CN1081183A - The synthetic method of N-phosphorous carbo-xymethyl glycine - Google Patents
The synthetic method of N-phosphorous carbo-xymethyl glycine Download PDFInfo
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- CN1081183A CN1081183A CN 92105782 CN92105782A CN1081183A CN 1081183 A CN1081183 A CN 1081183A CN 92105782 CN92105782 CN 92105782 CN 92105782 A CN92105782 A CN 92105782A CN 1081183 A CN1081183 A CN 1081183A
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Abstract
A kind of synthetic method of N-phosphorous carbo-xymethyl glycine is characterized in that:
Make trialkyl (or aryl) phosphorous acid ester and a kind of C that exists at triamine by glycine and trioxymethylene
1～C
4React the methylol glycine that is produced in the alkyl alcohol solution, after low temperature carries out esterification with strong acid or alkaline purification.
Description
The present invention relates to new synthetic method about N-phosphorous carbo-xymethyl glycine (N-phosphonomethylglycine).The N-phosphorous carbo-xymethyl glycine is to be used widely as the intermediate of weedicide manufacturing.The method of existing before this multiple this compound of manufacturing is developed, and its major part is to be starting raw material with imines two acetic acid.
The inventive method is with the method for making of a kind of glycine than imines two acetic acid cheapnesss and lower molecular weight as starting raw material.
The method for making of known use glycine starting raw material, for example in United States Patent (USP) the 4th, 237, disclose in No. 065, be trioxymethylene (paraformaldehyde) to be dissolved in one have in the hot alkyl alcohol solution that the 3rd alkali of catalyst amount exists, add glycine then and react, that continues adds dialkyl phosphites (be called for short DAP) again in reaction soln, and reaction is finished in heating.Add NaOH solution subsequently and carry out saponification in the ester that reaction generates, and remove the 3rd alkali, the alkaline solution acidification that makes acquisition is at last produced the N-phosphorous carbo-xymethyl glycine of purpose with the N-phosphorous carbo-xymethyl glycine precipitation that order generates.Its reaction is as follows:
The inventive method is not used the DAP of high price, and cheap trialkyl (or triaryl) phosphorous acid ester (hereinafter to be referred as TAP) is used in attempt, makes itself and methylol glycine react and carries out esterification.
The present invention relates to a kind of synthetic method of N-phosphorous carbo-xymethyl glycine, comprising: order has trialkyl (aryl) phosphorous acid ester of following general expression
With one by glycine and trioxymethylene at the triamine C that exists of triethylamine particularly
1～C
4In the alkyl alcohol, the methylol glycine that reaction generates, that is:
(a) a methylol glycine (claiming N-methylol glycine again), and
(b) dihydroxymethyl glycine (claiming N again, two (methylol) glycines of N-) or both mixtures in below 10 ℃, carry out esterification under especially 10 ℃～-6 ℃ the low temperature, again with strong ore deposit acid (especially hydrochloric acid) or alkaline purification.To the coarse crystallization of the N-phosphorous carbo-xymethyl glycine that obtained, use the deionized water wash below 5 ℃ of being cooled to of pH1.0～2.0, and purity is promoted to more than 95%.
The inventor is its possibility of research, when experimental result confirms that esterification is carried out under such as the low temperature below 10 ℃ in many ways, needn't can produce the purpose product N-phosphorous carbo-xymethyl glycine of 96～98% purity through the recrystallize program, thereby finish the inventive method.Simultaneously, discovery this method not only is suitable for and has C
1～C
4The trialkyl phosphite of alkyl (TAP), also being suitable for its aryl simultaneously is for example triarylphosphite such as methoxyphenyl, phenelyl, propoxy phenyl, butoxyphenyl, chloro-phenyl-, aminomethyl phenyl, ethylphenyl, propyl group phenyl of phenyl or derivatives thereof.
The currently known methods that uses trialkyl (or triaryl) phosphorous acid ester to make the N-phosphorous carbo-xymethyl glycine has the example that makes chloromethyl glycine and trialkyl (triaryl) phosphite reactions, but this is nothing but to utilize the Cl of chloromethyl glycine to remove the alkyl (or aryl) of trialkyl (or triaryl) phosphorous acid ester, obviously and the esterification of the inventive method, different on basic technological concept.In addition, by Cl take off alkyl (or aryl) reaction, its reactivity is 30～40% only, is not have economic worth fully.And the chloromethyl glycine that participates in reaction need utilize SOCl
2(or other chlorine compounds) make glycine methylol compound-formality of OH base chlorating, cause the increase of step and need use the acid-resistant system of high price again, increase cost.
The main idea of the inventive method for rely on allow TAP and (mono) or dihydroxymethyl glycine or the mixture of the two implementation low-temp reaction can reach expectation optionally only make a methylol esterification.This is to break acid and alcohol fully under the temperature more than the normal temperature, can reach the general chemical general knowledge of esterification through dehydrating condensation, and this trialkyl (or triaryl) phosphorous acid that does not have free acidic group is fully reached the esterification that exceeds general general knowledge with the alcohol reaction at low temperatures.
The inventive method is that the simple method that drips TAP with only depending on stirring at low temperatures just can be finished reaction and can make highly purified purpose product by high yield in the short period of time.
The basic theories of the inventive method can be done following explanation:
At first, the alcohol that participates in reaction is the methylol glycine by the reaction generation of glycine and trioxymethylene, and its combination is to exist with a methylol body or dihydroxymethyl body or its both mixture.Its chemical formula is:
(A) HOCH
2.NH.CH
2COOH (a methylol glycine)
(B)
(dihydroxymethyl glycine)
Utilize Karl Fisher to check above-mentioned (A), (B) result, can detect moisture, it measures the mole number for the trioxymethylene that is equivalent to add.Infer that by analytical results this moisture is to be produced by methylol glycine intramolecular dehydration, promptly infers the dehydration at intramolecularly generation following formula:
So, the H of this generation
2O should be with free H
2O and acting on.
Secondly, with trialkyl (or aryl) phosphorous acid ester, drip in H at low temperatures
2In the time of in the alcoholic solution that O exists, can cause that singly taking off alkyl (or aryl) changes reaction and generate dialkyl group (or aryl) phosphorous acid hydrogen ester, produce the heat (occasion of trishydroxymethyl phosphorous acid ester) of about 18.6kcal/mol simultaneously, promptly cause the reaction of following formula this moment:
(R=alkyl or aryl)
Dialkyl group (or aryl) the phosphorous acid hydrogen ester that generate this moment will carry out following reaction with the intramolecular dehydration thing of above-mentioned (A '), (B ') and produce object.At this moment, may since TAP take off alkyl (or aryl) time moment of taking place the heat of emitting promote esterification and carry out at low temperatures.For comparing experiment, only DAP is made an addition at low temperatures above-mentioned (A), (B), but any reaction does not take place in the result, but almost react completely during TAP.
Another characteristics of the inventive method are, above-mentioned it (reaction of B ") is selectively carried out at low temperatures.In other words, even there is the dihydroxymethyl glycine to exist, only have the first methylol body to participate in reaction, and the second methylol body does not participate in reaction, this point is confirmed by TLC or HPLC.
Conclusion is as follows in addition with above-mentioned:
Glycine and trioxymethylene are reacted in the solution that methylol glycine of generation or dihydroxymethyl glycine or both mixtures exist under proper condition, drip TAP, remain in suitable low temperature this moment.By dripping, alkyl (or aryl) effect of taking off that causes because of TAP only takes place on a methylol body.Though can produce reaction heat this moment, only be moment, this moment the reaction heat that takes place promote the combining of the methylol body that takes off an alkyl (or aryl) body and intramolecular dehydration of TAP, and because low temperature, so etc. reaction will selectively carry out to the direction of expecting.The result can high-level efficiency make the few high purity product of impurity amount.Above reaction condition can chase after comprehensive with TLC or HPLC.
Each reaction conditions of the inventive method is as follows:
The solvent that uses is for having C
1～C
4The alcohol of alkyl, for example methyl alcohol, ethanol, Virahol, butanols and isopropylcarbinol.By economical and be easy to the viewpoint that distillation reclaims, the most desirable with methyl alcohol.
Again, need trioxymethylene is dissolved in this alkyl alcohol, but owing to can directly not dissolve, so need interpolation alkali or amine as catalyst.Amine is more desirable with alkylamine, but is considered by easiness economic and that reclaim, and is preferable with triethylamine, can dissolve at short notice by its trioxymethylene and to add glycine subsequently, in 20～50 ℃, best 25～45 ℃ are stirred down, then promptly are dissolved into clear solution in 20～30 minutes.The usage quantity of trioxymethylene and glycine needs glycine is used 0.8～3.0 at least, especially 1.0～2.2 moles of trioxymethylenes doubly.Like this, almost can be with the complete methylolation of glycine.The reactant of this moment is a methylol body, dihydroxymethyl body or both mixtures; This available TLC or HPLC confirm.For seeking to react completely, the amount of alkyl alcohol is an important factor, promptly measures the generation chance that can increase polymkeric substance when very few, then meaningless increase equipment in the time of too much, and lose time on the solvent recuperation more.Therefore, the consumption of alkyl alcohol should be glycine and trioxymethylene total amount 1～10 times, best 2～5 times of capacity.Through experimental result, when 2～5 times of whens amount and 5～10 times of amounts, its receipts amount does not increase to some extent because of the increase of alcohol amount.This is also provable, because of the inventive method adopts low-temp reaction, so can not cause unwanted side reaction.Again, the alkyl alcohol of use when the state of the moisture that contains several %, also can react, but preferably uses anhydrous state, can obtain stable reaction result like this, avoids according to the variation that the receipts amount batch is arranged.
Through carrying out controlled trial, only make glycine and trioxymethylene in alkyl alcohol without amine (comprising triethylamine), with the identical conditions reaction, the interior at one time major part of result is not dissolved, and the result can't obtain the result of tool practicality.
Amine especially is selected from the usage quantity of the triethylamine in the triamine, through test-results, when the reaction of trioxymethylene and glycine, not influenced by specific mol ratio, all can obtain same result.Promptly, occasion at the addition of (for glycine) below 1 mole or more than 1 mole, though reaction times and reactant receipts amount are all identical, but the time next with the reaction of TAP, to the occasion that glycine adds 0.5～4.0 mole triethylamine, the result is preferable, especially 0.9～2.5 mole, special when 0.9～1.1 mole consumption, the gained result is ideal.This is dialkyl group (or aryl) the phosphorous acid hydrogen ester formation acid amide of the dealkylation compound of tribasic triethylamine and TAP, thus the reactivity of increase and methylol.In controlled trial, in the test of the consumption of minimizing triethylamine, along with the minimizing of triethylamine amount, the receipts amount also reduces.In view of above-mentioned result, use triethylamine in the methods of the invention, its purpose is promoting and is stablizing the methylolation of glycine by it, the effect of depolymerizing of trioxymethylene, and then in ensuing N-phosphorization, bring into play catalysis with TAP.
Triethylamine serves as catalyst and acts on a joint in the esterification of methylol glycine be to refer in United States Patent (USP) 4,237, in No. 065, this be since dialkyl group (or aryl) the phosphorous acid hydrogen ester of the phosphorus that uses due to pyroreaction.Dialkyl group (or aryl) phosphoric acid hydrogen ester is reacted also Fails To Respond at order itself and methylol glycine of the low temperature of the characteristics of the inventive method and tribasic existence, and the receipts amount of pyroreaction is low than the inventive method also.This species diversity be because of the required energy of the esterification of currently known methods be to rely on indirect heating, but the inventive method is with under low temperature environment, TAP is dripped occasion in the alkyl alcohol that contains the methylol body, the H that intramolecular dehydration produced of TAP and methylol glycine
2O phase reaction and the heat release of moment of producing are as the energy.Again, triethylamine has boiling point not high, and is little to the solubleness of water, reclaims characteristics such as easy.
After the methylol glycine generated, ensuing reaction was to make it in containing the alkyl alcohol solution of methylol glycine and triethylamine, with the TAP reaction that drips.
The methylol glycine consist of a methylol body and dihydroxymethyl body or both mixtures, more desirable mol ratio is a trioxymethylene: glycine=2.0～2.2: 1, can get the highest receipts amount in this scope.Through confirming the result with TLC and HPLC, the compound of reaction of trioxymethylene and glycine is the dihydroxymethyl glycine, and other are a methylol glycine below 20%, and the unreacted glycine is below 1%, i.e. methylolation fully almost.The polymerization of minute quantity trioxymethylene is only arranged.
To this solution, when dripping TAP at low temperatures, temperature can sharply rise, and therefore needs to be cooled off from the outside.Suitable temperature of reaction is 10 ℃～-10 ℃, and in this extraneous occasion, receipts amount thing can reduce gradually.Shi Yi temperature range is+5 ℃～-5 ℃ especially, and in this scope, temperature is whenever fallen 2 ℃, and then yield increases approximately 1%, in other words, knows via experiment, and yield is about 78～80% in the time of 10 ℃, but the highest-5 ℃ the time can about 85%.A presumption of act thus to the mixture of a methylol body and dihydroxymethyl body, can only selectively be carried out combination to a methylol body, and influence yield thus when low temperature.
Making us feeling marvellous is, when this temperature was added dialkyl group (or aryl) phosphoric acid hydrogen ester, esterification was carried out hardly or only a little, and is heated to more than the room temperature, the beginning of esterification beginning, but yield is relatively poor during than TAP.This one relatively is to obtain to confirm as embodiment and comparative example 1.
Above-mentioned reaction is described as follows with chemical equation.
(A) of TAP and above-mentioned page 4, (B) reaction are shown in down once again:
End reaction only has (A ' ") and (B ' ") selectively to carry out, and this is through confirming with TLC.Confirm according to TLC, do not find above-mentioned (A ' ") and (B ' ") reaction other reactions in addition, this does not see when the mole number with TAP adds 1.1 moles excessive state to glycine yet the tendency of TAP to second methylol (dihydroxymethyl) reaction, TAP is still residual with unreacted state, and this checks via TLC and confirms.When rising to temperature more than 10 ℃, find to have two-(inferior phosphorus methylol) body, more than 20 ℃ then superfluous add almost all become two-(inferior phosphorus carboxymethyl) body.This proof is only selectively carried out the esterification of a methylol at low temperature, is the feature that forms the inventive method.
In the occasion that low temperature adds TAP, esterification also finishes when interpolation finishes, checks according to TLC, carves unreacted methylol glycine all unconfirmed and TAP at this moment.For obtaining the N-phosphorous carbo-xymethyl glycine of object, need to carry out engaging methylolization and dealkylation with ore deposit acid thus, this available currently known methods carries out.Again, also available known method obtains crystallization, but thus gained be coarse crystallization, purity is generally 90～93% scope, for obtaining purity 95% when above, needs go the recrystallize processing.
Be recrystallize, need equipment and can handle the loss that causes some % because of recrystallize.For eliminating this shortcoming, the result that the impurity of crystallization and existence is discussed on inspection knows that impurity is based on NaCl and contains micro-phosphoric acid and phosphorous acid.Though the available simple washing of these impurities and being removed needs a large amount of washing water, and the molten shortcoming of losing in washing water of effective ingredient is arranged.For preventing this loss, use the cold water of pH1.0～2.0, then solubleness can be suppressed at inferior limit, promptly the iso-electric point of N-phosphorous carbo-xymethyl glycine is pH1.0～2.0, this is a meaning, at this pH, the solubleness minimum.
The occasion of pH more than above-mentioned will form the alkali salt of N-phosphorous carbo-xymethyl glycine, and the occasion of pH below above-mentioned then forms hydrochlorate, and these salt all can be dissolved in water and become loss.
In above-mentioned pH scope, when being cooled to below 5 ℃, the lossing solution of water-soluble components can be suppressed at below 0.7%.If these washing water are not abandoned, serve as the crystallization water of handling next time and use, then can prevent the loss of effective ingredient fully, thereby increase the receipts amount.
With these washing water that are cooled to pH1.0～2.0 below 5 ℃, spray while filter, then just crystalline purity can be promoted to more than 96% through 2～3 times sprinkling.
The reaction mechanism of methylol glycine and TAP is illustrated above; Following embodiment can actual its result of proof.Again, special for more certain proof to resultant of reaction implementation fusing point (M.P.), HPLC.UV inspection, and
1Hnmr,
13Cnmr, IR and ultimate analysis really are that N-phosphorous carbo-xymethyl glycine and purity are really more than 96% with the proved response resultant.
Embodiment 1
Take into account 200 milliliters of the methyl alcohol of packing in 1000 milliliters of Florence flasks of addition funnel, triethylamine 50.5 grams, trioxymethylene 30 grams in having reflux exchanger, temperature, place on the magnetic stirring apparatus, stirred 20～30 fens in 30～35 ℃, this moment, content was transparence, adding glycine 37.5 grams subsequently continues to stir, then temperature slowly rises, and it is transparent that content is, and optionally cooled off.Can confirm that with TLC glycine almost completely disappears, major part is a methylol glycine of dihydroxymethyl glycine and small portion.
Then, flask is placed ice bath, be cooled to-5 ℃, and under agitation drip trimethyl phosphite (be called for short TMP), temperature rises gradually, so it is remained between-5～10 ℃, continues to drip TMP, promptly finish though when TMP dropwises, react, can optionally continue again to stir 5～10 fens.Confirm a methylol and the completely dissolve of dihydroxymethyl glycine and dimethyl ester and the dimethyl ester of the inferior phosphorus carboxylic acid methyl of N-methylol N-glycine and the dimethyl ester of the inferior phosphorus carboxylic acid methyl of N-methylol N-glycine of the inferior phosphorus carboxylic acid methyl of newly-generated N-glycine are arranged with the TLC check result.
Then, add dense HCl, slowly add temperature and still can sharply rise, so, drip while cool off, promptly took off dihydroxymethyl effect (temperature is avoided rising to more than 40 ℃) in 30 minutes at stir about below 40 ℃.In this stage, methylol almost becomes the dimethyl ester of the inferior phosphorus carboxylic acid methyl of the N-glycine of pure generation entirely with regard to disengaging.
Subsequently more again enriching HCl and heated and stirred remove residual methyl alcohol with gold-plating, then can confirm to have become the hydrochloride of the inferior phosphorus carboxylic acid methyl of N-glycine.In this distillation residue, add water (or coarse crystallization washing water) ph is adjusted to 1.0～2.0, and cooled off the inferior phosphorus carboxylic acid methyl of the N-glycine precipitation of promptly seeing the white crystals shape.Adopt centrifuging or vacuum filtration and utilize the deionized water below 5 ℃ of being cooled to of previously prepared pH1.0～2.0,, and give the dry white micro-crystals shape purpose product 70 of purity 96% or more that promptly obtain and restrain by crystallized product top hydro-peening 2～3 times.
The analytical results of this product is as follows:
HPLC：96.7%，UV：96.9%，M.P.：226℃
(a) ultimate analysis
C????H????N????P????O
Theoretical value 21.31 4.77 8.28 18.32 47.32
Analytical value 20.91 4.76 8.15 18.60-
(b)
1Hnmr(is with 1%D
2The O measured in solution)
δ (ppm) integrating ratio
1.7(impurity?)
3.93 H
2C.P
4.13 amplifying for 10 times, HOD(side peak, direction of principal axis measure)
4.6(benchmark value) HOD
5.6 amplifying for 10 times, HOD(side peak, direction of principal axis measure)
(c)
13Cnmr (restrains and D with Isopropylamine (IPA) 0.1 in N-phosphorous carbo-xymethyl glycine 0.3 gram
2Measure after the O0.8 gram stirring and dissolving)
1150cm
-1VsP:O -P=O
910cm
-1VsP:O -P-OH
1440cm
-1δ
3CH
2H
2C-P
1490cm
-1δ
3CH
2H
2C-N
Embodiment 2～5
Use outside ethanol, n-propyl alcohol, Virahol and the methyl alcohol of propyl carbinol with alternate embodiment 1, all the other are all undertaken by the method for embodiment 1, and the result is as follows:
| Embodiment | Alkyl alcohol | Receipts amount (g) | Purity check value (%) | Yield (%) | M.P ℃ | |
| HPLC | UV | |||||
| 2 | Ethanol | 70.2 | 97.5 | 97.6 | 80.8 | 227.5-228.0 |
| 3 | N-propyl alcohol | 70.0 | 97.8 | 98.0 | 81.0 | 228 |
| 4 | Virahol | 70.5 | 97.2 | 97.5 | 81.0 | 227-227.5 |
| 5 | Propyl carbinol | 71.0 | 96.3 | 96.5 | 80.9 | 226 |
(yield is to calculate as benchmark with the HPLC analytical value)
As representative, results of elemental analyses is as follows with the crystallization of embodiment 2 gained:
Ultimate analysis C H N P O
Theoretical value 21.02 4.77 8.19 18.32 47.32
Analytical value 20.90 4.83 8.09 18.70-
1Hnmr,
13Cnmr, the analytical results of IR is identical with embodiment 1.
Embodiment 6～12
As solvent, and outside using as TAP with TMP, all by the method operation of embodiment 1, just the dropping temperature of TMP difference is as shown in the table, the results are shown in following table for all the other with 200 ml methanol:
By above test-results, the sample of embodiment 9 is carried out ultimate analysis as representative, the result is as follows:
Ultimate analysis C H N P O
Theoretical value 21.31 4.77 8.28 18.32 47.32
Analytical value 20.89 4.75 8.10 18.80-
1Hnmr,
13Cnmr, the analytical value of IR is identical with embodiment 1.
Embodiment 17-19
With methyl alcohol as solvent; And with triethyl phosphorite, tributyl phosphorous acid ester and triphenyl phosphorous acid ester as trialkyl (or aryl) phosphorous acid ester, respectively with etc. mol ratio add experimental result such as following table (TAP dropping temperature 0～-2 ℃).
| Embodiment | Phosphorous acid ester | Receipts amount (g) | Purity check value (%) | Yield (%) | M.P. | |
| HPLC | UV | |||||
| 17 | Triethyl phosphorite | 70.8 | 97.1 | 97.3 | 81.3 | 227.0 |
| 18 | The tributyl phosphorous acid ester | 70.5 | 97.0 | 97.2 | 80.9 | 227.0 |
| 19 | The triphenyl phosphorous acid ester | 71.5 | 97.2 | 97.3 | 81.6 | 227.0 |
The crystalline results of elemental analyses of embodiment 19 is as follows:
Ultimate analysis C H N P O
Theoretical value 21.3 4.77 8.28 18.32 47.32
Analytical value 20.84 4.75 8.08 18.90-
Comparative example
Method according to the embodiment 1 of Japanese kokai publication sho 56-68688 is carried out, as a comparison.
Take into account the glycines that add 37.5 grams in the hot solution that is added with 500 milliliters of methyl alcohol, triethylamine 47 grams, trioxymethylene 30 grams in the three-necked flask of addition funnel in having reflux exchanger, temperature, and in the N of gained, two (methylol) glycines of N-(are N, N-dimethyl glycine) add dimethyl phosphorous acid hydrogen ester 55 grams in, stirring reaction also makes boiling 1 hour.
Contain dialkyl group (N-(N-hydroxy methylene glycine) in gained) add 210 milliliters of concentrated hydrochloric acids in the solution of methylene radical phosphite, heated 1.5 hours, make its hydrolysis become the N-phosphorous carbo-xymethyl glycine.This reaction mixture is handled, and the N-phosphorous carbo-xymethyl glycine that obtains with crystalloid.With this crystallisate, with the cold water washing drying of pH1.0～2.0, the result obtains 60 gram products.
Purity 96.5%(HPLC), yield 68.5%.
With this experiment three times repeatedly, do not adopt for the first time, adopt the 2nd and the 3rd time, the result is above-mentioned.This result does not reach the purity 98.2 ± 1.5% that Japanese kokai publication sho 56-68688 embodiment 1 is put down in writing, yield (calculating) 76.2% level.
Embodiment 21(coarse crystallization washing method)
To heating up in a steamer except that behind the alkyl alcohol by embodiment 20 same procedure, the distillation leftover that preparation enters the crystallization program adds the recovery filtrate 100 milliliters (containing water-soluble components 0.65%) of the foregoing description 20 as the crystallization water.When this crystalline vacuum filtration, similarly to Example 20,, be divided into 2 parts (50 milliliters every part) washing coarse crystallization with being adjusted to 2 ℃ 100 milliliters of the deionized waters of being cooled to of pH1.0～2.0 in advance, give vacuum attraction simultaneously.The gained result is as follows:
100 milliliters of filtrate yields; Component content 0.6%(UV)
Receipts amount 70.2 grams, purity 96.8%(HPLC), yield 80.4%
Embodiment 22(coarse crystallization washing method)
Heavily cover the method for embodiment 21, promptly heat up in a steamer except that behind the alkyl alcohol, in residue, add to reclaim filtrate effect crystallization water, with the coarse crystallization of leaching, by 2 ℃ cold deionized water wash secondary and the vacuum attraction of same main points with pH1.0～2.0 by the method for embodiment 21.
The filtrate yield: 100 milliliters, component content: 0.65%(UV)
The receipts amount: 70.5 grams, purity: 97.0(HPLC), yield: 80.9%
Embodiment 23.(coarse crystallization washing method)
Heating up in a steamer of obtaining of the method for embodiment 1 removed residue behind the alkyl alcohol, 100 milliliters of the recovery filtrates of adding embodiment 22 are as the crystallization water, utilize the centrifuge separator fractional crystallization, utilize this moment 50 milliliters of 2 ℃ of cold deionized waters of pH1.0～2.0 to spray coarse crystallization in the washing separator, when waiting not have filtrate more again with 50 milliliters of sprinklings.This centrifugation is filtered than vacuum, and the crystalline water content after the separation is 4～6%, and the result is as follows:
Filtrate yield: 100 milliliters, composition: 0.65%(UV)
The receipts amount: 70.6 grams, purity: 97.2%, yield: 81.2%
Embodiment 24(coarse crystallization washing method)
Heavily cover the operation of embodiment 23, the crystallization water is to use 100 milliliters of the recovery filtrates of the foregoing description 23, and the gained result is as follows:
The filtrate yield: 100 milliliters, component content: 0.65%
The receipts amount: 71.0 grams, purity: 97.0%, yield: 81.5%.
Claims (2)
1, a kind of synthetic method of N-phosphorous carbo-xymethyl glycine is characterized in that, comprising: order has trialkyl (aryl) phosphorous acid ester of following general expression
(in the formula, R=C
1～C
4Alkyl or phenyl)
With one by glycine and trioxymethylene at the triamine C that exists of triethylamine particularly
1～C
4In the alkyl alcohol, the methylol glycine that reaction generates, that is:
(a) a methylol glycine (claiming N-methylol glycine again), and
(b) dihydroxymethyl glycine (claiming N again, two (methylol) glycines of N-) or both mixtures in below 10 ℃, carry out esterification under especially 10 ℃～-6 ℃ the low temperature, again with strong ore deposit acid (especially hydrochloric acid) or alkaline purification.
2, method as claimed in claim 1 is characterized in that, it also comprises: to the coarse crystallization of the N-phosphorous carbo-xymethyl glycine that obtained, use the deionized water wash below 5 ℃ of being cooled to of pH1.0～2.0, and purity is promoted to a washing step more than 95%.
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643437A (en) * | 2008-08-04 | 2010-02-10 | 李坚 | Preparation and application of oximide acetic acid and salts thereof |
-
1992
- 1992-07-10 CN CN 92105782 patent/CN1081183A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643437A (en) * | 2008-08-04 | 2010-02-10 | 李坚 | Preparation and application of oximide acetic acid and salts thereof |
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