AU607040B2 – Process for preparing n-phosphono-methyl-imino-diacetic acid
– Google Patents
AU607040B2 – Process for preparing n-phosphono-methyl-imino-diacetic acid
– Google Patents
Process for preparing n-phosphono-methyl-imino-diacetic acid
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Publication number
AU607040B2
AU607040B2
AU28798/89A
AU2879889A
AU607040B2
AU 607040 B2
AU607040 B2
AU 607040B2
AU 28798/89 A
AU28798/89 A
AU 28798/89A
AU 2879889 A
AU2879889 A
AU 2879889A
AU 607040 B2
AU607040 B2
AU 607040B2
Authority
AU
Australia
Prior art keywords
imino
diacetic acid
acid
phosphono
methyl
Prior art date
1988-02-08
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired – Fee Related
Application number
AU28798/89A
Other versions
AU2879889A
(en
Inventor
Sandor Balint
Janosne Benczik
Bela Karacsonyi
Csaba Kayos
Zoltan Kolonics
Sandor Laszlo
Laszlo Lendvai
Jeno Polyva
Csaba Suptei
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nitrokaelepek
Original Assignee
Nitrokaelepek
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
1988-02-08
Filing date
1989-01-25
Publication date
1991-02-21
1989-01-25
Application filed by Nitrokaelepek
filed
Critical
Nitrokaelepek
1989-08-10
Publication of AU2879889A
publication
Critical
patent/AU2879889A/en
1991-02-21
Application granted
granted
Critical
1991-02-21
Publication of AU607040B2
publication
Critical
patent/AU607040B2/en
2009-01-25
Anticipated expiration
legal-status
Critical
Status
Expired – Fee Related
legal-status
Critical
Current
Links
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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 System
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, i.e. RP(=X)(XH)2 (X = S, Se)
C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
Description
A,
jA» 0 7 0 4 0 COMMONWEALTH OF AUSTRALIA Patents Act 1952 Name of Applicant(s): Address of Applicant(s): Actual Inventor(s): NITROKEMIA IPARTELEPEK
«C
C
CC
CCCC
C C C Cc C at a C CCC a cc SC C a ea at C at I CC
FUZFOGYARTELEP
H-8184, HUNGARY JENO PELYVA CSABA SUPTEI ZOLTAN KOLONICS BELA KARACSONYI SANDOR BALINT JANOSNE BENCZIK OSABA KAYOS LAS ZLO LENDVAI SANDOR LAS ZLO LThis document contns the aMendne~nts mad,(e uinder Scction 49 H141 is cturtect for prii CC C C Ce, C C C C aC 0C CC C C C Address for Service: CULLEN CO., Patent Trade Mark Attorneys, 240 Queen Sw,-eet, Br~isbane, Q16. 4000, Australia.
COMPLETE SPECIFICATION FOR THE INVENTION ENTITLED: PROCESS FOR PREPARING N-PHOSPHONO-METHYL-IMINO-DIACETIC ACID The following statement is a full description of the invention including the best method of performing it known to ‘4.
-la- PROCESS FOR PREPARING N-PHOSPHONO-TETHYL- IINO- -DIACETIC ACID 0 00 0000 0 004 00 0 00 0 0 0 00 0 00 0 0 The invention relates to the preparation 0000 0 0 0 00 0 of N-phosphono-methyl-imino-diacetic acid starting 0 00 0 00 from the acidic calcium salt of imino-acetic 0 O0 u acid.
N-phosphono-methyl-imino-diacetic acid 000 o» is an important intermediate during the preparation 000 0 %00, 0 of N-phosphono-methyl-glycine (glyphosate) of wide activity spectrum. HU-PS No. 177,155 relates to the preparation of N-phosphono-methyl-imino-diacetic acid, wherein the acidic calcium salt of imino-diacetic acid is described. According’ to this patent specification the double salt of, formula A #1 -2-
A.
Ca 0 1 O=c
I
0 1 c=o
I
C C C
CC
V C C 0 C 0. 4 0 0 4C a 000 004a a0 0 HN
NH
C-CH2y O H C L C I
?H
2 0
II
O H is prepared by adding calcim-hydroxcide to the ammonium salt of monochioro-acetic acid in aqueous medium in a given molar ratio removing ammonia from beside the soluble imino-diacetic acid calcium salt, and adjusting the pH-value of the solution with hydrochloric acid to a value between 2 to 6. Purpose of the preparation of the doiuble salt is to prepare N-phosphono-methyl-imino-diacetic acid during which the aqueous suspension of the double salt is subjected to double decomposition with a sodiumsulphate solution in a molar excess of 30 the gypsum formed is centrifuged and the aqueous solution of imino-diacetic acid monosodium salt is reacted with paraformaldehyde in a molar excess of 50 and with phosphorus-trichloride in a molar excess of 5 After the reaction aqueous sodium-hydroxide solution is added and the product is separated by cooling.
Yield is about 60 calculated for monochloric acetic acid. Disadvantage of the described process is that by adding sodium salt used to double decomposition the amount of the inorganic salt forming in the process and polluting the environment strongly increases. From the great amount of phosphorus trichlorid used by reacting double calcium salt hydrochloric acid is -C formed, which should be neutralized by using sodiumhydroxide in order to achieve the precipitation of N-phosphono-methyl-imino-diacetic acid with suitable yield. By adding sodium hydroxide a further amount C of sodium-chloride is formed in the process, which pollutes the end-product. Because of the use of phosphorus-trichloride the binding of the significant amount of hydrochlorid acid requires considerable costs.
Subject of the invention is to prepare Nphosphono-methyl-imino-diacetic acid on one side by simplified synthesis, on the other side for eliminating -4i the formation of side products polluting the eni vironment.
i The process according to the invention i for preparing N-phosphono-methyl-imino-diacetic acid by using the imino-diacetic acid calcium salt formed from monochloric acetic acid, ammonia and calcium- -hydroxide can be characterized by heating the cal- I cium salt of imino-diacetio acid with concentrated hydrochlorid acid in a molar ratio of 2-3:1 at a temperature between 50-100°C, separating the obtained imino-diacetic acid hydrochloride, then dissolving it in water and optionally after purification reacting it with phosphorous acid in a molar ratio of 1.0-1.2:1 and with the aqueous solution of formaldehyde in a molar ratio of 1.0-1.4:1 under boiling, isolating the obtained product optionally after evaporating the mix- C ture.
The process according to the invention is carried out as follows: Into the aqueous solution of 60% monochlor- C 0 t -acetic acid ammonia is added at 20-30 C in a molar r c ratio of 0.6:1. After the addition is finished calciumhydroxide is added to the reaction mixture in small doses at 35-40°C in a molar ratio of 1.05:1 under cooling.
The imino-diacetic acid calcium saltformed during the reaction is transformed into imino-diacetic acid hydrochloride by using concentrated hydrochloric acid in a molar ratio of 2.5:1 by boiling the mixture at 60-80°C. After the reaction the mixture is cooled i0 to l0-20OC the precipitated imino-diacetic acid hydrochloride is filtered, then after transformation into imino-diacetic acid it is dissolved in water, the mechanical impurities are removed and phosphorous acid is added in a molar ratio of 1.05:1. The mixture obtained is heated to its boiling point and formaldehyde is added in a molar ratio of 1.2:1 in the form of aqueous solution. The N-phosphonomethyl-imino-diacetic acid obtained is filtered.
Advantages of th. process according to the invention can be summarized as follows: the end-product can be prepared with good yield in a simplified synthesis, isolating of imino-diacetic acid is not necessary, the process can be carried out in less steps and much less side-product are formed, fr neither the preparation of imino-diacetic acid from its hydrochloride, nor the transformation of ithe calcium salt of imino-diacetic acid into sodium salt are necessary, the imino-diacetic acid hydrochloride intermediate can directly be used as the starting ria-.
terial of the process according to the invention without purification and drying, the technical difficulties, such as the _I -6 c cc
‘CO
L CC C CC C CC Ce C C neutralization of the great amount of hydrochloric acid formed during preparation can be eliminated by using phosphorous acid, the process can be carried out in simple apparatuses/equipments.
The process according to the invention is described in detail in the following non-limiting Examples.
Example 1 Into a coolable, heatable, enamelled autoclave with a volume of 500 litre equipped with a stirrer, thermometer, and reflux condenser 190 kg of 50 aqueous monochloro-acetic acid solution kmole) was introduced. After cooling 12.75 kg (0.75 kmole) of ammonia gas was introduced into the solution under stirring. While keeping the temperature of the reaction mixture at 35-40 0 C, 77.7 kg (1.05 kmole) of calcium-hydroxide was added in equal doses within 2.5 hours. The reaction mixture obtained is then stirred for 6 hours at a temperature between 40-500C.
litre of this mixture was then distilled off in vacuo at a temperature around 800C for removing the ammonia excess. 200 litre of 37 hydrochloric acid was then added to the reactor and it was stirred for one hour at 60-800 The reaction mixture obtained was cooled to 10-200C and after stirring for 2-3 hours the imino-diacetic acid hydrogen chloride was filtered out.
-7 Imino-diacetic acid-hydrogen chloride was obtained in an amount of 101 kg, containing humidity. Thereafter it was solved in 100 litre of water, filtered from the mechanical impurities, then analyzed. The aqueous solution contains about 68 kg of imino-diacetic acid-hydrochloride, which is 80 of the theoretical amount.
The aqueous solution was then heated with 34.1 kg (0=4 kmole) of 96 phosphorous acid in an autoclave equipped with heatable-coolable cooler and reflux condenser and stirrer at the temperature of the boiling point of the mixture. 39.7 kg (0.45 I kmole) of a 34 aqueous formaldehyde solution was added within an hour then stirred for further 2 hours at boiling point. Therafter it was cooled to 10-15°C and the precipitated N-phosphono-methyl-imino-diacetic acid was filtered out, washed with water then dried.
78,6 kg of product are obtained which is of 98.2 Yield of the phosphonomethylating step is 85.1 the yield calculated for monochlor-acetic acid is 1 67.9 C Example 2 Into an enamelled apparatus of a volume of 500 litre equipped with coolable-heatable stirrer, cooler and refluxing cool,,r 154.5 kg (1.0 kmole) of aqueous monochlor-acetio acid solution was introduced. 11.1 kg (0.65 kmole) of ammonia gas was intro- 8duced into the apparatus under cooling and stirring.
The temperature of the reaction mixture was kept at 35-400C and 77.7 kg (0,05 kmole) of calcium-hydroxide are added in equal parts within 2 hours. The reaction mixture obtained was stirred at 45-50°C for 7 hours, 200 litre of a 37 aqueous hydrochloric acid solution was added, thEnstirred for an hour at 60-80°C. The reaction mixture obtained was cooled to crystallized for 3-4 hours then filtered.
105 kg of solid product was obtained with 30 humidity.
S•»This product was dissolved in 100 litre of water, the mechanical impurities were filtered out o O 0 and introduced into an autoclave equipped with a coolable-heatable cooler and reflux condenser and stirrer.
On the basis of analysis imino-diacetic acid-hydrogenchloride amount in the solution obtained was 69.7 kg (0.41 kmole). 19.7 kg (0.2 kmole) of a 37 hydrochloric acid and 40.3 kg (0,49 kmole) of phosphorous acid were added to the solution. The reaction mixture obtained was heated to its boiling point and at the temperature of the boiling point 43.4 kg (0,49 kmole) of 34% aqueous formaldehyde solution was added within an hour then the reaction mixture was boiled for further 2 hours. It was then evaporated to 2/3 of its original volume, cooled to 10-15°C, the precipitated crystals were filtered, washed with water and dried.
t -9- 79.4 kg of f-phosphono-methyl-imino-diaoetic acid was obtained with a purity of 98 which decomposes at 208-2090.* Yield of the phosphonomethylating step is 83.6 %,yield calculated to monochioxr-acetic acid is 68.0 C C
Claims (3)
1. Process for preparing N-phosphono-methyl-imino- diacetic acid by using imino-diacetic acid calcium salt formed from monochlor-acetic acid, ammonia and calcium hydroxide, which comprises heating the calcium salt of imino- diacetic acid with concentrated hydrochloric acid in a molar ratio of 2-3:1 at a temperature between 50-100’C, isolating the obtained imino-diacetic acid hydrogen chloride, then dissolving it in water and reacting it after purification co,t if necessary with phosphorous acid in a molar ratio of C C t 1.2:1 calculated for imino-diacetic acid hydrogenchloride and with an aqueous solution of formaldehyde in a molar ratio of S» 1.0-1.4:1 under stirring, then if necessary after evaporation of the mixture isolating N-phosphono-methyl- imino-diacetic acid.
S2. A process for preparing N-phosphono-methyl-imino- 0 c diacetic acid substantially as herein described in either of S. Examples 1 and 2.
3. N-phosphono-methyl-imino-diacetic acid whenever prepared by a process as defined in claim 1 or claim 2. DATED this 2nd day of November 1990 NITROKEMIA IPARTELEPEK By their Patent Attorneys CULLEN CO.
AU28798/89A
1988-02-08
1989-01-25
Process for preparing n-phosphono-methyl-imino-diacetic acid
Expired – Fee Related
AU607040B2
(en)
Applications Claiming Priority (2)
Application Number
Priority Date
Filing Date
Title
HU88562A
HU200780B
(en)
1988-02-08
1988-02-08
Process for producing n-phosphonomethyl iminodiacetic acid from double salt of iminodiacetic acid
HU562/88
1988-02-08
Publications (2)
Publication Number
Publication Date
AU2879889A
AU2879889A
(en)
1989-08-10
AU607040B2
true
AU607040B2
(en)
1991-02-21
Family
ID=10950170
Family Applications (1)
Application Number
Title
Priority Date
Filing Date
AU28798/89A
Expired – Fee Related
AU607040B2
(en)
1988-02-08
1989-01-25
Process for preparing n-phosphono-methyl-imino-diacetic acid
Country Status (18)
Country
Link
US
(1)
US4931585A
(en)
JP
(1)
JPH01228996A
(en)
CN
(1)
CN1035293A
(en)
AU
(1)
AU607040B2
(en)
BE
(1)
BE1002095A5
(en)
BR
(1)
BR8900621A
(en)
DE
(1)
DE3903715A1
(en)
DK
(1)
DK39789A
(en)
ES
(1)
ES2010396A6
(en)
FR
(1)
FR2626883B1
(en)
GB
(1)
GB2215720B
(en)
GR
(1)
GR890100070A
(en)
HU
(1)
HU200780B
(en)
IT
(1)
IT1229522B
(en)
NL
(1)
NL8900280A
(en)
NZ
(1)
NZ227703A
(en)
PL
(1)
PL277488A1
(en)
PT
(1)
PT89578B
(en)
Families Citing this family (9)
* Cited by examiner, † Cited by third party
Publication number
Priority date
Publication date
Assignee
Title
US5312972A
(en)
*
1992-10-29
1994-05-17
Hampshire Chemical Corp.
Conversion of hydroxymethyl-iminodiacetic acid to phosphonomethyl-iminodiacetic acid
US5312973A
(en)
*
1993-03-25
1994-05-17
Finchimica S.P.A.
Process for producing n-phosphono-methyl-imino-diacetic acid
ES2172660T3
(en)
*
1995-06-07
2002-10-01
Monsanto Technology Llc
PROCEDURE TO PREPARE N-PHOSPHONOMETILIMINOACETIC ACID.
IES980552A2
(en)
1998-07-09
1999-08-11
Agritech Chemical Ltd
Improved process for preparing N-phosphonomethyl iminodiacetic acid
US6118022A
(en)
*
1998-09-08
2000-09-12
Hampshire Chemical Corp.
Synthesis of phosphonomethyliminodiacetic acid with reduced effluent
RU2674022C9
(en)
2012-07-17
2019-01-24
МОНСАНТО ТЕКНОЛОДЖИ ЭлЭлСи
Method for synthesis of alpha-aminoalkylenephosphonic acid
RU2694047C2
(en)
2012-07-17
2019-07-09
МОНСАНТО ТЕКНОЛОДЖИ ЭлЭлСи
Method for synthesis of aminoalkylene phosphonic acid
CN104854117B
(en)
2012-07-17
2018-12-25
孟山都技术有限责任公司
Method for synthesizing N- phosphonomethyliminoacidetic acidetic
US9676799B2
(en)
2012-07-17
2017-06-13
Straitmark Holding Ag
Method for the synthesis of N-(phosphonomethyl)glycine
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Priority date
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Assignee
Title
US3455675A
(en)
*
1968-06-25
1969-07-15
Monsanto Co
Aminophosphonate herbicides
EP0019445A2
(en)
*
1979-05-11
1980-11-26
Nitrokemia Ipartelepek
Process for the preparation of N-phosphonomethyl glycine
GB2154589A
(en)
*
1984-02-27
1985-09-11
Monsanto Co
Improved process for preparing n,n-diacetic acid aminomethylenephosphonic acid
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Assignee
Title
US2895989A
(en)
*
1956-06-22
1959-07-21
Dow Chemical Co
Method for the preparation of iminodiacetic acid
US4657705A
(en)
*
1985-09-23
1987-04-14
Monsanto Company
Process for the preparation of N-substituted aminomethylphosphonic acids
1988
1988-02-08
HU
HU88562A
patent/HU200780B/en
not_active
IP Right Cessation
1989
1989-01-24
NZ
NZ227703A
patent/NZ227703A/en
unknown
1989-01-25
AU
AU28798/89A
patent/AU607040B2/en
not_active
Expired – Fee Related
1989-01-27
GB
GB8901806A
patent/GB2215720B/en
not_active
Expired – Fee Related
1989-01-27
DK
DK039789A
patent/DK39789A/en
not_active
Application Discontinuation
1989-01-31
PT
PT89578A
patent/PT89578B/en
active
IP Right Grant
1989-01-31
PL
PL27748889A
patent/PL277488A1/en
unknown
1989-02-01
FR
FR898901265A
patent/FR2626883B1/en
not_active
Expired – Fee Related
1989-02-02
US
US07/306,032
patent/US4931585A/en
not_active
Expired – Fee Related
1989-02-03
BE
BE8900121A
patent/BE1002095A5/en
not_active
IP Right Cessation
1989-02-03
BR
BR898900621A
patent/BR8900621A/en
unknown
1989-02-03
IT
IT8919299A
patent/IT1229522B/en
active
1989-02-03
CN
CN89100720.2A
patent/CN1035293A/en
active
Pending
1989-02-06
NL
NL8900280A
patent/NL8900280A/en
not_active
Application Discontinuation
1989-02-06
GR
GR890100070A
patent/GR890100070A/en
unknown
1989-02-07
ES
ES8900421A
patent/ES2010396A6/en
not_active
Expired
1989-02-07
JP
JP1028531A
patent/JPH01228996A/en
active
Pending
1989-02-08
DE
DE3903715A
patent/DE3903715A1/en
not_active
Withdrawn
Patent Citations (3)
* Cited by examiner, † Cited by third party
Publication number
Priority date
Publication date
Assignee
Title
US3455675A
(en)
*
1968-06-25
1969-07-15
Monsanto Co
Aminophosphonate herbicides
EP0019445A2
(en)
*
1979-05-11
1980-11-26
Nitrokemia Ipartelepek
Process for the preparation of N-phosphonomethyl glycine
GB2154589A
(en)
*
1984-02-27
1985-09-11
Monsanto Co
Improved process for preparing n,n-diacetic acid aminomethylenephosphonic acid
Also Published As
Publication number
Publication date
IT8919299D0
(en)
1989-02-03
CN1035293A
(en)
1989-09-06
AU2879889A
(en)
1989-08-10
BE1002095A5
(en)
1990-06-26
BR8900621A
(en)
1989-10-10
HU200780B
(en)
1990-08-28
FR2626883A1
(en)
1989-08-11
JPH01228996A
(en)
1989-09-12
ES2010396A6
(en)
1989-11-01
PT89578B
(en)
1994-01-31
PL277488A1
(en)
1989-10-16
HUT49360A
(en)
1989-09-28
FR2626883B1
(en)
1991-02-22
DE3903715A1
(en)
1989-08-17
NL8900280A
(en)
1989-09-01
GB2215720B
(en)
1991-07-10
GB8901806D0
(en)
1989-03-15
PT89578A
(en)
1989-10-04
US4931585A
(en)
1990-06-05
GR890100070A
(en)
1994-03-31
NZ227703A
(en)
1990-11-27
DK39789D0
(en)
1989-01-27
GB2215720A
(en)
1989-09-27
IT1229522B
(en)
1991-09-03
DK39789A
(en)
1989-08-09
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