CN108610366A - A method of preparing bicycloheptyl phosphinic acids - Google Patents
A method of preparing bicycloheptyl phosphinic acids Download PDFInfo
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- CN108610366A CN108610366A CN201611151324.0A CN201611151324A CN108610366A CN 108610366 A CN108610366 A CN 108610366A CN 201611151324 A CN201611151324 A CN 201611151324A CN 108610366 A CN108610366 A CN 108610366A
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- phosphinic acids
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- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000002253 acid Substances 0.000 title claims abstract description 21
- 150000007513 acids Chemical class 0.000 title claims abstract description 20
- ARUKYTASOALXFG-UHFFFAOYSA-N cycloheptylcycloheptane Chemical group C1CCCCCC1C1CCCCCC1 ARUKYTASOALXFG-UHFFFAOYSA-N 0.000 title claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 230000036571 hydration Effects 0.000 claims abstract description 9
- 238000006703 hydration reaction Methods 0.000 claims abstract description 9
- 239000000047 product Substances 0.000 claims abstract description 9
- 238000001514 detection method Methods 0.000 claims abstract description 6
- MAWOHFOSAIXURX-UHFFFAOYSA-N cyclopentylcyclopentane Chemical group C1CCCC1C1CCCC1 MAWOHFOSAIXURX-UHFFFAOYSA-N 0.000 claims abstract description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 36
- 238000000605 extraction Methods 0.000 claims description 28
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 239000012044 organic layer Substances 0.000 claims description 15
- 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 claims description 11
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 239000010410 layer Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 239000006227 byproduct Substances 0.000 abstract description 8
- 150000001336 alkenes Chemical class 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000010865 sewage Substances 0.000 abstract description 4
- 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 abstract description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000036632 reaction speed Effects 0.000 abstract description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 abstract description 2
- 238000006467 substitution reaction Methods 0.000 abstract description 2
- 239000003999 initiator Substances 0.000 abstract 1
- 229910052770 Uranium Inorganic materials 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 8
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 6
- 239000000284 extract Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000000638 solvent extraction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- -1 metals ion Chemical class 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003747 Grignard reaction Methods 0.000 description 3
- 239000007818 Grignard reagent Substances 0.000 description 3
- 150000004795 grignard reagents Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229910052776 Thorium Inorganic materials 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 206010051093 Cardiopulmonary failure Diseases 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 208000005392 Spasm Diseases 0.000 description 1
- 206010044565 Tremor Diseases 0.000 description 1
- 206010047700 Vomiting Diseases 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical compound CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 210000000936 intestine Anatomy 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 231100000518 lethal Toxicity 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000956 solid--liquid extraction Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002351 wastewater 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)]
- C07F9/303—Cycloaliphatic acids
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 preparing bicycloheptyl phosphinic acids, and using a hydration sodium hypophosphite and alkene as primary raw material, acetic acid is solvent, and di-tert-butyl peroxide is initiator, and a small amount of industry mixing decene synthesizes bicyclopentyl phosphinic acids；A small amount of mixing decene is added in the preparation method of the present invention, greatly accelerate reaction speed, yield is improved to 91% or more, in addition to having a small amount of monosubstituted by-product generation (＜ 5%) when some olefin reacts, essentially eliminate the influence of a substitution by-product, reactions steps of this method is simple, yield higher.Products application of the present invention is in water quality detection and sewage treatment industry.
Description
Technical field
The invention belongs to technical field of phosphorous chemical industry, and in particular to the preparation of trialkyl phosphorus intermediate dialkyl phosphinic acid
Method.
Background technology
Extraction refers to compound because of the solubility in two kinds of mutual solubility very littles or fairly insoluble solvent
(distribution coefficient) is different, to partially or completely enter one of which solvent.When the number of extraction is enough, compound will be complete
Enter one of which solvent entirely.
Extractant is various in style, generally comprises inorganic and organic extractant.And most of used in industrial production are
Organic extractant has good dissolubility in organic solvent.It is allowed to be dissolved in organic solvent to be waited for metal to increase it
Extract the dissolubility of object, and enhance its extraction ability, while its volatility can also be weakened, viscosity, and it is water-soluble.Organic extractant
It is largely used to non-ferrous metal hydrometallurgy industry, is mainly used for extracting copper and various noble metals and rare earth.
There are many kinds of the methods of extraction, generally comprises solvent extraction, solid-liquid extraction (leaching), chemical precipitation method, tree
Fat method, aqueous two-phase method, oxidation-reduction method, floatation and electric stripping process.
What is be wherein most widely used is the precipitation method and solvent extraction.The precipitation method are mainly used for sewage disposal, method master
If adding specific chemical reagent into sewage, it is made to react with the substance to be handled being dissolved in waste water, generated
It is insoluble in the precipitation of salts of water, to which success is removed from sewage.But due to the use of a large amount of chemical reagent, which can cause greatly
The secondary pollution of amount is unfavorable for the green environment advocated energetically now close friend and sustainable development, and is of limited application.
Solvent-extracted extraction process is full liquid process, and two kinds of liquid phases of participation process are respectively water phase and organic phase.Water
The density of phase is typically larger than used organic phase density so that after static layering, organic phase is always located in above water phase.Solvent
The element that extraction can be used to handle tonne in the industry, can be used for laboratory treatment gram and the element of milligram grade separation and
Enrichment.Solvent extraction is because of spies such as its operation is very simple while cheap, rate of extraction fast, high selectivity, separation rate height
Point has become an indispensable basic fundamental, industrially in the Separation ＆ Purification of current every field
It has been obtained for being widely applied, and wherein most has obtained good effect.Solvent extraction is research in recent years
Red heat point.
Organic phosphates extractant is one of several main extractants of solvent extraction extracting metals ion now, so far for
Only it is widely used to numerous areas.Organic phosphates extractant is various in style, various structures, but generally speaking, in being generally divided into
Property phosphorous and acidic phosphorus type two major classes.
At 1945, people have found that tributyl phosphate (TBP) has effects that extract uranium for the first time.From then on, TBP is gradually
It is taken seriously, till now, is used to post-process nuclear fuel in the world, extract the elements such as thorium therein, uranium.
TBP can degrade under high temperature and radiation and generate dibutylphosphoric acid ester (DBP) and monobutyl phosphate (MDP), but DBP and MDP to zirconium,
Niobium member is known as higher mating capability, in addition, DBP and MDP can be combined into thorium, zirconium etc. both it is not soluble in water be also insoluble in it is organic molten
The substance of agent, a large amount of precipitation can cover whole system, extraction efficiency caused to drastically reduce.Therefore, the use of TBP extractants
Service life is very short.
Therefore, people begin one's study modified technique flow, and have carried out research extensively and profoundly to phosphorus-contained extractant.People
It was found that when using D2When EHPA makees extractant, two different amine solvents are screened, such as ethylene diamine, 1,2- propane diamine, 1,3- the third two
The extraction yield of amine etc., uranium can promote 18~36 times.On the other hand, if in neutral ligand, such as dihexyl-N, N- diethyl
Tributyl phosphate and trioctylphosphine oxide are added in base-carbamyl phosphate methyl esters, the extraction efficiency of uranium ion can be greatly improved.When
Tributyl phosphate (TBP), trioctylphosphine oxide (TOPO), D2EHPA is mixed when making extractant, and effect of extracting is very good.
The uranium mill in China is all extracting uranium ion using eluex process mostly, which uses organophosphor as extraction
Agent, the i.e. di-(2-ethylhexyl)phosphoric acid (D of 0.2mol/L2EHPA) with the trialkyl phosphorus of 0.1mol/L (TRPO) system,
The uranium product purity obtained by this flow is high not enough, wherein still containing various metals impurity.This crude product need to pass through TBP
Purified product can be obtained after extraction process is refined, it is pure to reach core.
Trioctylphosphine oxide is widely used in the extraction of uranium in industry, usually with the D of different proportion2EHPA is combined, extraction effect
Rate is all very high, but has realized that industrialized trialkyl phosphorus also only has trioctylphosphine oxide therefore to research and develop other at present
The industrialized production route of trialkyl phosphorus has great importance to finding new efficient extractant.
There are two types of the methods of the synthesis trialkyl phosphorus of mainstream in the world：Grignard reagent method and hydrogen phosphide synthetic method are led to
It crosses grignard reaction and prepares trioctylphosphine oxide, the biggest advantage is to need to only can be obtained product by single step reaction, and produce
Object purity is very high.It is well known that grignard reaction has disadvantages that：Operation difficulty is high, and the condition for preparing Grignard Reagent is very tight
Lattice, for Grignard Reagent to water and oxygen all extreme sensitivities, yield is generally very low.Grignard reaction condition is too harsh, is not suitable for out very much
Send out into industrial manufacture process.Hydrogen phosphide addition process, product purity is relatively low, there is many impurity and by-product.In addition, used original
Expect phosphatization.Hydrogen is also violent in toxicity, not only irritant but also be system.Toxic agent, if sucking can be to heart, respiratory system.Kidney, intestines
Stomach, nervous system.Damaged with liver, gently then cause to shed tears, cough, dizziness, headache, the symptoms such as nausea and vomiting, it is heavy then can
It can cause to tremble, spasm, cardiorespiratory failure and death.Concentration reaches 9.7mg/m3It will cause to be poisoned above；550~
830mg/m3Dead, 2798mg/m occurs for 0.5~1.0 hour for contact3It can be rapid lethal.And the hydrogen phosphide of trace in air can
Spontaneous combustion, the aerial concentration of hydrogen phosphide reach 1.8% (26g/m3) more than can explode.
Neutral organophosphorus extractant is widely used in the extraction process of uranium, they generally have very high selectivity to uranium
With certain chemical radiation stability, but carried out currently on the market industrialized production only three n-octyl phosphorous oxides, and
Production method is more toxic or low yield, it is still desirable to be improved, and be needed to develop a greater variety of trialkyl phosphorus
Production method.
Invention content
In view of this, the purpose of the present invention is to provide a kind of systems of trialkyl phosphorus intermediate bicycloheptyl phosphinic acids
Preparation Method, using a hydration sodium hypophosphite and alkene as primary raw material, acetic acid is solvent, and di-tert-butyl peroxide is to cause
Agent, a small amount of industry mixing decene synthesize bicycloheptyl phosphinic acids.
To achieve the above object, the present invention provides the following technical solutions：
A method of preparing bicycloheptyl phosphinic acids, be added in polytetrafluoro autoclave a hydration phosphinic acids sodium,
Acetic acid, cycloheptene, di-tert-butyl peroxide, and a small amount of industry mixing decene is added, stirring and dissolving is warming up to 130~140 DEG C
Reaction,31The reaction was complete for P-NMR detections, and the dissolving washing of 5~15wt% dilute sulfuric acids is added in reaction solution, chloroform extraction is used in combination,
Organic layer is washed with water to neutrality, and chloroform and unreacted solvent is evaporated off in Rotary Evaporators, with 5~15wt% potassium hydroxide
Solution dissolving crude product takes organic layer, water layer to be adjusted to neutrality with chloroform extraction, with chloroform extraction, distillation washing
It washs, merges organic layer, solvent is evaporated off in Rotary Evaporators, is dried in vacuo, obtains light yellow product bicyclopentyl phosphinic acids.
Preferably, the addition of the di-tert-butyl peroxide is be hydrated phosphinic acids sodium and cycloheptene gross mass 5
~8%.
Preferably, the addition of the described industry mixing decene be hydration phosphinic acids sodium and cycloheptene gross mass 2~
5%.
Preferably, a hydration phosphinic acids sodium, acetic acid, cycloheptene, di-t-butyl mistake are added in polytetrafluoro autoclave
Oxide, and a small amount of industry mixing decene is added, stirring and dissolving is warming up to 135 DEG C of reactions.
Preferably, a concentration of 8wt% of the dilute sulfuric acid.
Preferably, a concentration of 8wt% of the potassium hydroxide solution.
A small amount of mixing decene is added in the preparation method of the present invention, greatly accelerates reaction speed, improves yield to 91%
More than, in addition to a small amount of monosubstituted by-product generation (＜ 5%) is had when some olefin reacts, essentially eliminate a substitution by-product
Influence, reactions steps of this method is simple, yield higher.
Specific implementation mode
Technical solution in the embodiment of the present invention is described in detail below, it is clear that described embodiment is only
It is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill
The every other embodiment that personnel are obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1
2g mono- is added in polytetrafluoro autoclave and is hydrated phosphinic acids sodium (0.019mol), 4g acetic acid, cycloheptene
(4.5g, 0.047mol), 0.2g di-tert-butyl peroxides mix decene on a small quantity, and stirring and dissolving is warming up to 140 DEG C, reaction 24
Hour,31The reaction was complete for P-NMR detections, has a small amount of monosubstituted by-product to generate (＜ 5%).It is molten that 5wt% dilute sulfuric acids are added in reaction solution
Solution washing, is used in combination chloroform extraction, and organic layer is washed with water to neutrality, and chloroform and unreacted is evaporated off in Rotary Evaporators
Solvent.With 5wt% potassium hydroxide solutions dissolving crude product organic layer is taken with chloroform extraction.Water layer is adjusted to neutrality, with three
Chloromethanes extracts, and distills water washing, merges organic layer, and solvent is evaporated off in Rotary Evaporators, is dried in vacuo, obtains light yellow product.
Yield 91.4%.
Embodiment 2
2g mono- is added in polytetrafluoro autoclave and is hydrated phosphinic acids sodium (0.019mol), 4g acetic acid, cycloheptene
(4.5g, 0.047mol), 0.5g di-tert-butyl peroxides mix decene on a small quantity, and stirring and dissolving is warming up to 130 DEG C, reaction 24
Hour,31The reaction was complete for P-NMR detections, has a small amount of monosubstituted by-product to generate (＜ 5%).15wt% dilute sulfuric acids are added in reaction solution
Dissolving washing, is used in combination chloroform extraction, organic layer to be washed with water to neutrality, chloroform and unreacted is evaporated off in Rotary Evaporators
Solvent.With 15wt% potassium hydroxide solutions dissolving crude product organic layer is taken with chloroform extraction.Water layer is adjusted to neutrality, uses
Chloroform extraction distills water washing, merges organic layer, and solvent is evaporated off in Rotary Evaporators, is dried in vacuo, obtains faint yellow production
Product.Yield 91.8%.
Embodiment 3
2g mono- is added in polytetrafluoro autoclave and is hydrated phosphinic acids sodium (0.019mol), 4g acetic acid, cycloheptene
(4.5g, 0.047mol), 0.3g di-tert-butyl peroxides mix decene on a small quantity, and stirring and dissolving is warming up to 135 DEG C, reaction 24
Hour,31The reaction was complete for P-NMR detections, has a small amount of monosubstituted by-product to generate (＜ 5%).It is molten that 8wt% dilute sulfuric acids are added in reaction solution
Solution washing, is used in combination chloroform extraction, and organic layer is washed with water to neutrality, and chloroform and unreacted is evaporated off in Rotary Evaporators
Solvent.With 8wt% potassium hydroxide solutions dissolving crude product organic layer is taken with chloroform extraction.Water layer is adjusted to neutrality, with three
Chloromethanes extracts, and distills water washing, merges organic layer, and solvent is evaporated off in Rotary Evaporators, is dried in vacuo, obtains light yellow product.
Yield 93.0%.
For those skilled in the art, it is clear that invention is not limited to the details of the above exemplary embodiments, and not
In the case of the spirit or essential attributes of the present invention, the present invention can be realized in other specific forms.Therefore, no matter from
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended right
It is required that rather than above description limit, it is intended that all changes that will be fallen within the meaning and scope of the equivalent requirements of the claims
Change is included within the present invention.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiment being appreciated that.
Claims (6)
1. a kind of method preparing bicycloheptyl phosphinic acids, which is characterized in that include the following steps：
A hydration phosphinic acids sodium, acetic acid, cycloheptene, di-tert-butyl peroxide are added in polytetrafluoro autoclave, and adds
Entering a small amount of industry mixing decene, stirring and dissolving is warming up to 130~140 DEG C of reactions,31The reaction was complete for P-NMR detections, in reaction solution
The dissolving washing of 5~15wt% dilute sulfuric acids is added, chloroform extraction, organic layer is used in combination to be washed with water to neutrality, Rotary Evaporators
Chloroform and unreacted solvent is evaporated off, dissolves crude product with 5~15wt% potassium hydroxide solutions, with chloroform extraction,
It takes organic layer, water layer to be adjusted to neutrality, with chloroform extraction, distills water washing, merge organic layer, Rotary Evaporators are evaporated off molten
Agent, vacuum drying, obtains light yellow product bicyclopentyl phosphinic acids.
2. according to the method described in claim 1, it is characterized in that：The addition of the di-tert-butyl peroxide is hydration
The 5~8% of phosphinic acids sodium and cycloheptene gross mass.
3. according to the method described in claim 1, it is characterized in that：The addition of the industry mixing decene is hydration time phosphine
The 2~5% of sour sodium and cycloheptene gross mass.
4. according to the method described in claim 1, it is characterized in that：A hydration phosphinic acids are added in polytetrafluoro autoclave
Sodium, acetic acid, cycloheptene, di-tert-butyl peroxide, and a small amount of industry mixing decene is added, stirring and dissolving is warming up to 135 DEG C instead
It answers.
5. according to the method described in claim 1, it is characterized in that：A concentration of 8wt% of the dilute sulfuric acid.
6. according to the method described in claim 1, it is characterized in that：A concentration of 8wt% of the potassium hydroxide solution.
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Application publication date: 20181002 |