IE912921A1 - Process for the preparation of aminomethylphosphonic acid¹and aminomethylphosphinic acids from N-hydroxymethylamides - Google Patents
Process for the preparation of aminomethylphosphonic acid¹and aminomethylphosphinic acids from N-hydroxymethylamidesInfo
- Publication number
- IE912921A1 IE912921A1 IE292191A IE292191A IE912921A1 IE 912921 A1 IE912921 A1 IE 912921A1 IE 292191 A IE292191 A IE 292191A IE 292191 A IE292191 A IE 292191A IE 912921 A1 IE912921 A1 IE 912921A1
- Authority
- IE
- Ireland
- Prior art keywords
- formula
- reaction
- phenyl
- acid
- preparation
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 22
- 238000002360 preparation method Methods 0.000 title claims description 8
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical class NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 title claims description 7
- OHWRASKXEUIFFB-UHFFFAOYSA-N NCP(O)=O Chemical class NCP(O)=O OHWRASKXEUIFFB-UHFFFAOYSA-N 0.000 title description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 33
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- VNWKTOKETHGBQD-YPZZEJLDSA-N carbane Chemical group [10CH4] VNWKTOKETHGBQD-YPZZEJLDSA-N 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 10
- MGRVRXRGTBOSHW-UHFFFAOYSA-N (aminomethyl)phosphonic acid Chemical compound NCP(O)(O)=O MGRVRXRGTBOSHW-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- HWJHZLJIIWOTGZ-UHFFFAOYSA-N n-(hydroxymethyl)acetamide Chemical compound CC(=O)NCO HWJHZLJIIWOTGZ-UHFFFAOYSA-N 0.000 description 2
- UOUBPDZUBVJZOQ-UHFFFAOYSA-N n-(hydroxymethyl)benzamide Chemical compound OCNC(=O)C1=CC=CC=C1 UOUBPDZUBVJZOQ-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- HKYGSMOFSFOEIP-UHFFFAOYSA-N dichloro(dichloromethoxy)methane Chemical compound ClC(Cl)OC(Cl)Cl HKYGSMOFSFOEIP-UHFFFAOYSA-N 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- KNQVWTDLQQGKSV-UHFFFAOYSA-O hydroxy-oxo-phenylphosphanium Chemical compound O[P+](=O)C1=CC=CC=C1 KNQVWTDLQQGKSV-UHFFFAOYSA-O 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical class CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- PMVVRSKJCGEFIY-UHFFFAOYSA-N methylphosphonous acid Chemical compound CP(O)O PMVVRSKJCGEFIY-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-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)]
- C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
-
- 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
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
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)
Description
HOECHST AKTIENGESELLSCHAFT HOE 90/F 250 Dr. WE/fe
Description
Process for the preparation of aminomethylphosphonic acid and aminomethylphosphinic acids from N-hydroxymethyl5 amides
Herbicidal and plant-growth-regulating actions are known of aminomethylphosphonic acid; aminomethylphosphinic acids are also industrially valuable compounds having a biological activity or can be used as intermediates for the preparation of biologically active compounds (see the article by L. Maier Advances in the Chemistry of Aminophosphinic Acids in the periodical Phosphorus and Sulfur 1983, Vol. 14, p. 295-322, in particular 317-323 and literature cited therein). Aminomethylphosphonic acid is furthermore valuable as an intermediate for the preparation of N-phosphonomethylglycine (see EP-A-214,578) .
To date, aminomethylphosphonic acid is accessible, for example, by reacting N-hydroxymethylamides with phosphorus trichloride, followed by hydrolysis, to give acylaminomethylphosphonic acids which subsequently give the end product by further hydrolysis by heating in hydrochloric acid (US-A-2,304,156; US-A-2,328,358). A particular disadvantage of this process consists in the formation of bischloromethyl ether as undesirable byproduct, which is known as being carcinogenic. The byproduct is formed in the hydrolysis steps by reaction of hydrochloric acid with formaldehyde, traces of which are contained in the N-hydroxymethylamides or the acylamino30 methylphosphonic acids, due to the preparation process.
However, the removal of remainders of this by-product requires a special purification step, and handling in the production process requires particular safety measures.
There is therefore a demand for industrially applicable processes which exclude the formation of this by-product.
- 2 The invention relates to a process for the preparation of compounds of the formula I i?/R h2nch2p
OH (I) in which R1 is hydroxyl, C^-C^-alkyl or phenyl, which 5 comprises reacting N-hydroxymethylamides of the formula II
RZ-CONHCH2OH (II) in which R2 is hydrogen, alkyl having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, benzyl or phenyl, unsubstituted or substituted by one or more radicals from the group comprising Cj-C^-alkyl, C^-C^-alkoxy and halogen, with phosphorous acid or phosphonous acids of the formula III
H
(HI) in which R1 is as defined above, in the presence of an at least equimolar amount of acetic anhydride, based on the compound of the formula II, and the reaction product obtained after the reaction is subsequently reacted with water at 80 to 300’C, preferably 150 to 250’C.
R1 is preferably hydroxyl, methyl or phenyl. R2 is preferably CH3 or phenyl which can be substituted by methyl or halogen; R2 is, in particular, unsubstituted phenyl.
Examples of suitable starting compounds in the process according to the invention are: N-hydroxymethyl25 formamide, N-hydroxymethylacetamide and, in particular,
- 3 N-hydroxymethylbenzamide. Examples of acids of the formula III are phosphorous acid, methylphosphonous acid and benzenephosphonous acid. The compounds of the formulae II and III are generally known and commercially available or readily accessible by known processes.
The molar ratio of the components to one another is a particularly important factor for the yield. The starting substances N-hydroxymethylamide of the formula II, acid of the formula III and acetic anhydride are preferably employed in a molar ratio of 1:1:1.5 to 1:(1-1.1):8, in particular in a molar ratio of 1:1:1.5 to 1:1:4. A further excess of acetic anhydride is possible.
If appropriate, the reaction of II and III can be carried out in an organic solvent.
Examples of suitable solvents are polar protic and aprotic organic solvents such as acetic acid, acetonitrile, tetrahydrofuran or dioxane. Acetic acid is preferred as a solvent. It is also possible to dispense with the use of solvents.
For example, the process is advantageously carried out in such a way that the reactants are mixed in a temperature range from 5 to 60°C, if appropriate with cooling. In this process, the sequence of the addition of the components is not critical. For example, the solution of the acid of the formula III, dissolved in an organic solvent such as acetic acid, can be metered into the acetic anhydride, and the N-hydroxymethylamide of the formula II, which may be dissolved in a solvent, can then be added batchwise or continuously to this mixture. When mixing has ended, stirring may be continued, for example in the temperature range from 10 to 60’C, and the mixture is then preferably refluxed.
When the reaction is complete, it may make sense to remove the organic solvent which may have been added in
- 4 the previous reactions, but also excess acetic anhydride, as well as acetic acid which has formed, for example by distillation, if appropriate under reduced pressure. When the reaction is complete, it can furthermore be expedient to hydrolyze the amount of excess acetic anhydride, which is contained in the reaction mixture, for example by adding water. In some cases, in particular after the last-mentioned hydrolysis, it is also possible for the reaction material in crystalline form to be separated from the organic solvent by filtration with suction. The crude product or the purified product from the reaction of the compounds of the formulae II and III is then treated with, water, if appropriate with an excess of water, and reacted at 80 to 300°C, preferably 150-250°C.
The extent of the excess of water is not particularly critical for the reaction; for example, for reasons of better handling, it may be advantageous to use a 2 to 30 molar, preferably 10 to 25 molar, excess of water. The reaction temperatures are 80 to 300°C, preferably 150 to
250 °C. The reaction times depend on the substrate, reaction temperature and pressure and are generally in the range from 5 to 40 hours, preferably 10 to 35 hours.
Working-up after this reaction is straightforward; for example, a carboxylic acid such as benzoic acid can generally be removed in the form of a solid, and acetic acid can be removed by means of distillation. The resulting aminomethylphosphonic acid and the aminomethylphosphinic acids can, if appropriate, be subjected to ultrapurification by customary methods such as, for example, crystallization.
Example 1 g (0.64 mol) of acetic anhydride were cooled to 10°C and treated dropwise with a mixture of 16.4 g (0.2 mol) of phosphorous acid in 40 ml of acetic acid, with stirring. 30.2 g (0.2 mol) of N-hydroxymethylbenzamide were subsequently added in portions at approx. 10°C in the course of 10 to 15 minutes. The reaction mixture was subsequently maintained under reflux for 2.5 hours. After concentration under reduced pressure, the residue was
51 g, which were subsequently dissolved in 120 ml of hot water (= 171 g). 53 g of this solution were maintained in a sealed tube for 20 hours at 200°C. After cooling and digestion with water, benzoic acid was removed by filtration. The filtrate was concentrated under reduced pres10 sure until it had reached an internal temperature of
95°C, and the residue was digested with methanol. 6 g of aminomethylphosphonic acid of a decomposition point of 290°C were obtained. Based on the total amount (171 g instead of 53 g), this corresponds to a yield of 19.4 g (87 % of theory) of aminomethylphosphonic acid.
Example 2
40.8 g (0.4 mol) of acetic anhydride were cooled to 10eC. To this, there was first added dropwise a mixture of
16.4 g (0.2 mol) of phosphorous acid in 40 ml of acetic acid in the course of 5 minutes and subsequently at 10°C
17.8 g (0.2 mol) of N-hydroxymethylacetamide in the course of 10 minutes, with stirring. After this, the batch was allowed to come to room temperature. The mixture was subsequently refluxed for 2.5 hours. After this, the mixture was cooled to room temperature, and 50 g of water were added slowly. On adding water, the temperature rose to 30’C. The mixture was then again refluxed to hydrolyze the excess acetic anhydride. To remove the solvent, the mixture was finally concentrated under reduced pressure until it had reached an internal temperature of 95’C. The resulting residue of 30.3 g was dissolved in 30 g of water and the mixture was refluxed for 2 hours. The reaction mixture was subsequently maintained in a sealed tube for 20 hours at 200eC. After cooling, it was concentrated under reduced pressure until it had reached an internal temperature of 95°C. The residue was digested with a mixture of 30 ml of methanol
- 6 and 10 ml of water. 16.1 g (72.5 % of theory) of amino methylphosphonic acid were obtained.
HOE 90/F 250
Claims (5)
1. A process for the preparation of compounds of the formula I 0 R J H 2 NCH 2 P (I) OH 5 in which R 1 is hydroxyl, C 1 -C 4 -alkyl or phenyl, which comprises reacting N-hydroxymethylamides of the formula II R 2 -CONHCH 2 OH (II) in which R 2 is hydrogen, alkyl having 1 to 6 carbon 10 atoms, benzyl or phenyl, unsubstituted or substituted by one or more radicals from the group comprising Ci-C^-alkyl, Cx-C^-alkoxy and halogen, with phosphorous formula III acid or phosphonous acids of the H 0 R 1 - / ^OH (III) in which R 1 is as defined above, in the presence of an at least equimolar amount of acetic anhydride, based on the compound of the formula II, and the reaction product obtained after the reaction is 20 subsequently reacted with water at 80 to 300°C.
2. The process as claimed in claim 1, in which R 1 is hydroxyl.
3. The process as claimed in claim 1, in which R 1 is methyl, ethyl or phenyl.
4. 4.
5. 5. 5 6. 5 6. 7. 7. 8. 8. 9. 9. 10. 10. The process as claimed in claim 1, 2 or 3, in which R 2 is H, Ci-Ca-alkyl, benzyl or phenyl. The process as claimed in claim 1, 2 or 3, in which R 2 is phenyl. The process as claimed in one or more of claims 1 to 5, in which the reaction temperature for the reaction with water is 150 to 250°C. The process as claimed in one of claims 1 to 6, in which the compounds of the formulae II and III and acetic anhydride are reacted in a molar ratio of 1:1:1.5 to 1:(1-1.1):8. The process as claimed in claim Ί, in which the molar ratio is from 1:1:1.5 to 1:1:4. The process as claimed in one of claims 1 to 7, in which the reaction of the compounds of the formulae II and III is carried out in the presence of an organic solvent. The process as claimed in claim 9, in which the solvent is acetic acid. A process according to claim 1 for the preparation of a compound of the formula (I) given and defined therein, substantially as hereinbefore described and exemplified. A compound of the formula (I) given and defined in claim 1, whenever prepared by a process claimed in a preceding claim.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4026028A DE4026028A1 (en) | 1990-08-17 | 1990-08-17 | METHOD FOR PRODUCING AMINOMETHANEPHOSPHONIC ACID AND AMINOMETHYL PHOSPHINIC ACIDS FROM N-HYDROXYMETHYL AMIDES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| IE912921A1 true IE912921A1 (en) | 1992-02-26 |
Family
ID=6412400
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IE292191A IE912921A1 (en) | 1990-08-17 | 1991-08-16 | Process for the preparation of aminomethylphosphonic acid¹and aminomethylphosphinic acids from N-hydroxymethylamides |
Country Status (8)
| Country | Link |
|---|---|
| CN (1) | CN1029616C (en) |
| AU (1) | AU8309891A (en) |
| DE (1) | DE4026028A1 (en) |
| IE (1) | IE912921A1 (en) |
| IL (1) | IL99201A (en) |
| PT (1) | PT98701B (en) |
| WO (1) | WO1992003448A1 (en) |
| ZA (1) | ZA916501B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2683222B1 (en) * | 1991-10-31 | 1995-05-19 | Rhone Poulenc Agrochimie | PROCESS FOR PRODUCING AMINOALKANEPHOSPHONIC ACIDS, SALTS AND / OR ESTERS. |
| US5233080A (en) * | 1992-09-25 | 1993-08-03 | E. I. Du Pont De Nemours And Company | Preparation of N-acylaminomethylphosphonic acids and aminomethylphosphonic acids |
| GB9307235D0 (en) * | 1993-04-07 | 1993-06-02 | Zeneca Ltd | Process |
| CN104762689B (en) * | 2015-04-09 | 2017-01-04 | 泰索新材料科技（杭州）有限公司 | A kind of fire-retardant Nylon 6 fiber and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3824961A1 (en) * | 1988-07-22 | 1990-01-25 | Basf Ag | Process for the preparation of bis(aminomethyl)phosphinic acid, and acidic or basic salts thereof |
| HU203360B (en) * | 1988-11-25 | 1991-07-29 | Monsanto Co | Process for producing n-acylamino methylphosphonates |
-
1990
- 1990-08-17 DE DE4026028A patent/DE4026028A1/en not_active Withdrawn
-
1991
- 1991-08-07 AU AU83098/91A patent/AU8309891A/en not_active Abandoned
- 1991-08-07 WO PCT/EP1991/001493 patent/WO1992003448A1/en active Application Filing
- 1991-08-15 IL IL9920191A patent/IL99201A/en active IP Right Grant
- 1991-08-16 IE IE292191A patent/IE912921A1/en unknown
- 1991-08-16 CN CN91105716A patent/CN1029616C/en not_active Expired - Fee Related
- 1991-08-16 ZA ZA916501A patent/ZA916501B/en unknown
- 1991-08-16 PT PT98701A patent/PT98701B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| ZA916501B (en) | 1992-04-29 |
| AU8309891A (en) | 1992-03-17 |
| PT98701B (en) | 1999-01-29 |
| PT98701A (en) | 1992-07-31 |
| DE4026028A1 (en) | 1992-02-20 |
| IL99201A (en) | 1995-10-31 |
| WO1992003448A1 (en) | 1992-03-05 |
| CN1059146A (en) | 1992-03-04 |
| IL99201A0 (en) | 1992-07-15 |
| CN1029616C (en) | 1995-08-30 |
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