CN107021982A - The synthetic method of three substitution phosphine oxide compounds or three two phosphine oxide compounds of substitution - Google Patents
The synthetic method of three substitution phosphine oxide compounds or three two phosphine oxide compounds of substitution Download PDFInfo
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- CN107021982A CN107021982A CN201611004785.5A CN201611004785A CN107021982A CN 107021982 A CN107021982 A CN 107021982A CN 201611004785 A CN201611004785 A CN 201611004785A CN 107021982 A CN107021982 A CN 107021982A
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- phosphine oxide
- phosphine
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- 238000006467 substitution reaction Methods 0.000 title claims abstract description 51
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000010189 synthetic method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- -1 phosphine oxide compound Chemical class 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 8
- 239000011630 iodine Substances 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 230000002152 alkylating effect Effects 0.000 claims abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 74
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 40
- 125000000524 functional group Chemical group 0.000 claims description 15
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 18
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 231100000053 low toxicity Toxicity 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000011160 research Methods 0.000 abstract description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 abstract 1
- 150000001298 alcohols Chemical class 0.000 abstract 1
- 125000001743 benzylic group Chemical group 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 102
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 238000000926 separation method Methods 0.000 description 32
- 239000002585 base Substances 0.000 description 22
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 20
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 17
- 238000005160 1H NMR spectroscopy Methods 0.000 description 17
- 238000004679 31P NMR spectroscopy Methods 0.000 description 17
- 238000012544 monitoring process Methods 0.000 description 17
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical compound C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 14
- 150000002118 epoxides Chemical class 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 4
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 4
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical class OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 3
- ASUOLLHGALPRFK-UHFFFAOYSA-N phenylphosphonoylbenzene Chemical class C=1C=CC=CC=1P(=O)C1=CC=CC=C1 ASUOLLHGALPRFK-UHFFFAOYSA-N 0.000 description 3
- 150000003003 phosphines Chemical class 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- MFGWMAAZYZSWMY-UHFFFAOYSA-N (2-naphthyl)methanol Chemical compound C1=CC=CC2=CC(CO)=CC=C21 MFGWMAAZYZSWMY-UHFFFAOYSA-N 0.000 description 2
- UIMJANTUJQGSEX-UHFFFAOYSA-N 2,2'-biphenyldimethanol Chemical compound OCC1=CC=CC=C1C1=CC=CC=C1CO UIMJANTUJQGSEX-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- AVPVRXORILGHNM-UHFFFAOYSA-N chlorobenzene;methanol Chemical class OC.ClC1=CC=CC=C1 AVPVRXORILGHNM-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- NXGAOFONOFYCNG-UHFFFAOYSA-N diphenylphosphorylmethylbenzene Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)CC1=CC=CC=C1 NXGAOFONOFYCNG-UHFFFAOYSA-N 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- FSWNRRSWFBXQCL-UHFFFAOYSA-N (3-bromophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1 FSWNRRSWFBXQCL-UHFFFAOYSA-N 0.000 description 1
- FYGNFHZYXFIZCA-UHFFFAOYSA-N 1-(diphenylphosphorylmethyl)-2-methylbenzene Chemical compound CC1=CC=CC=C1CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 FYGNFHZYXFIZCA-UHFFFAOYSA-N 0.000 description 1
- DAYNEXDUWXFMQB-UHFFFAOYSA-N 2-(diphenylphosphorylmethyl)thiophene Chemical class C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)CC1=CC=CS1 DAYNEXDUWXFMQB-UHFFFAOYSA-N 0.000 description 1
- XUVVJGXDYCSORU-UHFFFAOYSA-N 2-diphenylphosphorylethylbenzene Chemical class C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)CCC1=CC=CC=C1 XUVVJGXDYCSORU-UHFFFAOYSA-N 0.000 description 1
- OKSIVSNKUUISMW-UHFFFAOYSA-N 3-diphenylphosphorylprop-1-enylbenzene Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)CC=CC1=CC=CC=C1 OKSIVSNKUUISMW-UHFFFAOYSA-N 0.000 description 1
- 125000004217 4-methoxybenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1OC([H])([H])[H])C([H])([H])* 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
- RNAHHZKZQBECKV-UHFFFAOYSA-N O=P(Cc1ccccc1CP(c1ccccc1)(c1ccccc1)=[U])(c1ccccc1)c1ccccc1 Chemical compound O=P(Cc1ccccc1CP(c1ccccc1)(c1ccccc1)=[U])(c1ccccc1)c1ccccc1 RNAHHZKZQBECKV-UHFFFAOYSA-N 0.000 description 1
- YWMLORGQOFONNT-UHFFFAOYSA-N [3-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC(CO)=C1 YWMLORGQOFONNT-UHFFFAOYSA-N 0.000 description 1
- FXJGFZBEOYKOGL-UHFFFAOYSA-N [heptyl(phenyl)phosphoryl]benzene Chemical compound C=1C=CC=CC=1P(=O)(CCCCCCC)C1=CC=CC=C1 FXJGFZBEOYKOGL-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical class BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000007832 transition metal-catalyzed coupling reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5325—Aromatic phosphine oxides or thioxides (P-C aromatic linkage)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
- C07F9/5063—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds
- C07F9/5081—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds from starting materials having the structure >P-Het, Het being an heteroatom different from Hal or Metal
-
- 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
- C07F9/6553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms
- C07F9/655345—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms the sulfur 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)
- Crystallography & Structural Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides the synthetic method of three substitution phosphine oxide compounds or three two phosphine oxide compounds of substitution.This method is alkylating reagent using cheap and easy to get, wide material sources, the alcohol of stable low toxicity or glycol, and using salt compounded of iodine cheap and easy to get as catalyst, without solvent, three substitution phosphine oxides or two phosphine oxide compounds are directly obtained by selective reaction.The reaction method is simple, mild condition, without solvent, easily operated.Requirement of this method to reaction condition is relatively low, is alkylating reagent using benzylic type, allyl type and lard type alcohols, the synthesis of target phosphine oxide compound can be achieved, with the wider scope of application.This method can also easily amplify 20 times of productions, and prepared by gram level for carrying out product, therefore should also have certain research and prospects for commercial application.
Description
Technical field
The invention belongs to the field of chemical synthesis, the synthetic method of three substitution phosphine oxides and two phosphine oxides is specifically referred to, is particularly related to
The lower alkoxy phosphine of salt compounded of iodine catalysis reacts with alcohol prepares three green synthesis methods for replacing phosphine oxide and two phosphine oxide compounds.
Background technology
Three substitution phosphine oxide compounds can very easily be reduced to three substitution phosphine compounds, can widely should as part
In being synthesized for transition metal-catalyzed coupling reaction, asymmetry catalysis, and three substitution phosphine oxides or three substitution phosphine compounds
Can be directly as some organic reactions of catalyst.Three substitution phosphine oxide structures are present in natural products and pharmacological activity chemical combination
In thing.Therefore, the synthesis of three substitution phosphine oxide compounds also result in the attention of organic chemists.
The existing method for preparing three substitution phosphine oxide compounds mainly has using the corresponding three substitutions phosphine compound system of oxidation
It is standby, but three substitution phosphine compounds need multistep to synthesize, price is higher, so method does not possess actual application value.Three substitution phosphine oxides
Compound can also be synthesized by the A Erbuzuofu of halogenated hydrocarbons and alkoxy phosphine under the high temperature conditions, but need to use toxicity
Greatly, the halogenated hydrocarbons of stability difference is as alkylating reagent, and reaction can produce active height, the small molecule halogenated hydrocarbons of low boiling point is pair
Product, produces pollution.Also there is the method for transition metal-catalyzed coupling in recent years, but transition-metal catalyst is costly, together
Also need addition part and substantial amounts of alkali in Shi Fanying, the accessory substance of reaction is more, pollution greatly.Also there is document report stepped approach,
Previously prepared alkylphosphine oxide, then issues the rearrangement reaction of raw intramolecular to realize the conjunction of three substitution phosphine oxides in Louis acid catalysis
Into, but stepwise reaction cycle length is, it is necessary to which substantial amounts of isolate and purify work, inefficiency, and can be produced largely in this process
Accessory substance, cause Atom economy low and pollute.Therefore these methods be still have the shortcomings that it is many, it would be highly desirable to improve.
Therefore, find a kind of new method and replace phosphine oxide using low toxicity, the synthesis three of the step of raw material one cheap and easy to get is stablized
Compound is all significantly to study for organic synthesis, biochemical and Pharmaceutical Chemist.
The content of the invention
The invention aims to overcome prior art exist shortcoming and defect, and provide one kind three replace phosphine oxide and
The synthetic method of two phosphine oxides, raw material sources that this method is used are extensive, cheap and easy to get, stable low toxicity, course of reaction environmental protection.
To achieve the above object, the technical scheme is that the synthesis side of a kind of three substitution phosphine oxide or three two phosphine oxides of substitution
Method,
Using alcohol or glycol as alkylating reagent, using salt compounded of iodine as catalyst, alkoxy phosphine is obtained with alcohol or glycol directly reaction
Three substitution phosphine oxides or three two phosphine oxides of substitution, reaction temperature is 30~160 DEG C, and the reaction time is 1~60 hour, and its reaction equation is：
Wherein：
R1It is phenyl or other substituted aryls, condensed ring that various functional groups are substituted in 2-, 3-, 4-, 5- or 6-, or it is various
The heteroaryl of functional group's substitution, can also be the alkyl of various carbon chain lengths and pendant functional groups' substitution；
Glycol is the aliphatic glycol that carbon number is more than or equal to 2, or the substitution of various functional groups benzene dimethanol, fragrant diformazan
Alcohol, heteroaryl dimethanol；
R2、R3Be the alkyl or the aryl of all kinds of functional groups substitution of the substitution of various straight or branched functional groups, condensed ring and
The heteroaryl of all kinds of functional group's substitutions；
R4It is the alkyl of straight or branched substitution or the aryl of all kinds of functional groups substitution.
Further set is that the catalyst is inorganic salt compounded of iodine or organic salt compounded of iodine.
Further set is that the consumption of catalyst is 0.1~100mol%.
Further setting is course of reaction without solvent.
It is that reaction temperature is 60~150 DEG C further to set, and the reaction time is 12~48 hours.
It is nontransition metal catalyst that technical scheme, which provides a kind of salt compounded of iodine, is tried by alkylation of the alcohol of green
Agent, with alkoxy phosphine compound in solvent-free lower the substitution phosphine oxides of progress high selectivity reaction synthesis three and two phosphine oxide compounds
New method.
It is an advantage of the invention that：Compared with traditional literature method, cheap and easy to get, wide material sources, stably can be used in this method
Low toxicity, the alcohol of green or diol compound are alkylating reagent, and without using transition-metal catalyst and part, reaction is without activation
Agent, without using organic solvent, accessory substance is small molecular alcohol, green pollution-free.Therefore, requirement of this method to reaction condition
The relatively low, scope of application is wider, with the obvious advantage compared with known method, and prospect is widely applied with potential.
This method can also easily amplify 20 times of productions, prepared by gram level for carrying out product, therefore should also have certain
Research and prospects for commercial application.
The present invention is described further with reference to embodiment.
Embodiment
The present invention is specifically described below by embodiment, is served only for that the present invention is further described, no
It is understood that for limiting the scope of the present invention, the technician in the field can be according to the content of foregoing invention to the present invention
Make some nonessential modifications and adaptations.
Embodiment 1
Hexichol base oxethyl phosphine and phenmethylol prepare benzyldiphenyl phosphine oxide
Hexichol base oxethyl phosphine (115.0mg, 0.50mmol), phenmethylol are sequentially added in 20mL tubular reactors
(108.0mg, 1.0mmol, 2.0equiv.) and tetrabutylammonium iodide (3.7mg, 0.01mmol, 2mol%), vacuumizes nitrogen guarantor
Shield, is then heated to 90 DEG C of reaction 24h under condition of no solvent.After TLC monitoring reactions completely, product is carried with pillar layer separation
It is pure, separation yield 89%.1H NMR(500MHz,CDCl3)δ7.84–7.60(m,4H),7.60–7.36(m,6H),7.27–7.13
(m, 3H), 7.18-6.92 (m, 2H), 3.66 (d, J=14.0Hz, 2H)13C NMR(125MHz,CDCl3) δ 132.24 (d, J=
98.4Hz), 131.79 (d, J=2.7Hz), 131.19 (d, J=9.1Hz), 130.16 (d, J=5.2Hz), 128.49 (d, J=
11.7Hz), (d, the J=66.3Hz) of 128.37 (d, J=2.5Hz), 126.79 (d, J=2.9Hz), 38.1531P NMR
(202MHz,CDCl3)δ29.45(s)。
Embodiment 2
Hexichol base oxethyl phosphine and 4- methoxy benzyl alcohols prepare 4- (methoxyl group) benzyldiphenyl phosphine oxide
Hexichol base oxethyl phosphine (115.0mg, 0.50mmol), 4- methoxybenzene first are sequentially added in 20mL tubular reactors
Alcohol (138.0mg, 1.0mmol, 2.0equiv.) and tetrabutylammonium iodide (3.7mg, 0.01mmol, 2mol%), vacuumize nitrogen
Protection, is then heated to 90 DEG C of reaction 24h under condition of no solvent.After TLC monitoring reactions completely, product is carried with pillar layer separation
It is pure, separation yield 91%.1H NMR(500MHz,CDCl3)δ7.87–7.61(m,4H),7.60–7.36(m,6H),7.02(dd,J
=8.5,2.0Hz, 2H), 6.73 (d, J=8.5Hz, 2H), 3.74 (s, 1H), 3.59 (d, J=13.5Hz, 1H)13C NMR
(125MHz,CDCl3) δ 158.54 (d, J=2.9Hz), 132.42 (d, J=98.0Hz), 131.76 (d, J=2.7Hz),
131.19 (d, J=9.3Hz), 131.13 (d, J=5.8Hz), 128.49 (d, J=11.6Hz), 122.91 (d, J=8.1Hz),
113.91 (d, J=2.5Hz), 55.20,37.12 (d, J=67.5Hz)31P NMR(202MHz,CDCl3)δ29.44(s)。
Embodiment 3
Hexichol base oxethyl phosphine and 4- chlorobenzene methanols prepare 4- (chlorine) benzyldiphenyl phosphine oxide
Hexichol base oxethyl phosphine (115.0mg, 0.50mmol), 4- chlorobenzene methanols are sequentially added in 20mL tubular reactors
(142.0mg, 1.0mmol, 2.0equiv.) and tetrabutylammonium iodide (3.7mg, 0.01mmol, 2mol%), vacuumizes nitrogen guarantor
Shield, is then heated to 90 DEG C of reaction 24h under condition of no solvent.After TLC monitoring reactions completely, product is carried with pillar layer separation
It is pure, separation yield 72%.1H NMR(500MHz,CDCl3) δ 7.70 (d, J=7.5Hz, 2H), 7.67 (d, J=8.0Hz, 2H),
7.55-7.42 (m, 6H), 7.15 (d, J=8.5Hz, 2H), 7.04 (d, J=8.0Hz, 2H), 3.61 (d, J=13.5Hz, 2H)
.13C NMR(125MHz,CDCl3) δ 132.86 (d, J=3.6Hz), 132.02 (d, J=98.9Hz), 131.96 (d, J=
2.7Hz), 131.38 (d, J=5.3Hz), 131.11 (d, J=9.2Hz), 129.72 (d, J=8.1Hz), 128.60 (d, J=
11.9Hz), 128.54 (d, J=3.6Hz), 37.48 (d, J=66.2Hz)31P NMR(202MHz,CDCl3)δ29.07(s)。
Embodiment 4
Hexichol base oxethyl phosphine and 3- bromobenzenes methanol prepare 3- (bromine) benzyldiphenyl phosphine oxide
Hexichol base oxethyl phosphine (115.0mg, 0.50mmol), 3- bromobenzene methanol are sequentially added in 20mL tubular reactors
(186.0mg, 1.0mmol, 2.0equiv.) and tetrabutylammonium iodide (3.7mg, 0.01mmol, 2mol%), vacuumizes nitrogen guarantor
Shield, is then heated to 90 DEG C of reaction 24h under condition of no solvent.After TLC monitoring reactions completely, product is carried with pillar layer separation
It is pure, separation yield 83%.1H NMR(500MHz,CDCl3)δ7.73–7.65(m,4H),7.59–7.39(m,6H),7.34–7.25
(m, 2H), 7.12-6.98 (m, 2H), 3.60 (d, J=14.0Hz, 2H)13C NMR(125MHz,CDCl3) δ 133.6 (d, J=
7.9Hz), 133.0 (d, J=5.4Hz), 132.3,132.0 (d, J=2.7Hz), 131.5,131.1 (d, J=9.2Hz),
129.9 (dd, J=17.2,2.7Hz), 128.8 (d, J=5.1Hz), 128.6 (d, J=11.8Hz), 122.3 (d, J=
2.9Hz), 37.8 (d, J=65.8Hz)31P NMR(202MHz,CDCl3)δ29.21(s)。
Embodiment 5
Hexichol base oxethyl phosphine and 2- methylbenzyl alcohols prepare 2- (methyl) benzyldiphenyl phosphine oxide
Hexichol base oxethyl phosphine (115.0mg, 0.50mmol), 2- methylbenzyl alcohols are sequentially added in 20mL tubular reactors
(122.0mg, 1.0mmol, 2.0equiv.) and tetrabutylammonium iodide (3.7mg, 0.01mmol, 2mol%), vacuumizes nitrogen guarantor
Shield, is then heated to 90 DEG C of reaction 24h under condition of no solvent.After TLC monitoring reactions completely, product is carried with pillar layer separation
It is pure, separation yield 85%.1H NMR(500MHz,CDCl3)δ7.62–7.55(m,4H),7.46–7.28(m,6H),7.00(s,
2H), (s, the 1H) of 6.93-6.78 (m, 2H), 3.59 (d, J=14.0Hz, 2H), 2.0613C NMR(125MHz,CDCl3)δ
137.5 (d, J=5.4Hz), 132.5 (d, J=98.4Hz), 131.8 (d, J=2.7Hz), 131.2 (d, J=9.1Hz),
130.7 (d, J=4.6Hz), 130.4 (d, J=2.6Hz), 129.7 (d, J=8.2Hz), 128.5 (d, J=11.6Hz),
127.0 (d, J=3.1Hz), 125.7 (d, J=2.8Hz), 35.3 (d, J=66.7Hz), 20.0.31P NMR(202MHz,
CDCl3)δ29.64(s)。
Embodiment 6
Hexichol base oxethyl phosphine and 2- naphthalenes methanol prepare 2 menaphthyl diphenyl phosphine oxides
Hexichol base oxethyl phosphine (115.0mg, 0.50mmol), 2- naphthalene methanol are sequentially added in 20mL tubular reactors
(158.0mg, 1.0mmol, 2.0equiv.) and tetrabutylammonium iodide (3.7mg, 0.01mmol, 2mol%), vacuumizes nitrogen guarantor
Shield, is then heated to 90 DEG C of reaction 24h under condition of no solvent.After TLC monitoring reactions completely, product is carried with pillar layer separation
It is pure, separation yield 79%.1H NMR(500MHz,CDCl3) δ 7.77-7.64 (m, 7H), 7.57 (s, 1H), 7.50 (t, J=
7.5Hz, 2H) (d, J=14.0Hz, the 2H) of 7.44-7.37 (m, 6H), 7.24 (t, J=8.0Hz, 1H), 3.8113C NMR
(125MHz,CDCl3) δ 133.33 (d, J=2.6Hz), 132.33 (d, J=98.4Hz), 132.26 (d, J=2.0Hz),
131.85 (d, J=2.6Hz), 131.20 (d, J=9.1Hz), 129.03 (d, J=6.7Hz), 128.78 (d, J=8.2Hz),
128.54 (d, J=11.7Hz), 128.21 (d, J=4.2Hz), 127.95 (d, J=1.9Hz), 127.60 (d, J=9.4Hz),
125.83 (d, J=39.6Hz), 38.37 (d, J=66.4Hz)31P NMR(202MHz,CDCl3)δ29.46(s)。
Embodiment 7
Hexichol base oxethyl phosphine and 2- thenyl alcohols prepare 2- thenyl diphenyl phosphine oxides
Hexichol base oxethyl phosphine (115.0mg, 0.50mmol), 2- thenyl alcohols are sequentially added in 20mL tubular reactors
(114.0mg, 1.0mmol, 2.0equiv.) and tetrabutylammonium iodide (9.3mg, 0.025mmol, 5mol%), vacuumizes nitrogen
Protection, is then heated to 90 DEG C of reaction 24h under condition of no solvent.After TLC monitoring reactions completely, product is carried with pillar layer separation
It is pure, separation yield 58%.1H NMR(500MHz,CDCl3)δ7.80–7.68(m,4H),7.58–7.43(m,6H),7.15–7.08
(m, 1H), 6.88-6.84 (m, 2H), 3.89 (d, J=11.5Hz, 2H)13C NMR(125MHz,CDCl3)δ131.97,
131.24 (d, J=8.8Hz), 128.57 (d, J=11.5Hz), 127.44 (d, J=6.5Hz), 127.01,124.87,32.71
(d, J=70.9Hz)31P NMR(202MHz,CDCl3)δ31.38(s)。
Embodiment 8
Hexichol base oxethyl phosphine and cinnamyl alcohol prepare cinnamyl diphenyl phosphine oxide
Hexichol base oxethyl phosphine (115.0mg, 0.50mmol), cinnamyl alcohol are sequentially added in 20mL tubular reactors
(134.0mg, 1.0mmol, 2.0equiv.) and tetrabutylammonium iodide (3.7mg, 0.01mmol, 2mol%), vacuumizes nitrogen guarantor
Shield, is then heated to 90 DEG C of reaction 24h under condition of no solvent.After TLC monitoring reactions completely, product is carried with pillar layer separation
It is pure, separation yield 82%.1H NMR(500MHz,CDCl3) δ 7.76 (dd, J=11.5,8.0Hz, 4H), 7.63-7.37 (m,
6H), 7.30-7.06 (m, 5H), 6.42 (dd, J=16.0,4.0Hz, 1H), 6.29-5.98 (m, 1H), 3.29 (dd, J=
15.0,7.5Hz,2H).13C NMR(125MHz,CDCl3) δ 136.79 (d, J=3.1Hz), 135.64 (d, J=12.1Hz),
132.47 (d, J=98.3Hz), 131.91 (d, J=2.7Hz), 131.09 (d, J=9.2Hz), 128.64 (d, J=
11.7Hz), 128.47,127.57,126.24 (d, J=1.6Hz), 118.45 (d, J=9.7Hz), 35.60 (d, J=
68.7Hz).31P NMR(202MHz,CDCl3)δ30.06(s)。
Embodiment 9
Hexichol base oxethyl phosphine and 2 phenylethyl alcohol prepare 2- phenethyl diphenyl phosphine oxides
Hexichol base oxethyl phosphine (115.0mg, 0.50mmol), 2 phenylethyl alcohol are sequentially added in 20mL tubular reactors
(122.0mg, 1.0mmol, 2.0equiv.) and tetrabutylammonium iodide (18.5mg, 0.05mmol, 10mol%), vacuumizes nitrogen
Protection, is then heated to 130 DEG C of reaction 24h under condition of no solvent.After TLC monitoring reactions completely, product pillar layer separation
Purification, separation yield 73%.1H NMR(500MHz,CDCl3)δ7.82–7.72(m,4H),7.55–7.45(m,6H),7.27–
7.12(m,5H),2.97–2.90(m,1H),2.62–2.55(m,1H).13C NMR(125MHz,CDCl3) δ 141.18 (d, J=
15.3Hz), 132.78 (d, J=97.8Hz), 131.83 (d, J=2.7Hz), 130.80 (d, J=9.3Hz), 128.74 (d, J
=11.7Hz), 128.62,128.07,126.34,31.90 (d, J=69.9Hz), 27.55 (d, J=3.1Hz)31P NMR
(202MHz,CDCl3)δ31.64(s)。
Embodiment 10
Hexichol base oxethyl phosphine and n-heptanol prepare n-heptyl diphenyl phosphine oxide
Hexichol base oxethyl phosphine (115.0mg, 0.50mmol), n-heptanol are sequentially added in 20mL tubular reactors
(116.0mg, 1.0mmol, 2.0equiv.) and tetrabutylammonium iodide (18.5mg, 0.050mmol, 10mol%), vacuumizes nitrogen
Gas shielded, is then heated to 130 DEG C of reaction 24h under condition of no solvent.After TLC monitoring reactions completely, product column chromatography point
From purification, separation yield 67%.1H NMR(500MHz,CDCl3)δ7.77–7.71(m,4H),7.54–7.44(m,6H),2.30–
2.22 (m, 2H), 1.75-1.51 (m, 2H), 1.50-1.33 (m, 2H), 1.30-1.17 (m, 6H), 0.85 (d, J=6.5Hz,
3H).13C NMR(125MHz,CDCl3) δ 133.22 (d, J=97.7Hz), 131.61 (d, J=2.6Hz), 130.76 (d, J=
9.2Hz), 128.60 (d, J=11.6Hz), 31.53,30.92 (d, J=14.6Hz), 29.73 (d, J=72.1Hz), 28.72,
22.53,21.40 (d, J=3.9Hz), 14.00.31P NMR(202MHz,CDCl3)δ32.72(s)。
Embodiment 11
Diphenyl benzene epoxide phosphine and phthalyl alcohol prepare O-phthalic base (diphenyl) phosphine oxide
Diphenyl benzene epoxide phosphine (417.0mg, 1.5mmol, 1.5equiv.) is sequentially added in 20mL tubular reactors, it is adjacent
Benzene dimethanol (69.0mg, 0.5mmol) and tetrabutylammonium iodide (9.3mg, 0.025mmol, 5mol%), vacuumize nitrogen guarantor
Shield, is then heated to 90 DEG C of reaction 24h under condition of no solvent.After TLC monitoring reactions completely, product is carried with pillar layer separation
It is pure, separation yield 61%.1H NMR(500MHz,CDCl3) δ 7.68 (t, J=9.0Hz, 8H), 7.52-7.38 (m, 12H),
(d, J=12.5Hz, the 4H) of 6.90-6.83 (m, 2H), 6.75-6.68 (m, 2H), 3.9613C NMR(125MHz,CDCl3)δ
(133.0,132.2,131.8,131.7,131.2 d, J=9.1Hz), 128.5 (d, J=9.3Hz), 126.7,35.4 (d, J=
66.1Hz).31P NMR(202MHz,CDCl3)δ31.05(s)。
Embodiment 12
Diphenyl benzene epoxide phosphine and 1,3- benzene dimethanol prepare 1,3- xyxylenes (diphenyl) phosphine oxide
Sequentially add diphenyl benzene epoxide phosphine (417.0mg, 1.5mmol, 1.5equiv.) in 20mL tubular reactors, 1,
3- benzene dimethanols (69.0mg, 0.5mmol) and tetrabutylammonium iodide (9.3mg, 0.025mmol, 5mol%), vacuumize nitrogen guarantor
Shield, is then heated to 90 DEG C of reaction 24h under condition of no solvent.After TLC monitoring reactions completely, product is carried with pillar layer separation
It is pure, separation yield 63%.1H NMR(500MHz,CDCl3)δ7.74–7.56(m,8H),7.52–7.38(m,12H),7.15(s,
1H), (d, J=13.5Hz, the 4H) of 6.93 (t, J=7.5Hz, 1H), 6.84 (d, J=7.5Hz, 2H), 3.5813C NMR
(125MHz,CDCl3) δ 132.35 (d, J=15.7Hz), 132.26 (d, J=10.6Hz), 131.83,131.65,131.27
(d, J=10.1Hz), 131.15 (d, J=9.4Hz), 128.52 (d, J=12.0Hz), 128.30,37.82 (d, J=
66.3Hz).31P NMR(202MHz,CDCl3)δ30.93(s)。
Embodiment 13
Diphenyl benzene epoxide phosphine and 2,2 '-biphenyl dimethanol prepares 2,2 '-biphenyl dimethyl (diphenyl) phosphine oxide
Sequentially add diphenyl benzene epoxide phosphine (417.0mg, 1.5mmol, 1.5equiv.) in 20mL tubular reactors, 2,
2 '-biphenyl dimethanol (107.0mg, 0.5mmol) and tetrabutylammonium iodide (9.3mg, 0.025mmol, 5mol%), vacuumize nitrogen
Gas shielded, is then heated to 90 DEG C of reaction 24h under condition of no solvent.After TLC monitoring reactions completely, product pillar layer separation
Purification, separation yield 38%.1H NMR(500MHz,CDCl3) δ 7.60-7.24 (m, 24H), 7.06 (s, 2H), 6.40 (d, J=
7.0Hz,2H),3.42–3.24(m,4H)；13C NMR(125MHz,CDCl3) δ 140.62 (d, J=6.7Hz), 131.78 (d, J
=2.5Hz), 131.58 (d, J=2.4Hz), 131.11 (d, J=9.2Hz), 130.55 (d, J=4.3Hz), 130.48,
128.55 (d, J=11.6Hz), 128.33 (d, J=11.8Hz), 127.60 (d, J=2.1Hz), 126.76 (d, J=
2.2Hz), 33.90 (d, J=66.8Hz)31P NMR(202MHz,CDCl3)δ30.36(s)。
Embodiment 14
Diphenyl benzene epoxide phosphine and 1,4- butanediols prepare 1,4- bis- (diphenyl) phosphine oxide ethane
Diphenyl benzene epoxide phosphine (417.0mg, 1.5mmol, 1.5equiv.), second are sequentially added in 20mL tubular reactors
Glycol (31.0mg, 0.5mmol) and tetrabutylammonium iodide (18.5mg, 0.050mmol, 10mol%), vacuumize nitrogen protection,
Then 130 DEG C of reaction 24h are heated under condition of no solvent.After TLC monitoring reactions completely, product is purified with pillar layer separation,
Separation yield 28%.1H NMR(500MHz,CDCl3)δ7.75–7.67(m,8H),7.55–7.40(m,12H),2.55(s,4H)
.13C NMR(125MHz,CDCl3) δ 132.03,131.99 (d, J=100.4Hz) 130.80 (t, J=4.7Hz), 128.83 (t,
), J=5.8Hz 21.72 (t, J=32.6Hz)31P NMR(202MHz,CDCl3)δ32.70(s)。
Embodiment 15
Diphenyl benzene epoxide phosphine and 1,4- butanediols prepare 1,4- bis- (diphenyl) phosphine oxide butane
Sequentially add diphenyl benzene epoxide phosphine (417.0mg, 1.5mmol, 1.5equiv.) in 20mL tubular reactors, 1,
4- butanediols (45.0mg, 0.5mmol) and tetrabutylammonium iodide (18.5mg, 0.050mmol, 10mol%), vacuumize nitrogen guarantor
Shield, is then heated to 130 DEG C of reaction 24h under condition of no solvent.After TLC monitoring reactions completely, product is carried with pillar layer separation
It is pure, separation yield 48%.1H NMR(500MHz,CDCl3)δ7.77–7.52(m,8H),7.50–7.28(m,12H),2.31–
2.18(m,4H),1.75–1.60(m,4H).13C NMR(125MHz,CDCl3) δ 132.69 (d, J=98.5Hz), 131.77 (d,
J=2.5Hz), 130.73 (d, J=9.3Hz), 128.68 (d, J=11.7Hz), 29.32 (d, J=71.6Hz), 22.86 (dd,
J=15.5,3.6Hz)31P NMR(202MHz,CDCl3)δ33.14(s)。
Embodiment 16
Diphenyl benzene epoxide phosphine and 1,5- butanediols prepare 1,5- bis- (diphenyl) phosphine oxide pentane
Sequentially add diphenyl benzene epoxide phosphine (417.0mg, 1.5mmol, 1.5equiv.) in 20mL tubular reactors, 1,
5- butanediols (52.0mg, 0.5mmol) and tetrabutylammonium iodide (18.5mg, 0.050mmol, 10mol%), vacuumize nitrogen guarantor
Shield, is then heated to 130 DEG C of reaction 24h under condition of no solvent.After TLC monitoring reactions completely, product is carried with pillar layer separation
It is pure, separation yield 46%.1H NMR(500MHz,CDCl3)δ7.85–7.65(m,8H),7.54–7.42(m,12H),2.22(d,J
=3.2Hz, 4H), 1.62-1.48 (m, 6H)13C NMR(125MHz,CDCl3) δ 132.90 (d, J=98.3Hz), 131.71
(d, J=2.6Hz), 130.74 (d, J=9.3Hz), 128.65 (d, J=11.6Hz), 31.82 (t, J=14.1Hz), 29.27
(d, J=71.9Hz), 20.87 (d, J=3.8Hz)31P NMR(202MHz,CDCl3)δ33.73(s)。
Embodiment 17
Diphenyl benzene epoxide phosphine and phthalyl alcohol largely prepare O-phthalic base (diphenyl phosphine oxide)
Diphenyl benzene epoxide phosphine (8.34g, 30mmol, 1.5equiv.), adjacent benzene two are sequentially added in 20mL tubular reactors
Methanol (1.38g, 10mmol) and tetrabutylammonium iodide (185.0mg, 0.5mmol, 5mol%), vacuumize nitrogen protection, then
90 DEG C of reaction 24h are heated under condition of no solvent.After TLC monitoring reactions completely, reaction mixture is with ethyl acetate (100mL)
Washing, suction filtration, vacuum drying, separation yield 65%.1H NMR(500MHz,CDCl3) δ 7.68 (t, J=9.0Hz, 8H), 7.52-
(d, J=12.5Hz, the 4H) of 7.38 (m, 12H), 6.90-6.83 (m, 2H), 6.75-6.68 (m, 2H), 3.9613C NMR
(125MHz,CDCl3) δ 133.0,132.2,131.8,131.7,131.2 (d, J=9.1Hz), 128.5 (d, J=9.3Hz),
(126.7,35.4 d, J=66.1Hz)31P NMR(202MHz,CDCl3)δ31.05(s)。
Claims (5)
1. the synthetic method of a kind of three substitution phosphine oxide compound or three two phosphine oxide compounds of substitution, it is characterised in that：
Using alcohol or glycol as alkylating reagent, using salt compounded of iodine as catalyst, alkoxy phosphine obtains three and taken with alcohol or glycol directly reaction
For phosphine oxide compound or three two phosphine oxide compounds of substitution, reaction temperature is 30~160 DEG C, and the reaction time is 1~60 hour, and its is anti-
Ying Shiwei：
Wherein：
R1It is phenyl or other substituted aryls, condensed ring that various functional groups are substituted in 2-, 3-, 4-, 5- or 6-, or various functions
The heteroaryl of group's substitution, can also be the alkyl of various carbon chain lengths and pendant functional groups' substitution；
Glycol is the aliphatic glycol that carbon number is more than or equal to 2, or the benzene dimethanol of various functional groups substitution, fragrant dimethanol, miscellaneous
Fragrant dimethanol；
R2、R3It is the alkyl or the aryl of all kinds of functional groups substitution of the substitution of various straight or branched functional groups, condensed ring and all kinds of
The heteroaryl of functional group's substitution；
R4It is the alkyl of straight or branched substitution or the aryl of all kinds of functional groups substitution.
2. the synthetic method of a kind of three substitution phosphine oxide compound according to claim 1 or three two phosphine oxide compounds of substitution,
It is characterized in that：The catalyst is inorganic salt compounded of iodine or organic salt compounded of iodine.
3. the synthetic method of a kind of three substitution phosphine oxide compound according to claim 1 or three two phosphine oxide compounds of substitution,
It is characterized in that：The consumption of catalyst is 0.1~100mol%.
4. the synthetic method of a kind of three substitution phosphine oxide compound according to claim 1 or three two phosphine oxide compounds of substitution,
It is characterized in that：Course of reaction is without solvent.
5. the synthetic method of a kind of three substitution phosphine oxide compound according to claim 1 or three two phosphine oxide compounds of substitution,
It is characterized in that：Reaction temperature is 60~150 DEG C, and the reaction time is 12~48 hours.
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|---|---|---|---|---|
| CN109678901A (en) * | 2019-01-31 | 2019-04-26 | 信阳师范学院 | A kind of three replace the synthetic method of phosphine oxide compound |
| CN110294776A (en) * | 2019-06-20 | 2019-10-01 | 苏州大学 | A method of preparing aryl oxide phosphine-derivatives |
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| JPH06220071A (en) * | 1993-01-26 | 1994-08-09 | Mitsubishi Kasei Corp | Production of benzyl phosphonate derivative |
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- 2016-11-15 CN CN201611004785.5A patent/CN107021982A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH06220071A (en) * | 1993-01-26 | 1994-08-09 | Mitsubishi Kasei Corp | Production of benzyl phosphonate derivative |
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| REJEKAH M RICHARDSON ET AL.: "Synthesis of dialkyl and diaryl benzylphosphonates through a ZnI2-mediated reaction", 《TETRAHEDRON LETTERS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109678901A (en) * | 2019-01-31 | 2019-04-26 | 信阳师范学院 | A kind of three replace the synthetic method of phosphine oxide compound |
| CN109678901B (en) * | 2019-01-31 | 2021-05-28 | 信阳师范学院 | Synthesis method of tri-substituted phosphine oxide compound |
| CN110294776A (en) * | 2019-06-20 | 2019-10-01 | 苏州大学 | A method of preparing aryl oxide phosphine-derivatives |
| CN110294776B (en) * | 2019-06-20 | 2021-12-10 | 苏州大学 | Method for preparing aryl phosphine oxide derivative |
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