organic synthesis. In 2019, xu Keti groups invented alcohol as alkylating reagent, and under the catalysis of halosilane, the method of preparing trisubstituted phosphine oxide compound by reacting P (O) -H compound with alcohol is realized (in silence Ma Xiantao Yan Ran Xu Qing. A synthetic method of trisubstituted phosphine oxide compound. China. 2019. CN 109678901A). Although the method avoids using organic halide as raw material, halosilane sensitive to air and water is used as catalyst, and the dosage of partial reaction catalyst is larger. The low-cost metallic iron has abundant reserves on the earth, low price and quite high biocompatibility. Therefore, the method for synthesizing the organic phosphine oxide compound takes benzyl alcohol and P (O) -H compound as raw materials, and synthesizes the organic phosphine oxide compound through ferric acetylacetonate catalysis, and the method has the advantages of no need of special equipment requirements, simple operation, few additives, high yield and wide application range, and has certain industrial application value. At present, no published literature and patent for synthesizing organic phosphine oxide compounds by catalyzing ferric acetylacetonate exist at home and abroad.
[ invention ]
The invention aims to provide a method for efficiently synthesizing an organic phosphine oxide compound by taking ferric acetylacetonate as a catalyst and taking an alcohol compound and a P (O) -H compound as raw materials.
In order to achieve the above purpose, the present invention proposes the following technical scheme:
an organic phosphine oxide compound and a synthesis method thereof, wherein the organic phosphine oxide compound I has the following structural general formula:
wherein said R is 1 Phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl, 4-tert-butylphenyl, benzyl, furan; r is R 2 Phenyl, 4-methylphenyl, 4-methoxyphenyl. Wherein the synthesis method of the compound I is that,the method is characterized in that benzyl alcohol is used as a raw material, a P (O) -H compound III is used as a raw material, cyclohexane is used as a solvent, 5mol percent of ferric acetylacetonate is used as a catalyst, the reaction is effectively carried out at 130 ℃ for 24H, and the organic phosphine oxide compound I is obtained in high yield.
In the above synthetic method, the structural formulas of the raw material alcohols II and the P (O) -H compound III are as follows:
wherein said R is 1 Phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl, 4-tert-butylphenyl, benzyl, furan; r is R 2 Phenyl, 4-methylphenyl, 4-methoxyphenyl.
In the synthesis method, the iron catalyst is 5mol%, the cyclohexane is a solvent, the reaction time is 24h, and the reaction temperature is 130 ℃.
The synthesis method of the organic phosphine oxide compounds provided by the invention is a green and efficient synthesis way, and has the advantages that: the yield of the target product is high, the additive is few, the reaction operation is simple, and the method is green and pollution-free.
[ description of the drawings ]
The drawing shows a route pattern for preparing the organic phosphine oxide compound.
[ detailed description ] of the invention
The invention provides a synthesis method of an organic phosphine oxide compound, please refer to the accompanying drawings: alcohol compounds and P (O) -H compounds are used as raw materials, cyclohexane is used as a solvent, 5mol percent of ferric acetylacetonate is used as a catalyst, the mixture is placed into a reaction vessel, the mixture is heated to 130 ℃ in a nitrogen atmosphere, the reaction is carried out for 24 hours, and the corresponding target product is obtained through column chromatography separation and purification after the reaction is completed.
The invention is further illustrated below in connection with specific examples of preparation:
preparation example 1
To a 25 mL tube reactor was added 0.2 mmol of benzyl alcohol, 0.4 mmol of diphenylphosphorus oxide, and ethyl acetateIron acetylacetonate 5mol%, 1 mL cyclohexane, and heated to 130℃under nitrogen atmosphere to react 24 h. After the reaction is finished, the product is separated and purified by column chromatography, and the separation yield is 96%. 1 H NMR (400 MHz, CDCl 3 ): δ 7.64-7.59 (m, 4H), 7.46-7.41 (m, 2H), 7.38-7.34 (m, 4H), 7.14-7.09 (m, 3H), 7.05-7.02 (m, 2H), 3.58 (d, J= 14.0 Hz, 2H). 13 C NMR (100 MHz, CDCl 3 ): δ 132.8, 131.8 (d, J C-P = 2.6 Hz), 131.1 (d, J C-P = 9.1 Hz), 130.1 (d, J C-P = 5.2 Hz), 128.5, 128.4, 128.3 (d, J C-P = 2.4 Hz), 126.7 (d, J C-P =2.8 Hz), 38.1 (d, J C-P = 66.1 Hz). 31 P NMR (162 MHz, CDCl 3 ): δ29.4.
Preparation example 2
To a 25 mL tubular reactor was added 0.2 mmol of 4-methylbenzyl alcohol, 0.4 mmol of diphenyl phosphorus oxide, 5mol% of iron acetylacetonate, 1 mL cyclohexane, and the mixture was heated to 130℃under nitrogen atmosphere to react 24 h. After the reaction is finished, the product is separated and purified by column chromatography, and the separation yield is 95%. 1 H NMR (400 MHz, CDCl 3 ): δ 7.72-7.67 (m, 4H), 7.50-7.47 (m, 2H), 7.44-7.40 (m, 4H), 6.99 (s, 4H), 3.61 (d, J = 13.6 Hz, 2H), 2.25 (d, J = 1.6 Hz, 3H). 31 C NMR (100 MHz, CDCl 3 ) δ 136.2 (d, J C-P = 3.0 Hz), 132.3 (d, J C-P = 98.0 Hz), 131.6 (d, J C-P = 2.5 Hz), 131.1 (d, J C-P = 9.1 Hz), 129.9 (d, J C-P = 5.1 Hz), 129.0 (d, J C-P = 2.4 Hz), 128.4 (d, J C-P = 11.7 Hz), 127.8 (d, J C-P = 8.0 Hz), 37.5 (d, J C-P = 66.5 Hz), 20.9. 31 P NMR (162 MHz, CDCl 3 ): δ 29.4.
Preparation example 3
Into a 25 mL tubular reactor was charged 0.2 mmol of 4-methoxybenzyl alcohol, 0.4 mmol of diphenylphosphorus oxide, and acetylacetone was addedIron 5mol%, 1 mL cyclohexane, and heating to 130 ℃ under nitrogen atmosphere to react 24 h. After the reaction is finished, the product is separated and purified by column chromatography, and the separation yield is 85%. 1 H NMR (400 MHz, CDCl 3 ): δ 7.71-7.66 (m, 4H), 7.51-7.48 (m, 2H), 7.45-7.40 (m, 4H), 7.02-7.00 (m, 2H), 6.72 (d, J = 13.2 Hz, 2H), 3.73 (s, 3H), 3.59 (d, J = 13.2 Hz, 2H). 31 C NMR (100 MHz, CDCl 3 ): δ158.4 (d, J C-P = 2.7 Hz), 132.2 (d, J C-P = 98.0 Hz), 131.7 (d, J C-P = 2.4 Hz), 131.1 (d, J C-P = 9.0 Hz), 131.0 (d, J C-P = 3.1 Hz), 128.4 (d, J C-P = 11.6 Hz), 122.8 (d, J C-P = 8.0 Hz), 113.8 (d, J C-P = 2.1 Hz), 55.1, 37.0 (d, J C-P = 67.1 Hz). 31 P NMR (162 MHz, CDCl 3 ): δ 29.6.
Preparation example 4
To a 25 mL tubular reactor was added 0.2 mmol of 4-chlorobenzyl alcohol, 0.4 mmol of diphenylphosphorus oxide, 5mol% of iron acetylacetonate, 1 mL cyclohexane, and the mixture was heated to 130℃under nitrogen atmosphere to react 24 h. After the reaction is finished, the product is separated and purified by column chromatography, and the separation yield is 72%. 1 H NMR (400 MHz, CDCl 3 ): δ 7.71-7.66 (m, 4H)， 7.54-7.45 (m, 2H), 7.16-7.14 (m, 2H), 7.05-7.02 (m, 2H), 3.63-3.59 (m, 2H), 3.61 (d, J = 13.2 Hz, 2H). 31 C NMR (100 MHz, CDCl 3 ): δ 132.8 (d, J C-P = 3.5 Hz), 132.0 (d, J C-P = 98.8 Hz), 131.9 (d, J C-P = 2.5 Hz), 131.3 (d, J C-P = 5.1 Hz), 131.1 (d, J C-P = 9.1), 129.7 (d, J C-P = 8.0 Hz), 128.6 (d, J C-P = 12.0 Hz), 128.5 (d, J C-P = 3.0 Hz), 37.4 (d, J C-P = 65.8 Hz). 31 P NMR (162 MHz, CDCl 3 ): δ29.2
Preparation example 5
To a 25 mL tubular reactor was added 0.2 mmol of 4-t-butylbenzyl alcohol, 0.4 mmol of diphenylphosphine oxide, 5mol% of iron acetylacetonate, 1 mL cyclohexane, and the mixture was heated to 130℃under nitrogen atmosphere to react 24 h. After the reaction, the product was purified by column chromatography in a yield of 91%. 1 H NMR (400 MHz, CDCl 3 ): δ 7.71-7.67 (m, 4H), 7.50-7.46 (m, 2H), 7.43-7.39 (m, 4H), 7.20-7.18 (m, 2H), 7.04-7.01 (m, 2H), 3.62 (d, J = 13.6 Hz, 2H), 1.24 (s, 9H). 31 C NMR (100 MHz, CDCl 3 ): δ149.5 (d, J C-P = 3.2 Hz), 132.4 (d, J C-P = 98.0 Hz), 131.6 (d, J C-P = 2.6 Hz), 131.1 (d, J C-P = 9.1 Hz), 129.7 (d, J C-P = 5.3 Hz), 128.3 (d, J C-P = 11.6 Hz), 127.8 (d, J C-P = 8.1 Hz), 125.2 (d, J C-P = 2.6 Hz), 37.4 (d, J C-P = 66.6 Hz), 34.2, 37.2. 31 P NMR (162 MHz, CDCl 3 ): δ 29.6.
Preparation example 6
To a 25 mL tubular reactor was added 0.2 mmol of phenethyl alcohol, 0.4 mmol of diphenyl phosphorus oxide, 5mol% of iron acetylacetonate, 1 mL cyclohexane, and the mixture was heated to 130℃under nitrogen atmosphere to react 24 h. After the reaction, the product was purified by column chromatography in 67% yield. 1 H NMR (400 MHz, CDCl 3 ): δ 7.79-7.74 (m, 4H), 7.53-7.44 (m, 6H), 7.27-7.23 (m, 2H), 7.18-7.14 (m, 3H), 2.96-2.90 (m, 2H), 2.61-2.54 (m, 2H). 31 C NMR (100 MHz, CDCl 3 ): δ141.0 (d, J C-P = 15.2 Hz), 132.6 (d, J C-P = 97.9 Hz), 131.7 (d, J C-P = 2.5 Hz), 130.6 (d, J C-P = 9.3 Hz), 128.7, 128.5 (d, J C-P = 7.0 Hz), 127.9, 126.2, 31.2 (d, J C-P = 69.4 Hz), 27.4 (d, J C-P = 2.9 Hz). 31 P NMR (162 MHz, CDCl 3 ): δ 29.6.
Preparation example 7
To a 25 mL tubular reactor was added 0.2 mmol of 2-furanmethanol, 0.4 mmol of diphenyl phosphorus oxide, 5mol% of iron acetylacetonate, 1 mL cyclohexane, and the mixture was heated to 130℃under nitrogen atmosphere to react 24 h. After the reaction is finished, the product is separated and purified by column chromatography, and the separation yield is 45%. 1 H NMR (400 MHz, CDCl 3 ): δ 7.73-7.68 (m, 4H), 7.54-7.43 (m, 6H), 7.23 (s, 1H), 6.23-6.07 (m, 2H), 3.76 (d, J = 14.0 Hz, 2H). 31 C NMR (100 MHz, CDCl 3 ): δ145.3 (d, J C-P = 7.8 Hz), 141.9 (d, J C-P = 2.7 Hz), 132.1 (d, J C-P = 14.4 Hz), 132.0 (d, J C-P = 99.9Hz), 131.1 (d, J C-P = 9.4 Hz), 128.6 (d, J C-P = 11.8 Hz), 110.9 (d, J C-P = 2.4 Hz), 109.1 (d, J C-P = 5.8 Hz), 37.4 (d, J C-P = 69.0 Hz). 31 P NMR (162 MHz, CDCl 3 ): δ 28.2.
Preparation example 8
To a 25 mL tubular reactor was added 0.2 mmol of benzyl alcohol, 0.4 mmol of bis (4-methylphenyl) phosphine oxide, 5mol% of iron acetylacetonate, 1 mL cyclohexane, and the mixture was heated to 130℃under nitrogen atmosphere to react 24 h. After the reaction is finished, the product is separated and purified by column chromatography, and the separation yield is 90%. 1 H NMR (400 MHz, CDCl 3 ): δ7.58-7.53 (m, 4H), 7.23-7.21 (m, 4H), 7.18-7.16 (m, 3H), 7.11-7.09 (m, 2H), 3.61 (d, J C-P = 13.6 Hz, 2H), 2.37 (s, 6H). 31 C NMR (100 MHz, CDCl 3 ):δ 142.1 (d, J C-P = 2.6 Hz), 132.0 (d, J C-P = 10.1 Hz), 131.1 (d, J C-P = 9.4 Hz), 130.1 (d, J C-P = 5.2 Hz), 129.5 (d, J C-P = 12.8 Hz), 129.1 (d, J C-P = 100.7 Hz), 128.2 (d, J C-P = 2.2 Hz), 126.6 (d, J C-P = 2.8 Hz), 38.1 (d, J C-P = 66.3 Hz), 21.5 (d, J C-P = 0.9 Hz). 31 P NMR (162 MHz, CDCl 3 ): δ 30.0.
Preparation example 9
To a 25 mL tubular reactor was added 0.2 mmol of benzyl alcohol, 0.4 mmol of bis (4-methoxyphenyl) phosphine oxide, 5mol% of iron acetylacetonate, 1 mL cyclohexane, and the mixture was heated to 130℃under nitrogen atmosphere to react 24 h. After the reaction is finished, the product is separated and purified by column chromatography, and the separation yield is 85%. 1 H NMR (400 MHz, CDCl 3 ): δ 7.60-7.55 (m, 4H), 7.17-16 (m, 5H), 7.17-7.09 (m, 4H), 3.79 (s, 6H), 3.58 (d, J = 14.0 Hz, 2H). 31 C NMR (100 MHz, CDCl 3 ):δ 162.2 (d, J C-P = 2.7 Hz), 133.0 (d, J C-P = 10.4 Hz), 131.6 (d, J C-P = 7.8 Hz), 130.1 (d, J C-P = 5.2 Hz), 128.3 (d, J C-P = 2.3 Hz), 126.6 (d, J C-P = 2.8 Hz), 123.7 (d, J C-P = 104.9 Hz), 113.9 (d, J C-P = 12.6 Hz), 55.3, 38.6 (d, J C-P = 66.9 Hz). 31 P NMR (162 MHz, CDCl 3 ): δ 29.6.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (1)
1. The synthetic method of the organic phosphine oxide compound comprises the following steps of:
wherein said R is 1 Phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl, 4-tert-butylphenyl, benzyl, furan; r is R 2 Phenyl, 4-methylphenyl, 4-methoxyphenyl; the synthesis method of the compound I is characterized in that alcohol compounds II and P (O) -H compounds III are used as raw materials, cyclohexane is used as a solvent, 5mol% of ferric acetylacetonate is used as a catalyst, the reaction is effectively carried out for 24 hours at 130 ℃ in a nitrogen environment, and the organic phosphine oxide compound I is obtained in high yield.
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| CN1224019A (en) * | 1997-12-23 | 1999-07-28 | 弗·哈夫曼-拉罗切有限公司 | Process for manufacture of bis (phosphine oxide)- and bis (phosphonate) -compounds |
| EP2281860A1 (en) * | 2009-08-03 | 2011-02-09 | Morgan Adhesives Company | Adhesive compositions for easy application and improved durability |
| CN110143982A (en) * | 2019-07-05 | 2019-08-20 | 湖南第一师范学院 | A kind of synthetic method of diaryl benzyl phosphine oxide compound |
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| EP2281860A1 (en) * | 2009-08-03 | 2011-02-09 | Morgan Adhesives Company | Adhesive compositions for easy application and improved durability |
| CN110143982A (en) * | 2019-07-05 | 2019-08-20 | 湖南第一师范学院 | A kind of synthetic method of diaryl benzyl phosphine oxide compound |
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