CN107188904A - The preparation method of monoalkyl hypophosphorous acid - Google Patents
The preparation method of monoalkyl hypophosphorous acid Download PDFInfo
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- CN107188904A CN107188904A CN201710520873.9A CN201710520873A CN107188904A CN 107188904 A CN107188904 A CN 107188904A CN 201710520873 A CN201710520873 A CN 201710520873A CN 107188904 A CN107188904 A CN 107188904A
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- Prior art keywords
- monoalkyl
- hypophosphorous acid
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- reaction
- phosphatization
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- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- -1 hydrogen halides Chemical class 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 10
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 8
- 239000001257 hydrogen Substances 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 6
- 239000000243 solution Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000006837 decompression Effects 0.000 abstract description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 25
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 14
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 150000003009 phosphonic acids Chemical class 0.000 description 3
- 238000004679 31P NMR spectroscopy Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- REJGOFYVRVIODZ-UHFFFAOYSA-N phosphanium;chloride Chemical compound P.Cl REJGOFYVRVIODZ-UHFFFAOYSA-N 0.000 description 2
- 238000000607 proton-decoupled 31P nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- RARSHUDCJQSEFJ-UHFFFAOYSA-N p-Hydroxypropiophenone Chemical compound CCC(=O)C1=CC=C(O)C=C1 RARSHUDCJQSEFJ-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 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
A kind of preparation method of monoalkyl hypophosphorous acid, by dimethylsulfoxide oxidation monoalkyl phosphatization halogen acid salt solution, the wherein mol ratio of monoalkyl phosphatization halogen acid salt solution and dimethyl sulfoxide is 1: 2 or 1: 2.1, and reaction temperature is between 50 DEG C to 20 DEG C.The molecular formula of monoalkyl hypophosphorous acid is RP (H) OOH, and wherein R is straight chain, branch chain type alkyl group of the carbon number between 1 to 6.The preparation method for the monoalkyl hypophosphorous acid that the present invention is provided, reaction yield is more than 80%, reaction, which terminates rear water and hydrogen halides, can easily pass through decompression and steam, it can be reclaimed afterwards by sodium hydroxide solution, although the main contents of the present invention are not intended as, therefore method described in the invention is safe and environment-friendly and economical.
Description
Technical field
The present invention relates to a kind of method for producing organic phosphoric compound, more particularly to a kind of preparation side of monoalkyl hypophosphorous acid
Method, realizes that reaction is safely controllable.
Background technology
The monoalkyl hypophosphorous acid of trivalent can be considered as a hydrogen atom being connected in hypophosphorous acid with phosphorus by alkyl-substituted production
There is its corresponding interconvertible isomeric form in thing, such compound, shown in formula I:
Such compound can be esterified as corresponding monoesters easily, and its hydrogen being connected with phosphorus can be by further converting
To dialkyl group substitutive derivative, such as free radical addition with different alkene or Michael additions, such as Formula II, formula III and formula IV
It is shown
R-P (H) (=O) OH+R1OH → R-P (H) (=O) OR1+H2O Formula II
R-P (H) (=O) OR1+R2 2C=CHR3→R-P[C(CHR2 2)HR3] (=O) OR1Formula III
R-PH (=O) OR1+R4CH=CHC (=O) R5+Base→R-[CHR4{CH2C (=O) R5] (=O) OR1Formula IV
Mono-substituted methyl hypophosphorous acid and corresponding ester are the important intermediates for synthesizing organophosphorus chemistry product, are worth mentioning
Have the cremart produced by Bayer companies and Clariant companies production MEPAL (methyl hypophosphorous acid aluminium salt) product
(US3914345A)。
It is the well-known method of comparison from oxidized phosphine oxide, hypophosphorous acid and the phosphonic acids compounds of preparing of primary phosphine.By
Generally all it is very sensitive to oxide in primary phosphine, or even some primary phosphine oxides are all unstable in atmosphere, so such as
Fruit expects the reply of hypophosphorous acid or phosphate compound with regard to necessary extreme care.Because such oxidation reaction would generally be a large amount of
Heat release, it is sometimes even dangerous almost uncontrollable, therefore the selection of oxidant is very crucial.
The primary aerial oxidation of phosphine can obtain the mixture of phosphonic acids and phosphoric acid, also have a small amount of hypophosphorous acid, product
Species (US2584112 unrelated with the concentration of oxygen;J.Chem.Soc., 58,766,1890).Only can in considerably less report
With see primary phosphine can by oxygen selectivity be oxidized to oxide or hypophosphorous acid (Z.Naturforsch.49b, 1511-1524,
1994).Furthermore, gaseous primary phosphine compound is mutually met and get along well spontaneous combustion at once and uncontrollable (Organic in air or oxygen
Phosphorous Compounds, Vol 1, p95;Phosphorus compounds, Organic, Ullmann ' s
Encyclopedia of Industrial Chemistry, 2000, Wiley-VCH Verlag GmbH&Co.KgaA).
Found in the report of the past few decades, for the normal quilt of hydrogen peroxide especially its aqueous solution in primary phosphine oxidation reaction
As suitable oxidant to synthesize mono-substituted alkyl hypophosphorous acid (Eur.J.Med.Chem., 45,2010,849;
J.Med.Chem.2006,49,7799-7806;Carbohydrate Research, 194,1989,209-221;
J.Org.Chem.1985,50,3516-3521;US8884011).Nevertheless, for the primary of short chain (1 to 4 carbon atoms)
Phosphine, never finds that related report confirms to obtain selective monosubstituted hypophosphorous acid;It is due to that the middle of reaction is produced with regard to its reason
The primary phosphine oxide of thing is sensitive and unstable, easily occurs the disproportionation such as Formula V and meeting is highly exothermic so that being difficult to control to.
R-PH2+H2O2→ [R-P (=O) H2]→R-PH2+ R-P (H) (=O) OH → R-P (=O) (OH)2+ R-P (H) (=
O)OH
Formula V
Therefore being highly desirable to one new technique of searching can allow primary phosphine be converted into corresponding monosubstituted hypophosphorous acid,
Safety can be ensured and accessory substance phosphonic acids caused by peroxidating or disproportionation is avoided as far as possible.Dimethyl sulfoxide is as good
Solvent and reactant are by extensive research (Techinical Bulletin Reaction Solvent Dimethyl
sulfoxide)。
The content of the invention
The purpose of the present invention is the shortcoming for overcoming prior art to exist, and the present invention provides a kind of preparation of monoalkyl hypophosphorous acid
Method, realization safely prepares monoalkyl hypophosphorous acid, and yield is more than 80%.
As the chemicals of highly dangerous, primary phosphine compound is extremely sensitive for oxidant.Carbon number is within 8
It is spontaneous combustion that primary phosphine, which meets air,.Such compound (ppb grades) in the case that concentration is extremely low can all have strong smell, and
All it is poisonous, especially alkyl chain shorter (Organic Phosphorous Compounds, Vol 1, p106).We
Also recall that primary phosphine compound can be considered weak base, and can be formed accordingly with non-oxidizing inorganic acid reaction easily
Salt compounds are (such as:PKa value of the normal-butyl phosphine in water be -0.03, and n-octyl for 0.43).These salt compounds are general
It is all relatively stable, soluble in water and insipidness, therefore be highly convenient for using and operate.Such acid without oxidisability has iodate
The concentrated solution of hydrogen, hydrogen bromide and hydrogen chloride, usually gas or water.
Primary phosphine halogenation hydrogen compound can be easily oxidized, and this process can accomplish safely controllable, obtain corresponding
Monoalkyl hypophosphorous acid.Because 35%~37% concentrated hydrochloric acid is cheap, so by the first choice as us.We use city
The dimethyl sulfoxide sold, typical temperature is controlled between -30 DEG C to 0 DEG C.The primary phosphine chlorination hydrogen compound used in reaction can pass through
Concentrated hydrochloric acid is obtained with corresponding primary phosphine reaction.
In the present invention molecular formula of monoalkyl hypophosphorous acid be RP (H) OOH, wherein R be carbon number between 1 to 6 straight chain
Or branched alkyl group, i.e. CnH2n+1, wherein n is 1,2,3,4,5 and 6, such as:Methyl, ethyl, n-propyl, 2- propyl group, normal-butyl,
Isobutyl group, the tert-butyl group, n-pentyl, isopentyl, neopentyl and hexyl etc..
The mol ratio of monoalkyl phosphatization halogen acid salt solution and dimethyl sulfoxide is stoichiometric proportion in the present invention, somewhat excessively
Dimethyl sulfoxide can receive, generally excessive 1% is relatively adapted to.
Protected in reaction using nitrogen.Temperature range in -50 DEG C to 20 DEG C, especially -20 DEG C between 0 DEG C, to ensure
Reaction can successfully carry out and avoid the generation of peroxidating as far as possible.Limit can reach reaction in a low temperature of being used in reaction
The crystallization temperature of thing or product.
The present invention provides a kind of preparation method of monoalkyl hypophosphorous acid, passes through dimethylsulfoxide oxidation monoalkyl phosphatization halogen acids
Salting liquid, wherein monoalkyl phosphatization halogen acid salt solution and DMSO mol ratio are 1: 2 or 1: 2.1, and reaction temperature is between -50 DEG C
To 20 DEG C, reaction yield is more than 80%, especially 90%, even close to 100%.
The present invention provides the preparation method of another monoalkyl hypophosphorous acid, passes through dimethylsulfoxide oxidation monoalkyl phosphatization hydrogen salt
Acid salt solution, wherein monoalkyl phosphine hydrochloride solution and DMSO mol ratio are 1: 2 or 1: 2.1, and reaction temperature is between -20
DEG C to 0 DEG C, reaction yield is more than 80%, especially 90%, even close to 100%.
Reaction equation is as shown in Formula IV:
Reaction, which terminates rear water and hydrogen halides, can easily pass through decompression and steam, and can be returned afterwards by sodium hydroxide solution
Receive, although the main contents of the present invention are not intended as, therefore method described in the invention is safe and environment-friendly and economical.
Embodiment
Technical scheme described in detail below.The embodiment of the present invention be merely illustrative of the technical solution of the present invention and
It is unrestricted, although the present invention is described in detail with reference to preferred embodiment, it will be understood by those within the art that,
The technical scheme of invention can be modified or equivalent substitution, without departing from the spirit and scope of technical solution of the present invention,
It all should cover in scope of the presently claimed invention.
The synthesis of the methyl hypophosphorous acid of embodiment 1
The phosphine hydrochloride of methyl containing 21.2g is added into the three-necked flask equipped with two liters of mechanical agitation and dropping funel
The aqueous solution of (0.44mol), and 69 grams of dimethyl sulfoxides (0.89mol) of addition in dropping funel.Flask is placed into a setting temperature
Spend in the cooling bath for 0 DEG C to -20 DEG C.Dimethyl sulfoxide made flask interior temperature under agitation through 2 hours after completion of dropping
Rise to 50 DEG C.It is removed under reduced pressure after volatile matter and obtains 36.1 grams of colourless liquids, yield is close to 100%.
Nuclear magnetic data:31P{1H}NMR(CDCl3):32.35ppm(s);31P NMR(CDCl3):32.35ppm (dd,1JH, P=
557Hz,3JH, P=15Hz).
Total phosphorus content:36.7%, theoretical phosphorus amount:38.75%.
The synthesis of the isobutyl group hypophosphorous acid of embodiment 2
The phosphatization hydrogen salt of isobutyl group containing 568.7g is added into the three-necked flask equipped with two liters of mechanical agitation and dropping funel
The aqueous solution of hydrochlorate (1.05mol), and 170 grams of dimethyl sulfoxides (2.18mol) of addition in dropping funel.Flask is placed into one and set
Put in the cooling bath that temperature is 0 DEG C to -20 DEG C.Dimethyl sulfoxide made flask interior temperature reach room temperature through 6 hours after completion of dropping,
And continue stirring 8 hours.It is removed under reduced pressure after volatile matter and obtains 134.4 grams of colourless liquids, yield is close to 100%.
Nuclear magnetic data:31P{1H}NMR(CDCl3):δ=36.86ppm (s);31P NMR(CDCl3):δ=36.86ppm
(dm,1JH, P=546Hz).
Claims (6)
1. a kind of preparation method of monoalkyl hypophosphorous acid, it is characterised in that pass through dimethylsulfoxide oxidation monoalkyl phosphatization halogen acid salt
Solution, the wherein mol ratio of monoalkyl phosphatization halogen acid salt solution and hydrogen peroxide are 1: 2 or 1: 2.1, and reaction temperature is between -50
DEG C to 20 DEG C, reaction yield is more than 80%.
The molecular formula of described monoalkyl hypophosphorous acid be RP (H) OOH, wherein R be carbon number between 1 to 6 straight or branched
Type alkyl group.
2. the preparation method of monoalkyl hypophosphorous acid according to claim 1, it is characterised in that it is hydrogen chloride to use halogen acids.
3. the preparation method of monoalkyl hypophosphorous acid according to claim 1, it is characterised in that be using commercially available concentration
35%~37% hydrochloride aqueous solution.
4. the preparation method of monoalkyl hypophosphorous acid according to claim 1, it is characterised in that the temperature range is at -20 DEG C
To between 0 DEG C.
5. the preparation method of monoalkyl hypophosphorous acid according to claim 1, it is characterised in that the yield is more than 90%.
6. the preparation method of monoalkyl hypophosphorous acid according to claim 1, it is characterised in that the yield is close to 100%.
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Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4839105A (en) * | 1984-01-21 | 1989-06-13 | Hoechst Aktiengesellschaft | Process for the preparation of alkanephosphonous acids |
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2017
- 2017-06-29 CN CN201710520873.9A patent/CN107188904A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4839105A (en) * | 1984-01-21 | 1989-06-13 | Hoechst Aktiengesellschaft | Process for the preparation of alkanephosphonous acids |
Non-Patent Citations (2)
Title |
---|
尹志刚 主编: "《有机磷化合物》", 31 March 2011 * |
陈金龙 主编: "《精细有机合成原理与工艺》", 30 April 1992 * |
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