CN1257869A - Diphenylphosphinomethyl substituted aminoalkyl phosphonic acid, its salts and their synthesis process - Google Patents

Abstract

A process for synthesizing diphenyl phosphinomethyl substituted aminoalkyl phosphonic acid and its salts features that the quaternary phosphonium salt of dihydroxymethyl diphenyl phosphonium chloride reacts with aminoalkylphosphonic acid, aminoalkylphosphonate solution or suspension, and the reaction medium is regulated to alkaline by organic or inorganic alkali. The resultant product has strong complex power for Co, Ni, Pt, Rh, Pd, Ru and Ir. Its Na, K and ammonium salts are water-soluble and its Ti, Zr and Sn salts are the layer carrier with a certain specific surface area, which can be used to prepare water-soluble or solid-carried catalyst for complexing transition metals.

Description

The methyl substituted amine alkyl of diphenyl phosphine phosphonic acids, phosphonate and synthetic method thereof

The invention belongs to the new chemical materials field.The synthetic N-of institute diphenyl phosphine methyl substituted amine alkyl phosphonic acids of the present invention and salt thereof are the good ligand transition metals of a class, can be used for preparing water miscible and transition metal complex catalysts loading type, thereby realize the Separation and Recovery and the repeated use of transition-metal catalyst.The transition metal complex catalysts of the water-soluble or loading type that is made by product of the present invention is a class high-tech product, is again that a class is easy to Separation and Recovery and reusable environmental friendliness Green Chemistry is urged agent.

The catalytic hydrogenation of transition metal complex catalysts, oxidation, especially oxonation can be produced Chemicals thousands of and millions of tons.In national economy and social development, has extremely important status.The Separation and Recovery of these transition-metal catalysts and repeated use are the research focuses that recent two decades comes catalytic field, also are the biggest obstacles of these important reaction industry application.One of present terms of settlement both domestic and external is to trend towards developing water miscible phosphine part, to prepare corresponding water-soluble transition metal complex catalyst, catalyzed reaction is carried out at water-organic two-phase interface, rear catalyst and the product water-organic two-phase of living apart is automatically finished in reaction, and the Separation and Recovery process of catalyzer is simplified greatly.

Two of the way of solution transition-metal catalyst Separation and Recovery is that heterogenize is load, and the homogeneous phase complex catalyst is carried on the advantage that can not only keep original catalyzer on the solid material, can also keep or improve the stability of catalyzer.After reaction finished, catalyzer can separate with reaction system and reuse after filtration.

The methyl substituted amine alkyl of the N-diphenyl phosphine phosphonic acids of the present invention's development has following basic structure

Ph ₂PCH ₂-NR(CH ₂CH ₂Y) _m-(CH ₂) _n-PO ₃H ₂

Y=NR wherein, O; R=Ph ₂PCH ₂, alkyl, heterocyclic radical, the methyl substituted heterocyclic radical of N-diphenyl phosphine, (CH ₂) _nOH, (CH ₂) _nCO ₂H, (CH ₂) _nSO ₃H, m=0.1.2.3. ..., n=1.2.3.4. Its sodium, potassium, lithium, ammonium salt etc. are water miscible, its titanium, zirconium, tin,, lead, zinc, barium salt etc. is the solid that is insoluble in water.Owing to contain strong coordinating group such as diphenyl phosphine methyl and amine in the molecule, transition metal ions such as cobalt, nickel, platinum, rhodium, palladium, ruthenium, iridium there is very strong ligand complex ability, can be respectively applied for the transition metal complex catalysts for preparing water-soluble and loading type, thereby the Separation and Recovery and the repeated use of transition-metal catalyst are realized in the ground of killing two birds with one stone.This class is that the phosphine ligand molecular of structure is not seen bibliographical information both at home and abroad as yet, has international initiative.Synthesis technique of the present invention is as follows:

Dihydroxymethyl Er Ben Ji Phosphonium muriate quaternary alkylphosphonium salt is dissolved in methanol aqueous solution by calculated amount (calculated amount is and desires to carry out moles such as the methyl substituted N-H key of diphenyl phosphine); under nitrogen protection, add and contain in the solution or suspension of amine alkyl phosphonic acids or amine alkyl phosphonate; add organic or inorganic alkali conditioned reaction medium again to alkalescence; heating reflux reaction 1～5h; the conditioned reaction medium is to neutrality or slightly acidic; crystallisation by cooling is crossed the diafiltration washing and just can be obtained N-diphenyl phosphine methyl substituted amine alkyl phosphonic acids and salt thereof.

Embodiment one (standard method):

2-amine ethylphosphonic acid 25g (0.2mol) heating is dissolved in the 100ml deionized water, places the 500ml there-necked flask.Other gets dihydroxymethyl phenylbenzene muriate 113g (0.4mol) and is dissolved in 1: 2 methanol aqueous solution of 150ml, places dropping funnel.Under nitrogen protection; constantly stir down in room temperature; quaternary alkylphosphonium salt solution is splashed in the phosphonic acids aqueous solution; adding afterreaction liquid can become turbid, and slowly drips 0.4mol triethylamine (40.4g) and yellow soda ash 0.2mol (21.2g)/50ml aqueous solution, and this moment, the pH value of medium was about 8～9; heating reflux reaction 3h; cooling is acidified to pH=4～5 with 1: 1 hydrochloric acid soln, has a large amount of white crystals to separate out; cold filtration; methanol-water washing in 1: 2 merges washings and filtrate, and the big step of pressure reducing and steaming is divided methanol aqueous solution; the part crystal is separated out in cooling again; filtration washing merges crystal, and vacuum-drying to constant weight obtains N; the two diphenyl phosphine methylamine ethylphosphonic acid crystal 103.6g of N-, yield 99.5%.With N; the two diphenyl phosphine methylamine ethylphosphonic acids of N-are dissolved in an amount of methyl alcohol or ethanol; under nitrogen protection, add the sodium hydroxide solution that waits mole or two times of molar weights lentamente; stir, white crystal, filtration washing are separated out in cooling; vacuum-drying is to constant weight; can make N, the single sodium salt or the disodium salt of the two diphenyl phosphine methylamine ethylphosphonic acids of N-, transformation efficiency＞99%.Its sylvite, lithium salts, ammonium salt can prepare by the same method.Difficulty soluble salt solids such as corresponding titanium, zirconium, tin, lead, zinc, barium are by the method preparation of patent CN 95 1 11422.0 or CN 96 117605.9.Embodiment two:

By quadrol-N-ethylphosphonic acid and dihydroxymethyl Er Ben Ji Phosphonium muriate is raw material, by 1: 2 mol ratio, can make N ' by embodiment one, N '-two diphenyl phosphine methyl ethylenediamines-N-ethylphosphonic acid and salt thereof.Embodiment three: with unformed the mix phosphonic acids-phosphoric acid zirconates of quadrol-N-ethylphosphonic acid with phosphoric acid

Zr (HPO ₄) (O ₃PCH ₂CH ₂NHCH ₂CH ₂NH) _0.65H ₂O powder 0.1mol (34.7g) places there-necked flask to form suspension liquid with the 150ml deionized water; other gets dihydroxymethyl Er Ben Ji Phosphonium muriate and is dissolved in methanol aqueous solution; place dropping funnel; under nitrogen protection; constantly stir down in the suspension liquid of quaternary alkylphosphonium salt drips of solution adding there-necked flask in room temperature; slowly be added dropwise to triethylamine again to keep medium pH＞8; heating reflux reaction 5h; cooling; be acidified to pH=5～6 with 1: 1 hydrochloric acid soln; cold filtration, methanol-water washing in 1: 2, vacuum-drying is to constant weight; obtain part N-H key and be close to 100% by the transformation efficiency of the unformed mixed phosphate zirconates powder 50.5g quaternary alkylphosphonium salt of the methyl substituted quadrol of diphenyl phosphine-N-ethylphosphonic acid and phosphoric acid, the diphenyl phosphine methyl substituted rate of N-H key is close to 40%, and mainly be the surface and the interlayer face on the N-H key reaction has taken place.

Claims (7)

1, the methyl substituted amine alkyl of diphenyl phosphine phosphonic acids, phosphonate and synthetic method thereof; it is characterized in that the dihydroxymethyl Er Ben Ji Phosphonium muriate quaternary alkylphosphonium salt of calculated amount is dissolved in methanol aqueous solution; under nitrogen protection; add and contain in the solution or suspension of amine alkyl phosphonic acids or amine alkyl phosphonate; add organic bases or mineral alkali conditioned reaction medium again to alkalescence; add hot-fluid reaction 1-5h, cold filtration just can obtain N-diphenyl phosphine methyl substituted amine alkyl phosphonic acids and salt thereof.Contain strong coordinating group such as diphenyl phosphine methyl and amine in the products obtained therefrom molecule of the present invention, transition metal ions such as cobalt, nickel, platinum, rhodium, palladium, ruthenium, iridium are had very strong ligand complex ability.Its sodium, potassium, lithium, ammonium salt etc. are water miscible, its titanium, zirconium, tin, lead, etc. tetravalent metal salt be layered vector with certain specific surface area, the transition metal complex catalysts for preparing water-soluble and solid-carrying type be can be respectively applied for, thereby the Separation and Recovery and the repeated use of transition metal complex catalysts realized.

2, according to the described product of claim 1, it is characterized in that amine alkyl phosphonic acids, phosphonate that the present invention is used, mainly be to contain one to all kinds of replacements of several N-H keys and unsubstituted amine alkyl phosphonic acids, heterocyclic polyamines alkyl phosphonic acids RR ' N (CH2CH2Y) m-(CH2) n-PO3H2 (Y=NR wherein, O; R, R '=H, alkyl, heterocyclic radical, (CH2) nOH, (CH2) nCO2H, (CH2) nSO3H, n=1,2,3,4 ..., m=0,1,2,3,4 ...); Above-mentioned these phosphonic water-soluble salts such as sodium, potassium, lithium, ammonium salt; Also can be salt such as these phosphonic solid difficulty soluble salts such as titanium, zirconium, tin, lead, zinc, barium; Also to contain synthetic, the semi-synthetic or natural high moleculer eompound of N-H key and phosphonic.

3,, it is characterized in that the used reagent of the present invention is dihydroxymethyl Er Ben Ji Phosphonium muriate quaternary alkylphosphonium salt or its precursor raw material according to the described product of claim 1.Its usage quantity is and desires to carry out mole such as the methyl substituted N-H key of diphenyl phosphine.

4, according to the described product of claim 1, it is characterized in that the organic bases that uses among the present invention and mineral alkali can be all kinds of tertiary amines such as Trimethylamine 99, triethylamine, N, N one xylidene(s), pyridine also can be yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus, sodium hydroxide, potassium hydroxide etc.Its usage quantity is to make medium keep alkalescence in reaction.

5,, it is characterized in that the reaction medium that uses among the present invention can be water, methanol aqueous solution and other mixed solvents according to the described product of claim 1.

6, according to the described product of claim 1, it is characterized in that reaction of the present invention can be a homogeneous reaction, promptly amine alkyl phosphonic acids or its salt are dissolved in reaction medium solution entirely, and reagent dihydroxymethyl Er Ben Ji Phosphonium muriate also is dissolved in reaction medium solution entirely; Reaction also can be a heterogeneous reaction, and promptly amine alkyl phosphonic acids or its salt are partially soluble in or are insoluble to reaction medium solution, with the form participation reaction of suspension.

7, according to the described product of claim 1, the product that it is characterized in that gained of the present invention can be the open chain of each class formation and contain the methyl substituted amine alkyl of heterocyclic N-diphenyl phosphine phosphonic acids; Can be above-mentioned these phosphonic water-soluble salts such as sodium, potassium, lithium, ammonium salt; Also can be salt such as these phosphonic solid difficulty soluble salts such as titanium, zirconium, tin, lead, zinc, barium; Also can be that to contain all or part of N-H key be synthetic, the semi-synthetic or natural high moleculer eompound of methyl substituted amine of diphenyl phosphine and phosphonic.