CN102485729A

CN102485729A - Application of carboxylic acid in preparation of glyphosate, glufosinate-ammonium and intermediate thereof

Info

Publication number: CN102485729A
Application number: CN2010105826325A
Authority: CN
Inventors: 李坚
Original assignee: Individual
Current assignee: Individual
Priority date: 2010-12-03
Filing date: 2010-12-03
Publication date: 2012-06-06

Abstract

The invention relates to application of carboxylic acid as a catalyst in preparation of glyphosate, glufosinate-ammonium and intermediate products thereof. According to the invention, a reaction carried out under an acidic condition with carboxylic acid like chloroacetic acid and benzoic acid as a catalyst produces more excellent effects compared to a reaction carried out under a neutral or alkaline condition with triethylamine, pyridine and the like as a catalyst; the disadvantages of high cost and considerable discharge of waste water in the prior art are overcome, and industrial design standard for clean production can be meet.

Description

The application of carboxylic acid in preparation Glyphosate 62 IPA Salt, careless ammonium phosphine and midbody thereof

The present invention relates to a kind of carboxylic acid as the application of catalyzer in Glyphosate 62 IPA Salt, careless ammonium phosphine and intermediate product preparation thereof; Reaction under acidic conditions; With carboxylic acids such as Mono Chloro Acetic Acid, phenylformic acid is catalyzer, can reach than catalyzer such as triethylamine, pyridines and under neutrality or alkaline condition, react better effect, and it is higher to have improved the original technology cost of this series products; The shortcoming that wastewater discharge is bigger can reach the industrial design standard of cleaner production.

Background technology

On November 20th, 2010; Patent applicant of the present invention has applied for the patent of invention of denomination of invention for " a kind of application that is reflected in preparation Glyphosate 62 IPA Salt, the phosphine flame retardant "; Found the katalysis of organic acids such as phenylformic acid in the preparation Glyphosate 62 IPA Salt, patent of the present invention is replenishing this patent of invention.It is catalyzer that original technology is selected triethylamine for use; Combination dimethylphosphite, formaldehyde, glycocoll are that raw material carries out the prepared in reaction Glyphosate 62 IPA Salt under alkaline condition, yield lower (75～85%), and wastewater discharge is very big; Produce the effluent brine that one ton of Glyphosate 62 IPA Salt need discharge ten tons of high NaCl content; The technician in Glyphosate 62 IPA Salt field is well-known, and this waste water adds triethylamine because of needs and must reclaim this triethylamine again and produce, otherwise the adding triethylamine; Cancellation triethylamine recovery process, the production of Glyphosate 62 IPA Salt can reach the requirement that does not produce waste water basically.

Problem is no matter in alkalescence or reaction under acidic conditions, all must select the anhydrous response system; So must select Paraformaldehyde 96 and anhydrous glycine for use is raw material, but these two kinds of raw materials are insoluble or be slightly soluble in other solvent beyond dewatering, if do not select corresponding basic catalyst like one type of triethylamine; Though can reach the requirement that does not produce waste discharge; But reaction yield is less than 50%, and cost is higher, does not have advantage.

Summary of the invention

The objective of the invention is to use the catalyzer of carboxylic acids such as Mono Chloro Acetic Acid as this series products chemical reaction under acidic conditions; Under the prerequisite that does not produce discharge of wastewater; Improve the building-up reactions yield more than 10% than original technology simultaneously; And, again with Mono Chloro Acetic Acid etc. can be water-soluble carboxylic acid be the catalyzer of acid hydrolytic reaction or air oxidation reaction, improve the hydrolysis reaction yield more than 10%; Or substitute gac with Mono Chloro Acetic Acid and carry out oxidizing reaction as catalyzer, the Glyphosate 62 IPA Salt preparation cost can reduce more than 15%.

1, the preparation of Glyphosate 62 IPA Salt

1.1 combination dimethylphosphite or trimethyl phosphite or phosphorous acid or phosphorus trihalide and formaldehyde, glycocoll are raw material, under acidic conditions, carry out chemical reaction and prepare Glyphosate 62 IPA Salt, comprise the several steps of following order:

A, a kind of organic acid X of preparation, X comprises phenylformic acid, Mono Chloro Acetic Acid, dichloro acetic acid, trichoroacetic acid(TCA), nitrobenzoic acid, halogenated benzoic acid, all its acidity such as phosphate dialkyl ester are greater than the organic carboxyl acid of acetic acid; Prepare a kind of organic solvent RJ, RJ comprises ether, acetonitrile, methylal, ethylidene ether; Propyl ether, isopropyl ether, dimethyl methyl phosphonate, DMF, methyl alcohol; Ethanol, butyl ether, all can dissolve the organic solvent of carboxylic acid ethyl isobutyl ethers etc., X solute and RJ solvent are mixed with 10～30% solution;

In B, 10～30% solution input four-hole reaction flask, under nitrogen protection or under the condition of secluding air and water, start and stir the preparation of A step; 20～120 ℃ of controlled temperature drop into and equimolar glycocoll of solute X or aminoacetonitriles, drop into and equimolar Paraformaldehyde 96 of solute X or trioxymethylene again; Stirring reaction 1～15 hour; Slowly add dimethylphosphite or trimethyl phosphite or phosphorous acid or phosphorus trihalide with 1～1.1 mole of glycocoll then, continue stirring reaction 3～48 hours to terminal, reduce to normal temperature; Leave standstill more than 0.5～2 hour, filter, dry the white solid midbody;

C, molecule proportioning, midbody: HCl or Mono Chloro Acetic Acid=1: 1～3

B step gained solid intermediate is dropped in the four-hole reaction flask, start and stir, slowly add 10～30% hydrochloric acid of calculated amount or 5～15% the Mono Chloro Acetic Acid aqueous solution; 30 ℃～widely different stream of controlled temperature; Stirring reaction 2～28 hours is lowered the temperature, leaves standstill, filters, is dried, and gets glyphosate technicals.

1.2 with Cl ₂P (O) CH ₂NH ₂CH ₂COR (R representes Cl or OH) 1 or Cl ₂P (O) CH ₂NHCH ₂CN2 or (HO) (Cl) P (O) CH ₂NH ₂CH ₂COR (R representes Cl or OH) 3 is the raw material prepared in reaction Glyphosate 62 IPA Salt that is hydrolyzed, and comprises the several steps of following order:

Molecule proportioning 1 or 2 or 3: Mono Chloro Acetic Acid=1: 1

Raw material 1 or 2 or 3 is dropped in the water reaction kettles, slowly add all water-soluble carboxylic acids such as Mono Chloro Acetic Acid of calculated amount again, start and stir, controlled temperature 40～widely different stream slowly adds 30～70% methyl alcohol or aqueous ethanolic solution with 3～8 times of weight of 1 or 2 or 3.Stirring reaction 4～28 hours is lowered the temperature, leaves standstill, filters, is dried, glyphosate technicals or (HO) ₂P (O) CH ₂NHCH ₂The CN compound.

2, adopt the catalytic principle of above-mentioned carboxylic acid, can be applied to the preparation of amino acidses such as careless ammonium phosphine and pmida98 equally.

2.1 as Preparation of Catalyst grass ammonium phosphine, comprise the several steps of following order with carboxylic acid:

A, molecule proportioning methyl dichloro phosphine: Paraformaldehyde 96: acetaldehyde: phenylformic acid=1: 1: 1: 1

Ether or above-mentioned RJ solvent and phenylformic acid or all acidity are mixed with 10～20% solution greater than the organic acid of acetic acid, drop in the reaction flask, start and stir; Slowly drop into the Paraformaldehyde 96 or the trioxymethylene of calculated amount, slowly drop into the paraldehyde or the NS3 of calculated amount again, 20～100 ℃ of controlled temperature; Stirring reaction 1～12 hour drips methyl dichloro phosphine or phosphorus trichloride then, stirring reaction 4～28 hours; Lower the temperature, leave standstill, filter, dry, get (CH ₃) ClP (O) CH ₂CH ₂CHO, 17 or Cl ₂P (O) CH ₂CH ₂CHO, 16 compounds;

B, 17 compounds that the A step is obtained drop in the reaction flask, start and stir, and slowly add the water of 1～4 times of weight or 5～15% the Mono Chloro Acetic Acid aqueous solution; 30 ℃～widely different stream of controlled temperature, stirring reaction 1～12 hour slowly adds the equimolar ammoniacal liquor and the HCN aqueous solution then; Stirring reaction 2～16 hours adds 30～37% the concentrated hydrochloric acid of 1～3 mole of HCl, widely different stream reaction 4～12 hours again; Lower the temperature, leave standstill, filter, dry, get the former medicine of careless ammonium phosphine.

2.2 the preparation of pmida98 comprises the several steps of following order:

A, molecule proportioning NSC 263496: formaldehyde: phosphorus trichloride: Mono Chloro Acetic Acid=1: 1: 1: 1

To drop in the reaction flask with 99% methylal of the equimolar Mono Chloro Acetic Acid of formaldehyde and 6～9 times of amounts, and start and stir 30 ℃～widely different stream of controlled temperature; The NSC 263496 and Paraformaldehyde 96 or the trioxymethylene that slowly add calculated amount, stirring reaction 6～18 hours, then; Drip the phosphorus trichloride of calculated amount or slowly add equimolar phosphorous acid or dimethylphosphite or trimethyl phosphite; Stirring reaction 28 hours is lowered the temperature, leaves standstill, filters, is dried, and gets the midbody solids;

The technical characterictic of this step process process is under anhydrous condition, to react;

B, A step gained midbody is dropped in the reaction flask, slowly add 20～30% aqueous hydrochloric acid of 6～8 times of weight, widely different stream reaction 12～24 hours is lowered the temperature, leaves standstill, filters, is dried, the pmida98 solid.

3, the existing technology that pmida98 is oxidized to Glyphosate 62 IPA Salt has two:

Article 1, be to be oxygenant with the ydrogen peroxide 50, this technology by product is many, and yield is low; Another be with the gac be catalyzer with air or purity oxygen oxidation, the shortcoming of this technology is the recovery of activated carbon and utilizes relatively difficulty, because amount of activated is bigger; At recovered carbon and recycle in the process, increase preparation cost, and use water-soluble carboxylic acid to replace gac as catalyzer; Reaching under the prerequisite of same effect, preparation cost can reduce more than 5%.

With the Mono Chloro Acetic Acid is that catalyzer air or purity oxygen oxidation pmida98 prepare Glyphosate 62 IPA Salt, comprises a step of following order:

A, pmida98 and equimolar Mono Chloro Acetic Acid are dropped in the reaction kettle, add the deionized water of 6～9 times of weight, start and stir; 40 ℃～widely different stream of controlled temperature; Constantly bubbling air or purity oxygen reacted after 4～12 hours, lowered the temperature, leave standstill, filter, dried; Glyphosate technicals, dissolved that chloroacetic mother liquor is recyclable to be applied mechanically.

Specific embodiments

Embodiment 1

The Mono Chloro Acetic Acid of 0.2mol and 219 gram ether or glycol dimethyl ether are dropped in the reaction flask, start and stir, about 28 ℃ of controlled temperature slowly add equimolar glycocoll and the Paraformaldehyde 96 or the trioxymethylene that wait mole or 2 times of moles; Stirring reaction 12 hours slowly adds equimolar dimethylphosphite or trimethyl phosphite or phosphorous acid then, and 30 ℃～100 ℃ stirring reactions of controlled temperature 28～38 hours are lowered the temperature, leave standstill, filter, dried; Solid intermediate, in this solid, drop into 10～30% the hydrochloric acid or the Mono Chloro Acetic Acid aqueous solution of 1～3 times of mole, be warming up to widely different stream; Stirring reaction 2～18 hours, under vacuum, try one's best then clean hydrochloric acid of evaporate to dryness and water, cooling; The deionized water that adds 2～4 times of weight, leave standstill 12 hours after, filter, oven dry; Get glyphosate technicals, content 95%, yield 86%.

Embodiment 2

0.2mol raw material 1 or 2 or 3 is dropped in the hydrolytic reaction pot; Slowly 30%～70% methyl alcohol or the aqueous ethanolic solution or the pure water of adding and 1 or 2 or 3 heavy 8 times of amounts start and stir 30 ℃～widely different stream of controlled temperature; Mono Chloro Acetic Acid or other all water-soluble carboxylic acids of slowly adding 0.2mol again; Stirring reaction 4～28 hours is lowered the temperature, leaves standstill, filters, is dried, the former medicine of sweet phosphine or (HO) ₂P (O) CH ₂NHCH ₂The CN compound, yield 96%, content 98%.

Embodiment 3

The 0.2mol acid and 219 g of diethyl ether into a reaction kettle, starting stirring, controlling the temperature 20 ℃ ~ Hui stream, slowly adding 0.2mol paraformaldehyde or trioxane, and slowly adding 0.2mol or paraldehyde poly-aldehydes, the reaction was stirred for 8 hours and then methyl chloride was added dropwise 0.2mol phosphine or phosphorus trichloride was stirred for 22 hours, cooled, allowed to stand, filtered, and dried to give compound 17 or 16.

17 compounds are dropped in the reaction flask, start and stir, slowly add the water of 4 times of weight or 10% the Mono Chloro Acetic Acid aqueous solution; 30 ℃～widely different stream of controlled temperature, stirring reaction 8 hours slowly adds the ammoniacal liquor and the HCN aqueous solution of 0.2mol then; Stirring reaction 16 hours slowly adds 30% the aqueous hydrochloric acid of 3molHCl again, is warming up to widely different stream; Stirring reaction 12 hours is lowered the temperature, leaves standstill, filters, is dried, and gets the former medicine of careless ammonium phosphine; Content 95%, yield 85%.

Embodiment 4

Mono Chloro Acetic Acid and the 219 gram methylals of 0.2mol are dropped in the reaction flask, start and stir, 30 ℃～widely different stream of controlled temperature slowly adds 0.2mol NSC 263496 and 0.2mol Paraformaldehyde 96 or 0.2mol trioxymethylene; Stirring reaction 18 hours drips the 0.2mol phosphorus trichloride then or slowly adds 0.2mol phosphorous acid, and stirring reaction 28 hours is lowered the temperature, leaves standstill, filters, dried; Get midbody, content 98%, yield 98%; Then, drop into 30% aqueous hydrochloric acid with 5～8 times of weight of this midbody, back flow reaction 24 hours; Lower the temperature, leave standstill, filter, get pmida98 solid, hydrolysis yield 95%, content 96%.

Embodiment 5

The pmida98 of 0.2mol and the deionized water of 6 times of weight are dropped in the reaction kettle, drop into Mono Chloro Acetic Acid or the trichoroacetic acid(TCA) of 0.2mol again, start and stir; 40 ℃～widely different stream of controlled temperature, constantly bubbling air or purity oxygen reacted 5～12 hours; Lower the temperature, leave standstill, filter, dry, get glyphosate technicals, content 97%; Yield 95%, Mono Chloro Acetic Acid are dissolved in the water mother liquor, can apply mechanically.

Claims

1. combination dimethylphosphite or trimethyl phosphite or phosphorous acid or phosphorus trihalide and formaldehyde, glycocoll are raw material, under acidic conditions, carry out chemical reaction and prepare Glyphosate 62 IPA Salt, comprise the several steps of following order:

C, molecule proportioning, midbody: HCl or Mono Chloro Acetic Acid=1: 1～3

2. with Cl ₂P (O) CH ₂NH ₂CH ₂COR (R representes Cl or OH) 1 or Cl ₂P (O) CH ₂NHCH ₂CN2 or (HO) (Cl) P (O) CH ₂NH ₂CH ₂COR (R representes Cl or OH) 3 is the raw material prepared in reaction Glyphosate 62 IPA Salt that is hydrolyzed, and comprises the several steps of following order:

Molecule proportioning 1 or 2 or 3: Mono Chloro Acetic Acid=1: 1

3. adopt the catalytic principle of above-mentioned carboxylic acid, can be applied to the preparation of amino acidses such as careless ammonium phosphine and pmida98 equally.

As Preparation of Catalyst grass ammonium phosphine, comprise the several steps of following order with carboxylic acid:

4. the preparation of pmida98 comprises the several steps of following order:

To drop in the reaction flask with 99% methylal of the equimolar Mono Chloro Acetic Acid of formaldehyde and 6～9 times of amounts, and start and stir, 30 ℃～backflow of controlled temperature; The NSC 263496 and Paraformaldehyde 96 or the trioxymethylene that slowly add calculated amount, stirring reaction 6～18 hours, then; Drip the phosphorus trichloride of calculated amount or slowly add equimolar phosphorous acid or dimethylphosphite or trimethyl phosphite; Stirring reaction 28 hours is lowered the temperature, leaves standstill, filters, is dried, and gets the midbody solids;

5. be that catalyzer air or purity oxygen oxidation pmida98 prepare Glyphosate 62 IPA Salt with the Mono Chloro Acetic Acid, comprise a step of following order: