CN110330525A - A method of utilizing microwave technology one kettle way rapid synthesis alkyl phosphinic acid - Google Patents
A method of utilizing microwave technology one kettle way rapid synthesis alkyl phosphinic acid Download PDFInfo
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- CN110330525A CN110330525A CN201910510263.XA CN201910510263A CN110330525A CN 110330525 A CN110330525 A CN 110330525A CN 201910510263 A CN201910510263 A CN 201910510263A CN 110330525 A CN110330525 A CN 110330525A
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- acid
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- alkyl phosphinic
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- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 26
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 25
- -1 alkyl phosphinic acid Chemical compound 0.000 title claims abstract description 23
- 238000005516 engineering process Methods 0.000 title claims abstract description 16
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 39
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 30
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 230000035484 reaction time Effects 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 9
- 150000007522 mineralic acids Chemical class 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- VWSUVZVPDQDVRT-UHFFFAOYSA-N phenylperoxybenzene Chemical compound C=1C=CC=CC=1OOC1=CC=CC=C1 VWSUVZVPDQDVRT-UHFFFAOYSA-N 0.000 claims description 3
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 claims description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004519 grease Substances 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229940071870 hydroiodic acid Drugs 0.000 claims description 2
- 150000004978 peroxycarbonates Chemical class 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000002253 acid Substances 0.000 description 18
- 150000007513 acids Chemical class 0.000 description 16
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 16
- 238000011065 in-situ storage Methods 0.000 description 12
- 238000004679 31P NMR spectroscopy Methods 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000001514 detection method Methods 0.000 description 7
- 239000012230 colorless oil Substances 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000002825 nitriles Chemical class 0.000 description 4
- 238000007342 radical addition reaction Methods 0.000 description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000003009 phosphonic acids Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- DGLXNOJGOHKWTN-UHFFFAOYSA-N CCCP(O)=O Chemical compound CCCP(O)=O DGLXNOJGOHKWTN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical group C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- DRDKFCAHTAHYER-UHFFFAOYSA-N bis(2-methylpropyl)phosphinic acid Chemical compound CC(C)CP(O)(=O)CC(C)C DRDKFCAHTAHYER-UHFFFAOYSA-N 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- DWHUEFYNZKYMMY-UHFFFAOYSA-N decylphosphinic acid Chemical class CCCCCCCCCCP(O)=O DWHUEFYNZKYMMY-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- KTLIMPGQZDZPSB-UHFFFAOYSA-N diethylphosphinic acid Chemical class CCP(O)(=O)CC KTLIMPGQZDZPSB-UHFFFAOYSA-N 0.000 description 1
- YTMRJBAHYSIRMZ-UHFFFAOYSA-N dioctylphosphinic acid Chemical compound CCCCCCCCP(O)(=O)CCCCCCCC YTMRJBAHYSIRMZ-UHFFFAOYSA-N 0.000 description 1
- WMDPJKZHARKRQI-UHFFFAOYSA-N dipropylphosphinic acid Chemical class CCCP(O)(=O)CCC WMDPJKZHARKRQI-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
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 discloses a kind of methods using microwave technology one kettle way rapid synthesis alkyl phosphinic acid, using hypophosphorous acid solution and alcohol as raw material, by means of there are azeotropic points and immiscible organic solvent with water, under microwave-assisted, one kettle way fast implements the synthesis of alkyl phosphinic acid.The present invention has the advantages that the used time is short, energy consumption is low, process is simple, safety coefficient is high.
Description
Technical field
The present invention relates to a kind of methods using microwave technology one kettle way rapid synthesis alkyl phosphinic acid, belong to organic synthesis
Field.
Background technique
Dialkyl phosphinic acid and its salt are widely used in industrial production as important chemical raw material and product.Such as:
Aluminum diethylphosphinate is a kind of phosphorus flame retardant newly developed, by its environmental protection, efficient feature, be widely used in nylon,
The engineering plastics such as PBT, PET it is flame-retardant modified；Di-n-octyl phosphinic acid and two positive decyl phosphinic acids are as efficient cobalt, nickel ion
Extractant is widely used；In addition, also having been widely used in biological field dialkyl phosphinic acid and its salt.
Exploitation for dialkyl phosphinic acid and its product salt, key are the synthesis of alkyl phosphinic acid intermediate.Mesh
The synthetic method of preceding alkyl phosphinic acid mainly has Aluminium Trichloride as Catalyst method, Grignard Reagent conversion method and free radical addition method.Three
Aluminum chloride-catalyzed method generates many solid waste, difficult.Grignard reagent activity is high, and reaction acutely leads to danger coefficient significantly
It improves.Free radical addition method becomes the first choice of current synthesis of alkyl phosphinic acids.
CN102924508A, CN101891762A are disclosed using water as solvent, and Sodium Hypophosphite and ethylene are that reaction is former
Expect, under condition of high voltage, realizes the synthesis of diethyl phosphinic acids by radical initiator or photoinitiator；CN103772428A is disclosed
Sodium Hypophosphite and propylene are reaction raw materials, and acetic acid is solvent, nano-metal-oxide is catalyst, catalysis sodium hypophosphite with
The addition reaction of propylene synthesizes high-purity dipropyl phosphinic acids sodium；CN107652321A is disclosed using hypophosphorous acid and alcohol as raw material,
Organic solvent is as solvent, and under the catalysis of radical initiator, addition reaction occurs, synthesizes diisobutylphosphinicacid acid.
In the technique of conventional free radical addition process synthesis of alkyl phosphinic acids, existing main problem has: (1) technique is cumbersome,
It is realized, and reacted using the preparatory acidification or the concentration of aqueous hypophosphorous acid of sodium hypophosphite since phosphate raw material is more
It is repeatedly fed in journey, increases processing step；(2) use of raw material is easy limited, and the introducing of alkyl substituent is more
The primary product for selecting alkene to crack as reaction substrate, alkene as petrochemical industry, there are boiling points lower, Yi Ziju, difficult storage
The shortcomings that depositing.(3) the most of mixed liquor for all selecting acetic acid and water of solvent increases the difficulty of product separation and solvent recycling
Degree, brings biggish environmental protection pressure.(4) most of process choice reaction under high pressure, reaction risk factor increases.(5) when reacting
Between it is long, most of technique last for hours even tens of hours, to artificial, energy consumption is big, greatly increase process risk and at
This.
Microwave heating is a kind of efficient interior heating, reaction system can be made to be brought rapidly up, capacity usage ratio is high.It can be at
Hundred thousands of times of raising organic reaction rate improves conversion ratio and yield, make it is certain do not occur under the conditions of traditional heating it is anti-
It should be achieved.Some drawbacks that conventional free radical addition process synthesis of alkyl phosphinic acids is overcome using microwave technology, are greatly improved
The combined coefficient of alkyl phosphinic acid.
Summary of the invention
The purpose of the present invention is to provide a kind of methods using microwave technology one kettle way rapid synthesis alkyl phosphinic acid, originally
Invention the method synthetic product component is consistent with current process result, with the used time is short, energy consumption is low, process is simple, safety system
The high advantage of number.Technical scheme is as follows:
A method of using microwave technology one kettle way rapid synthesis alkyl phosphinic acid, using 50% hypophosphorous acid solution and alcohol
Alkyl is realized by the in-situ preparation of alkene by means of there are azeotropic points and immiscible organic solvent with water for raw material
The synthesis of phosphonic acids, the specific steps are as follows:
(1) by 50% aqueous hypophosphorous acid and for the first time be added alcohol, inorganic acid, dissolved with initiator organic solvent anti-
It answers in device and mixes, be subsequently placed in microwave reactor.Stirring is opened, microwave power, reaction temperature, reaction time are set.
(2) alcohol, inorganic acid, the organic solvent dissolved with initiator is then added for the second time into reactor, is subsequently placed in
In microwave reactor.Stirring is opened, microwave power, reaction temperature, reaction time are set.
(3) after completion of the reaction, system vacuum backspin is removed into solvent, obtains alkyl phosphinic acid grease, organic solvent recycling
It utilizes.
Alcohol in step of the present invention is the tert-butyl alcohol, isobutanol, any one of isopropanol；
The molar ratio of the alcohol and hypophosphorous acid that are added for the first time is 1~3:1, preferably 1.5:1；
The molar ratio of second of the alcohol being added and hypophosphorous acid is 1~3:1, preferably 1:1.
Initiator in step of the present invention is azodiisobutyronitrile or azobisisoheptonitrile, perbenzoic acid, mistake
Aoxidize one or more of dibenzoyl, di-tert-butyl peroxide, peroxycarbonates, peroxidized t-butyl perbenzoate；
It is preferred that azodiisobutyronitrile.
The molar ratio of the initiator and time hypophosphorous acid that are added twice is 0.01~0.10:1.
Inorganic acid in step of the present invention is one or more of sulfuric acid, hydrobromic acid, hydroiodic acid, preferably dense sulphur
Acid；
The molar ratio of the inorganic acid and hypophosphorous acid that are added twice is 0.05~0.3:1.
Organic solvent in step of the present invention is toluene, chlorobenzene, meta-xylene, one of paraxylene or several
Kind；It is preferred that chlorobenzene.
The mass ratio of the organic solvent and aqueous hypophosphorous acid that are added for the first time is 0.5~2.0:1；
The mass ratio of second of organic solvent being added and aqueous hypophosphorous acid is 0.5~1.0:1.
Reaction temperature is 75~105 DEG C in step of the present invention.
Microwave power control is at 150~200 watts in step of the present invention.
Reaction time control is heated in step of the present invention for the first time in 15~20min；Second of heating reaction time
Control is in 5~10min.
Compared with prior art, the invention has the following advantages that
(1) present invention using 50% hypophosphorous acid as raw material, it is easy to operate, avoid the concentration of hypophosphorous acid solution, energy consumption
It reduces and improves efficiency；
(2) present invention in alcohol use, not only can be used as solvent, be also used as the raw material of fabricated in situ alkene, have
It is inconvenient that effect solves common raw material low boiling point, Yi Ziju, difficult storage bring；
(3) in the present invention azeotrope with water and immiscible organic solvent use, efficiently solve what solvent was difficult to recycle
Problem；
(4) it avoids substantially reducing danger coefficient using high-tension apparatus in the present invention；
(5) one kettle way charging twice is taken in the present invention, it is simple, quick and microwave-assisted reaction is rapid, greatly improve conjunction
At efficiency, process risk and cost are reduced.
The present invention is under microwave-assisted, one kettle way rapid synthesis alkyl phosphinic acid.In the method for the invention, in addition to tool
For (alcohol in-situ preparation dehydration product the advantages of current method；It is easy as reaction substrate as solvent and alkene to eliminate acetic acid
Inconvenience brought by autohemagglutination；It avoids using high-tension apparatus；The use of azeotrope with water organic solvent, solves solvent recovery and repetition
The problem of utilization) outside, also have and one kettle way is taken to feed, it is simple, quick and microwave-assisted reaction is rapid, greatly improve synthesis effect
Rate, the advantages that reducing process risk and cost.Therefore, synthetic method of the present invention more energy-saving and environmental protection, efficiently.
Detailed description of the invention
Fig. 1 is before embodiment 1 adds material31PNMR (THF is in situ) nuclear magnetic spectrogram；
Fig. 2 is after embodiment 1 adds material31PNMR (THF is in situ) nuclear magnetic spectrogram；
Specific embodiment
Following embodiment is further described to of the invention, and the limitation to its power is not constituted.
Embodiment 1
1.05g hypophosphorous acid (50% aqueous solution) is added into reactor, the 0.9g tert-butyl alcohol, contains two isobutyl of 0.04g azo
The 1.04g chlorobenzene solution and the 0.1g concentrated sulfuric acid of nitrile, are placed in microwave reactor.Stirring is opened, setting microwave power is 150
Watt, reaction temperature is 75 DEG C, reaction time 15min.A small amount of reaction solution is taken to carry out it31PNMR (THF is in situ) detection shows:
Raw material hypophosphorous acid substantially completely converts, and the phosphinic acids content that double isobutyl groups replace is 48% or so, time that single isobutyl group replaces
Phosphonic acids content is 52% or so.(see Fig. 1)
Added into reactor the 0.6g tert-butyl alcohol, the 0.52g chlorobenzene solution containing 0.02g azodiisobutyronitrile and
The 0.05g concentrated sulfuric acid, is placed in microwave reactor.Stirring is opened, setting microwave power is 150 watts, and reaction temperature is 75 DEG C, reaction
Time is 10min.After reaction, system is spin-dried for, obtains colorless oil, as isobutylphosphinic.To its carry out31PNMR (THF is in situ) detection shows: raw material hypophosphorous acid substantially completely converts, and the phosphinic acids content that double isobutyl groups replace is
86% or so, the phosphinic acids content that single isobutyl group replaces is 14% or so.(see Fig. 2)
Embodiment 2
1.05g hypophosphorous acid (50% aqueous solution) is added into reactor, the 0.9g tert-butyl alcohol, contains 0.06g diphenyl peroxide
The 1.04g chlorobenzene solution and the 0.1g concentrated sulfuric acid of formyl, are placed in microwave reactor.Stirring is opened, setting microwave power is 150
Watt, reaction temperature is 85 DEG C, reaction time 15min.
Added into reactor the 0.6g tert-butyl alcohol, the 0.52g chlorobenzene solution containing 0.03g dibenzoyl peroxide and
The 0.05g concentrated sulfuric acid, is placed in microwave reactor.Stirring is opened, setting microwave power is 150 watts, and reaction temperature is 85 DEG C, reaction
Time is 10min.After reaction, system is spin-dried for, obtains colorless oil, as isobutylphosphinic.To its carry out31PNMR (THF is in situ) detection shows: raw material hypophosphorous acid substantially completely converts, and the phosphinic acids content that double isobutyl groups replace is
82% or so, the phosphinic acids content that single isobutyl group replaces is 18% or so.
Embodiment 3
1.05g hypophosphorous acid (50% aqueous solution) is added into reactor, the 0.9g tert-butyl alcohol, contains two isobutyl of 0.04g azo
The 1.04g toluene solution and the 0.1g concentrated sulfuric acid of nitrile, are placed in microwave reactor, open stirring, and setting microwave power is 200
Watt, reaction temperature is 75 DEG C, reaction time 15min.
Added into reactor the 0.6g tert-butyl alcohol, the 0.52g toluene solution containing 0.02g azodiisobutyronitrile and
The 0.05g concentrated sulfuric acid, is placed in microwave reactor.Stirring is opened, setting microwave power is 200 watts, and reaction temperature is 75 DEG C, reaction
Time is 10min.After reaction, system is spin-dried for, obtains colorless oil, as isobutylphosphinic.To its carry out31PNMR (THF is in situ) detection shows: raw material hypophosphorous acid substantially completely converts, and the phosphinic acids content that double isobutyl groups replace is
83% or so, the phosphinic acids content that single isobutyl group replaces is 17% or so.
Embodiment 4
1.05g hypophosphorous acid (50% aqueous solution) is added into reactor, the 0.9g tert-butyl alcohol, contains two isobutyl of 0.04g azo
The 1.04g meta-xylene solution and the 0.1g concentrated sulfuric acid of nitrile, are placed in microwave reactor, open stirring, and setting microwave power is
150 watts, reaction temperature is 85 DEG C, reaction time 20min.
To reactor add the 0.6g tert-butyl alcohol, the 0.52g meta-xylene solution containing 0.02g azodiisobutyronitrile and
The 0.05g concentrated sulfuric acid, is placed in microwave reactor.Stirring is opened, setting microwave power is 150 watts, and reaction temperature is 75 DEG C, reaction
Time is 5min.After reaction, system is spin-dried for, obtains colorless oil, as isobutylphosphinic.To its carry out31PNMR (THF is in situ) detection shows: raw material hypophosphorous acid substantially completely converts, and the phosphinic acids content that double isobutyl groups replace is
82% or so, the phosphinic acids content that single isobutyl group replaces is 18% or so.
Embodiment 5
1.05g hypophosphorous acid (50% aqueous solution) is added into reactor, 1.44g isopropanol, contains two isobutyl of 0.04g azo
The 1.04g chlorobenzene solution and the 0.1g concentrated sulfuric acid of nitrile, are placed in microwave reactor.Stirring is opened, setting microwave power is 200
Watt, reaction temperature is 75 DEG C, reaction time 15min.
Added into reactor 0.72g isopropanol, the 0.52g chlorobenzene solution containing 0.02g azodiisobutyronitrile and
The 0.05g concentrated sulfuric acid, is placed in microwave reactor.Stirring is opened, setting microwave power is 200 watts, and reaction temperature is 75 DEG C, reaction
Time is 10min.After reaction, system is spin-dried for, obtains colorless oil, as propylphosphinic acid.To its carry out31PNMR
(THF is in situ) detection shows: raw material hypophosphorous acid substantially completely converts, and the phosphinic acids content that double propyl replace is 83% or so,
The phosphinic acids content that single propyl replaces is 17% or so.
Embodiment 6
1.05g hypophosphorous acid (50% aqueous solution) is added into reactor, 1.50g isobutanol, contains 0.06g diphenyl peroxide
The 1.04g chlorobenzene solution and the 0.1g concentrated sulfuric acid of formyl, are placed in microwave reactor, open stirring, and setting microwave power is 200
Watt, reaction temperature is 100 DEG C, reaction time 15min.
Added into reactor 0.9g isobutanol, the 0.52g chlorobenzene solution containing 0.03g dibenzoyl peroxide and
The 0.05g concentrated sulfuric acid, is placed in microwave reactor.Stirring is opened, setting microwave power is 200 watts, and reaction temperature is 105 DEG C, instead
It is 10min between seasonable.After reaction, system is spin-dried for, obtains colorless oil, as isobutylphosphinic.To its carry out31PNMR (THF is in situ) detection shows: raw material hypophosphorous acid substantially completely converts, and the phosphinic acids content that double isobutyl groups replace is
82% or so, the phosphinic acids content that single isobutyl group replaces is 18% or so.
Claims (9)
1. a kind of method using microwave technology one kettle way rapid synthesis alkyl phosphinic acid, which is characterized in that with hypophosphorous acid solution
It is raw material with alcohol, by means of, there are azeotropic point and immiscible organic solvent, under microwave-assisted, one kettle way is fast implemented with water
The synthesis of alkyl phosphinic acid, the specific steps are as follows:
(1) by 50% aqueous hypophosphorous acid and for the first time be added alcohol, inorganic acid, dissolved with initiator organic solvent in reactor
Middle mixing, is placed in microwave reactor；Stirring is opened, setting microwave power is 150~200 watts, reaction temperature is 75~105
DEG C, the reaction time control in 15~20min；
(2) alcohol, inorganic acid, the organic solvent dissolved with initiator is then added for the second time into reactor, is placed in microwave reaction
In device；Stirring is opened, microwave power and reaction temperature are constant, and the reaction time controls in 5~10min；
(3) after completion of the reaction, system vacuum backspin is removed into solvent, organic solvent recycles, and obtains alkyl phosphinic acid grease.
2. the method according to claim 1 using microwave technology one kettle way rapid synthesis alkyl phosphinic acid, feature exist
In alcohol described in step is any one of the tert-butyl alcohol, isobutanol, isopropanol；Mole of the alcohol and hypophosphorous acid that are added twice
Than being 1~3:1.
3. the method according to claim 1 using microwave technology one kettle way rapid synthesis alkyl phosphinic acid, feature exist
In the molar ratio of the alcohol and hypophosphorous acid that are added for the first time is 1.5:1, and the alcohol of second of addition and the molar ratio of hypophosphorous acid are 1:1.
4. the method according to claim 1 using microwave technology one kettle way rapid synthesis alkyl phosphinic acid, feature exist
In initiator described in step is azodiisobutyronitrile or azobisisoheptonitrile, perbenzoic acid, diphenyl peroxide first
One or more of acyl, di-tert-butyl peroxide, peroxycarbonates, peroxidized t-butyl perbenzoate；In step twice
The initiator of addition and the molar ratio of hypophosphorous acid are 0.01~0.10:1.
5. the method according to claim 1 using microwave technology one kettle way rapid synthesis alkyl phosphinic acid, feature exist
In initiator described in step is azodiisobutyronitrile；The azodiisobutyronitrile and hypophosphorous acid being added twice rubs
Your ratio is 0.01~0.10:1.
6. the method according to claim 1 using microwave technology one kettle way rapid synthesis alkyl phosphinic acid, feature exist
In inorganic acid described in step is one or more of sulfuric acid, hydrobromic acid, hydroiodic acid；The inorganic acid being added twice
Molar ratio with hypophosphorous acid is 0.05~0.3:1.
7. the method according to claim 1 using microwave technology one kettle way rapid synthesis alkyl phosphinic acid, feature exist
In inorganic acid described in step is the concentrated sulfuric acid；The molar ratio of the concentrated sulfuric acid and hypophosphorous acid that are added twice is 0.05~
0.3:1。
8. the method according to claim 1-7 using microwave technology one kettle way rapid synthesis alkyl phosphinic acid,
It is characterized in that, organic solvent described in step is toluene, chlorobenzene, meta-xylene, one or more of paraxylene；The
The mass ratio of the organic solvent and aqueous hypophosphorous acid that are once added is 0.5~2.0:1；Second organic solvent being added and time
The mass ratio of phosphate aqueous solution is 0.5~1.0:1.
9. the method according to claim 1-7 using microwave technology one kettle way rapid synthesis alkyl phosphinic acid,
It is characterized in that, organic solvent described in step is chlorobenzene；The matter of the chlorobenzene and aqueous hypophosphorous acid is added for the first time
Amount is than being 0.5~2.0:1；Second of mass ratio that the chlorobenzene and aqueous hypophosphorous acid is added is 0.5~1.0:1.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694273A (en) * | 2013-01-10 | 2014-04-02 | 中国科学院上海有机化学研究所 | Preparation method and application of dialkyl phosphinate compounds and salts thereof |
| CN107652321A (en) * | 2017-09-30 | 2018-02-02 | 济南泰星精细化工有限公司 | A kind of preparation method and applications of graininess alkyl phosphinic acid aluminium |
| CN108864182A (en) * | 2018-07-24 | 2018-11-23 | 济南泰星精细化工有限公司 | The synthetic method of alkyl phosphinic acid and its aluminium salt under a kind of normal pressure, temperate condition |
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2019
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694273A (en) * | 2013-01-10 | 2014-04-02 | 中国科学院上海有机化学研究所 | Preparation method and application of dialkyl phosphinate compounds and salts thereof |
| CN107652321A (en) * | 2017-09-30 | 2018-02-02 | 济南泰星精细化工有限公司 | A kind of preparation method and applications of graininess alkyl phosphinic acid aluminium |
| CN108864182A (en) * | 2018-07-24 | 2018-11-23 | 济南泰星精细化工有限公司 | The synthetic method of alkyl phosphinic acid and its aluminium salt under a kind of normal pressure, temperate condition |
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| Title |
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| 郑春满等: "《高等合成化学-方法与实践》", 30 September 2018, 国防工业出版社 * |
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