HRP940884A2 - Method for preparation of salts of n-phosphonomethylglycine - Google Patents
Method for preparation of salts of n-phosphonomethylglycine Download PDFInfo
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- HRP940884A2 HRP940884A2 HRP940884A HRP940884A2 HR P940884 A2 HRP940884 A2 HR P940884A2 HR P940884 A HRP940884 A HR P940884A HR P940884 A2 HRP940884 A2 HR P940884A2
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- process according
- phosphonomethylglycine
- chloride
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- 238000000034 method Methods 0.000 title claims description 31
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical class OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims description 24
- 150000003839 salts Chemical class 0.000 title claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- OWUGVJBQKGQQKJ-UHFFFAOYSA-M trimethylsulfanium;chloride Chemical compound [Cl-].C[S+](C)C OWUGVJBQKGQQKJ-UHFFFAOYSA-M 0.000 claims description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 5
- 150000001805 chlorine compounds Chemical group 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical group [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical group I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052698 phosphorus Chemical group 0.000 claims description 4
- 239000011574 phosphorus Chemical group 0.000 claims description 4
- 125000005270 trialkylamine group Chemical group 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 3
- POYMFKJUYZDXAT-UHFFFAOYSA-N 1-(4-iodophenyl)pyrrolidine Chemical compound C1=CC(I)=CC=C1N1CCCC1 POYMFKJUYZDXAT-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000002955 isolation Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims 2
- 150000003973 alkyl amines Chemical class 0.000 claims 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 239000004009 herbicide Substances 0.000 description 17
- 239000002904 solvent Substances 0.000 description 10
- 241000196324 Embryophyta Species 0.000 description 7
- 125000005537 sulfoxonium group Chemical group 0.000 description 5
- 239000005648 plant growth regulator Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- SMYMJHWAQXWPDB-UHFFFAOYSA-N (2,4,5-trichlorophenoxy)acetic acid Chemical compound OC(=O)COC1=CC(Cl)=C(Cl)C=C1Cl SMYMJHWAQXWPDB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- -1 sulfoxonium halide Chemical class 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 239000003559 2,4,5-trichlorophenoxyacetic acid Substances 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- 239000005631 2,4-Dichlorophenoxyacetic acid Substances 0.000 description 1
- DFRHETNXRZJTGA-UHFFFAOYSA-N 2-(phosphanylmethylamino)acetic acid Chemical compound OC(=O)CNCP DFRHETNXRZJTGA-UHFFFAOYSA-N 0.000 description 1
- DLFKJPZBBCZWOO-UHFFFAOYSA-N 8-methyl-n,n-bis(8-methylnonyl)nonan-1-amine Chemical compound CC(C)CCCCCCCN(CCCCCCCC(C)C)CCCCCCCC(C)C DLFKJPZBBCZWOO-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- BWZOPYPOZJBVLQ-UHFFFAOYSA-K aluminium glycinate Chemical compound O[Al+]O.NCC([O-])=O BWZOPYPOZJBVLQ-UHFFFAOYSA-K 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 description 1
- USFRYJRPHFMVBZ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 USFRYJRPHFMVBZ-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 244000038559 crop plants Species 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- NTNZTEQNFHNYBC-UHFFFAOYSA-N ethyl 2-aminoacetate Chemical compound CCOC(=O)CN NTNZTEQNFHNYBC-UHFFFAOYSA-N 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical class CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 229960002523 mercuric chloride Drugs 0.000 description 1
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 1
- CLZGJKHEVKJLLS-UHFFFAOYSA-N n,n-diheptylheptan-1-amine Chemical compound CCCCCCCN(CCCCCCC)CCCCCCC CLZGJKHEVKJLLS-UHFFFAOYSA-N 0.000 description 1
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 description 1
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- VFJYIHQDILEQNR-UHFFFAOYSA-M trimethylsulfanium;iodide Chemical compound [I-].C[S+](C)C VFJYIHQDILEQNR-UHFFFAOYSA-M 0.000 description 1
Description
Osnova izuma The basis of the invention
Ovaj izum odnosi se na novi postupak za dobivanje trialkilsulfonij, sulfoksonij i organskih kvaternernih soli N-fosfonometilglicina na bazi dušika ili fosfata, spojeva koji su poznati herbicidi i regulatori rasta biljaka. This invention relates to a new process for obtaining trialkylsulfonium, sulfoxonium and organic quaternary salts of N-phosphonomethylglycine based on nitrogen or phosphate, compounds which are known herbicides and plant growth regulators.
Herbicide široko koriste poljoprivrednici, komercijalne poljoprivredne kompanije i druge industrije u cilju povećanja prinosa usjeva za takve usjeve kao što su soja, kukuruz, riža i slični, i za eliminiranje rasta korova duž autoputova, prostora pored željezničkih pruga i drugih površina. Herbicidi su efikasni u uništavanju ili kontroliranju neželjenih korova koji konkuriraju za hranjive sastojke zemljišta sa usjevnim biljkama, i zato što uništavaju korove, odgovorni su za poboljšanje estetskog izgleda okoline autoputova i željezničkih pruga. Postoji veći broj različitih tipova herbicida koji se trenutno prodaju komercijalno, i ovi spadaju u dvije opće kategorije. Kategorije su herbicidi prije nicanja i herbicidi poslije nicanja. Herbicidi sa djelovanjem prije nicanja primjenjuju se na zemljište prije nicanja korovnih biljaka iz zemljišta, a herbicidi sa djelovanjem poslije nicanja primjenjuju se na površine biljaka poslije nicanja korova ili drugih neželjenih biljaka iz zemljišta. Herbicides are widely used by farmers, commercial agricultural companies, and other industries to increase crop yields for such crops as soybeans, corn, rice, and the like, and to eliminate weed growth along highways, railroad tracks, and other areas. Herbicides are effective in killing or controlling unwanted weeds that compete for soil nutrients with crop plants, and because they kill weeds, they are responsible for improving the aesthetic appearance of highway and railroad environments. There are a number of different types of herbicides currently sold commercially, and these fall into two general categories. The categories are pre-emergence herbicides and post-emergence herbicides. Pre-emergence herbicides are applied to the soil before weed plants emerge from the soil, and post-emergence herbicides are applied to plant surfaces after weeds or other unwanted plants emerge from the soil.
Jedan od najranijih herbicida sa djelovanjem poslije nicanja koji je komercijalno korišten bio je 2,4-D (2,4-diklorfenoksioctena kiselina). Poslije većeg broja korištenja ovog i sličnih spojeva kao što je 2,4,5-T (2,4,5-triklorfenoksioctena kiselina), nađeno je da su izvjesni proizvodi raspadanja ovih herbicida bili dugotrajni i nisu se mogli biodegradirati. Mada je bilo izvjesnih nesporazuma između vladinih agencija i komercijalnih interesa u pogledu efekata rezidualnih proizvoda 2,4-D, 2,4,5-T i sličnih spojeva, agencije su svejedno ograničile korištenje ovih herbicida u Sjedinjenim Državama prije nekoliko godina. Od tog vremena, činjeni su napori da se razrade herbicidi koji su biorazgradivi u ne štetne sastojke unutar relativno kratkog vremenskog perioda poslije njihove primjene. One of the earliest postemergence herbicides to be used commercially was 2,4-D (2,4-dichlorophenoxyacetic acid). After a large number of uses of this and similar compounds such as 2,4,5-T (2,4,5-trichlorophenoxyacetic acid), it was found that certain decomposition products of these herbicides were long-lasting and could not be biodegraded. Although there has been some disagreement between government agencies and commercial interests regarding the effects of residual products of 2,4-D, 2,4,5-T and similar compounds, the agencies nevertheless restricted the use of these herbicides in the United States several years ago. Since that time, efforts have been made to develop herbicides that are biodegradable into non-harmful components within a relatively short period of time after their application.
Jedan takav spoj, za koji je nađeno da je biorazgradiv, a ipak je efikasan kao herbicid i regulator rasta biljaka kada se koristi u manjim obrocima, jeste N-fosfonometilglicin i njegove razne soli. N-fosfonometilglicin i njegove poljoprivredno efikasne soli prihvaćeni su za korištenje od strane Vlade Sjedinjenih Država i zato je ovaj herbicid postao komercijalno ekstremno uspješan. One such compound, which has been found to be biodegradable and yet effective as a herbicide and plant growth regulator when used in small doses, is N-phosphonomethylglycine and its various salts. N-phosphonomethylglycine and its agriculturally effective salts have been approved for use by the United States Government and that is why this herbicide has become extremely successful commercially.
N-fosfonometilglicin i izvjesne njegove soli su jedino efikasni i prihvaćeni herbicidi sa djelovanjem poslije nicanja na polju. Trenutno komercijalni spoj je izopropilaminska sol N-fosfonometilglicina i njeni derivati. Prilikom korištenja na polju normalno se primjenjuje u količinama od 0.01 do oko 20 funti po akru, poželjno 2 do 6 funti po akru. N-phosphonomethylglycine and certain of its salts are the only effective and accepted herbicides with post-emergence action in the field. The currently commercial compound is the isopropylamine salt of N-phosphonomethylglycine and its derivatives. When used in the field, it is normally applied at rates of 0.01 to about 20 pounds per acre, preferably 2 to 6 pounds per acre.
N-fosfonometilglicin i izvjesne njihove topljive soli mogu se pripremiti na veći broj različitih načina. N-phosphonomethylglycine and certain soluble salts thereof can be prepared in a number of different ways.
Jedan takav postupak, kao što je opisano u U.S. Patentu 3,160,632 (Toy et al., 8 prosinac, 1964) jest reakcija N-fosfinometilglicina (glicinmetilenfosfinske kiseline)sa merkuri-kloridom u vodenom otapalu na refluks temperaturi, i kasnije odvajanje reakcionih proizvoda. Drugi postupak jest reakcija etilglicinata sa formaldehidom i dietilfosfitom. Posljednji postupak opisan je u U.S. Patentu No. 3,799,758 (Franz, 26 ožujak, 1974). Dalje, postoji čitava serija patenta, koji se odnose na N-fosfonometilglicine, njihove soli i njihove derivate, i opisuje ih kao korisne herbicide i regulatore rasta biljaka. Takvi dodatni patenti koji se odnose na N-fosfonometilglicine, postupke za primjenu, postupke za izradu, soli i derivate, uključuju U.S. Patent 3,868,407, U.S. Patent 4,197,254 i U.S. Patent 4,199,354, između ostalih. One such procedure, as described in U.S. Pat. Patent 3,160,632 (Toy et al., December 8, 1964) is the reaction of N-phosphinomethylglycine (glycinemethylenephosphinic acid) with mercuric chloride in an aqueous solvent at reflux temperature, and the subsequent separation of the reaction products. Another procedure is the reaction of ethylglycinate with formaldehyde and diethylphosphite. The latter procedure is described in U.S. Patent No. 3,799,758 (Franz, March 26, 1974). Further, there is a series of patents relating to N-phosphonomethylglycines, their salts and their derivatives, describing them as useful herbicides and plant growth regulators. Such additional patents relating to N-phosphonomethylglycines, methods of use, methods of manufacture, salts and derivatives include U.S. Pat. U.S. Patent 3,868,407 4,197,254 and U.S. Pat. Patent 4,199,354, among others.
Trialkilsulfonij i sulfoksinij soli N-fosfonometilglicina, kako je nađeno, također su korisne i kao regulatori rasta biljaka i kao herbicidi. Ove soli opisane su u U.S. Patentu 4,315,765, Large. Kao što je opisano u tom patentu, spojevi se mogu napraviti iz N-fosfonometilglicina reakcijom posljednjeg sa srebro-oksidom tako da se formiraju srebrove soli ili sa natrij-hidroksidom tako da se formira natrijeva sol, i onda se tretira srebrova ili natrijeva sol sa trialkilsulfonij ili sulfoksonijhalogenidom. Poželjno je da se ovaj postupak pojednostavi, da se učini nepotrebnim izoliranje intermedijarnih proizvoda, i postupak iz sadašnjeg izuma ima za cilj da pojednostavi i učini manje skupim postotak za proizvodnju sulfonij i sulfoksonij soli, kao i izvjesnih organskih kvaternernih soli na bazi dušika ili fosfora. Trialkylsulfonium and sulfoxynium salts of N-phosphonomethylglycine have also been found to be useful as both plant growth regulators and herbicides. These salts are described in U.S. Pat. Patent 4,315,765, Large. As described in that patent, compounds can be made from N-phosphonomethylglycine by reacting the latter with silver oxide to form silver salts or with sodium hydroxide to form the sodium salt, and then treating the silver or sodium salt with trialkylsulfonium or sulfoxonium halide. It is desirable to simplify this process, to make it unnecessary to isolate the intermediate products, and the process of the present invention aims to simplify and make less expensive the percentage for the production of sulfonium and sulfoxonium salts, as well as certain organic quaternary salts based on nitrogen or phosphorus.
Izvod iz izuma Extract from the invention
Sada je otkriveno da se sulfonij i sulfoksonij soli i druge organske kvaternerne soli na bazi dušika ili fosfora N-fosfonometilglicina mogu proizvesti pomoću: It has now been discovered that the sulfonium and sulfoxonium salts and other nitrogen- or phosphorus-based organic quaternary salts of N-phosphonomethylglycine can be prepared by:
(1) reakcije N-fosfonometilglicina, spoja formule: (1) reactions of N-phosphonomethylglycine, compound of the formula:
[image] [image]
sa spojem koji je izabran iz grupe koji imaju formulu: with a compound selected from the group having the formula:
[image] [image]
gdje su R1, R2 i R3 isti ili različiti i to su alkil grupe koje imaju od 1 do 4 ugljikova atoma ili aralkil grupe, X je klorid, bromid ili jodid i Z je elektronski par ili kisik, ili where R1, R2 and R3 are the same or different and are alkyl groups having from 1 to 4 carbon atoms or aralkyl groups, X is chloride, bromide or iodide and Z is an electron pair or oxygen, or
[image] [image]
gdje su R1, R2 i R3 isti ili različiti i to su alkil grupe koje imaju od 1 do 4 ugljikova atoma i iste su kao u (a) gore, R4 je alkil grupa koja ima od 1 do 12 ugljikovih atoma, aril ili aralkil grupa, X je klorid, bromid ili jodid, i Y je dušik ili fosfor, pri čemu se spomenuta reakcija vrši u prisustvu trialkilamina formule where R1, R2 and R3 are the same or different and are alkyl groups having from 1 to 4 carbon atoms and are the same as in (a) above, R4 is an alkyl group having from 1 to 12 carbon atoms, an aryl or an aralkyl group , X is chloride, bromide or iodide, and Y is nitrogen or phosphorus, whereby the mentioned reaction is carried out in the presence of a trialkylamine of the formula
(R)3N (R)3N
gdje svaki R isti ili različiti i to je alkil grupa koja varira od 4 do 13 ugljikovih atoma, sve u prisustvu vode i nekog polarnog organskog otapala koje se ne miješa sa vodom, i where each R is the same or different and is an alkyl group varying from 4 to 13 carbon atoms, all in the presence of water and some polar organic solvent immiscible with water, and
(2) izoliranja krajnjeg proizvoda pomoću odvajanja faza. (2) isolation of the final product using phase separation.
Poželjni spojevi formule (a) prikazane gore za korištenje u postupku iz izuma uključuju trimetilsulfonijklorid, trimetilsulfoksonijklorid i trimetilsulfonijjodid, pri čemu je najpoželjniji spoj trimetilsulfonijklorid. Preferred compounds of formula (a) shown above for use in the process of the invention include trimethylsulfonium chloride, trimethylsulfoxonium chloride and trimethylsulfonium iodide, with the most preferred compound being trimethylsulfonium chloride.
Poželjni spojevi formule (b) kao što je prikazana gore, uključujući tetrametilamonijklorid, benziltributilamonijklorid, tetrabutilamonijjodid i benziltrifenilfosfonijklorid, pri čemu je najpoželjniji spoj tetrametilamonijklorid. Preferred compounds of formula (b) as shown above include tetramethylammonium chloride, benzyltributylammonium chloride, tetrabutylammonium iodide and benzyltriphenylphosphonium chloride, the most preferred compound being tetramethylammonium chloride.
Poželjni trialkilamini za korištenje u postupku iz izuma uključuju one sa alkil grupama (prvog niza ili račvastog) koje imaju 8 do 10 ugljikovih atoma. Komercijalne smjese kao što su predominantno C8 do C10 kao što je AlamineB, koji proizvodi Henkel Co., Minneapolis, Minn., su ekonomski podesne i najpoželjnije. Preferred trialkylamines for use in the process of the invention include those with alkyl groups (first chain or branched) having 8 to 10 carbon atoms. Commercial mixtures of predominantly C8 to C10 such as AlamineB, manufactured by Henkel Co., Minneapolis, Minn., are economically viable and most preferred.
Drugi podesni amini uključuju tributilamin, tripentilamin, triheksilamin, triheptilamin i triizodecilamin. Other suitable amines include tributylamine, tripentylamine, trihexylamine, triheptylamine and triisodecylamine.
Postoje izvjesni faktori koje treba poštovati koji su kritični za uspjeh postupka iz izuma. There are certain factors to be observed that are critical to the success of the process of the invention.
Polazni spoj je N-fosfonometilglicin. Ovaj spoje može se kupiti komercijalno ili se može napraviti većim brojem različitih načina kao što je ovdje ranije izloženo. The starting compound is N-phosphonomethylglycine. This compound can be purchased commercially or can be made in a number of different ways as set forth hereinbefore.
Trialkilamin koji se također koristi kao komponenta u postupku iz izuma, mora biti onaj koji je suštinski netopljiv u vodi i formira u vodi netopljivu sol HCl (klorovodikom) koja se odvaja od N-fosfonometilglicina i organske sumporne, dušične ili fosforne soli u cilju proizvodnje sulfonij ili sulfoksonij soli ili kvaternernih amonij ili fosfonij soli koje su krajnji proizvodi postupka iz izuma. The trialkylamine, which is also used as a component in the process of the invention, must be one that is essentially insoluble in water and forms a water-insoluble salt with HCl (hydrogen chloride) that is separated from N-phosphonomethylglycine and an organic sulfur, nitrogen or phosphorus salt in order to produce sulfonium or sulfoxonium salts or quaternary ammonium or phosphonium salts which are the end products of the process of the invention.
Otapalo za reaktante postupka kao što je naznačeno mora biti ono koje se ne miješa sa vodom. Nađeno je da je pogodno otapalo kombinacija toluola i amilalkohola u 7:3 težinskom odnosu, međutim, točan odnos ova dva otapala nije kritičan. Druga pogodna otapala uključuju metilenklorid, 1,2-dikloretan, metilizobutilketon, izobutilalkohol i n-amilalkohol. Otapalo mora biti ono koje je polarno i suštinski se ne miješa sa vodom. Može se koristiti nepolarno ko-otapalo za poboljšanje selektivnosti postupka u pogledu ograničavanja proizvodnje neželjenih sporednih proizvoda. The solvent for the process reactants as indicated must be one that is immiscible with water. A combination of toluene and amyl alcohol in a 7:3 weight ratio was found to be a suitable solvent, however, the exact ratio of these two solvents is not critical. Other suitable solvents include methylene chloride, 1,2-dichloroethane, methyl isobutyl ketone, isobutyl alcohol and n-amyl alcohol. The solvent must be one that is polar and essentially immiscible with water. A non-polar co-solvent can be used to improve the selectivity of the process in terms of limiting the production of unwanted side products.
Korištenjem poželjnih reaktanata, postupak iz izuma može se predstaviti prema sljedećoj formuli: Using the desired reactants, the process of the invention can be represented according to the following formula:
[image] [image]
[image] [image]
Prilikom provođenja postupka iz izuma, N-fosfonometilglicin i trimetilsulfonijklorid reagira u približno stehiometrijskim količinama, dok je amin prisutan u višku. When carrying out the process of the invention, N-phosphonomethylglycine and trimethylsulfonium chloride react in approximately stoichiometric amounts, while the amine is present in excess.
Količina korištenog otapala mora biti zadovoljavajuća da olakša odvajanje faza komponenata, i govoreći općenito poželjno je višak otapala. The amount of solvent used must be sufficient to facilitate phase separation of the components, and generally speaking an excess of solvent is desirable.
Poželjno se reakcija vrši na temperaturama koje variraju od oko 20 do oko 40°C, i tokom vremenskog perioda koji varira od oko 0.5 do oko 4 sata. Preferably, the reaction is carried out at temperatures varying from about 20 to about 40°C, and during a time period varying from about 0.5 to about 4 hours.
Ovaj izum će biti bolje shvaćen imajući za referencu sljedeći primjer koji služi da ilustrira izum ali nije namijenjen da ga ograniči. This invention will be better understood by reference to the following example which serves to illustrate the invention but is not intended to limit it.
Primjer I Examples
Uzme se balon sa okruglim dnom i u taj balon se doda 8.62 grama (g) 98.1% fosfonometilglicina (0.05 mola) suspendiranog u 12 mililitara (ml) vode i ovome se doda 7.7 g 72.9% vodene otopine trimetilsulfonijklorida (5.63 g, 0.05 mola) i 29.4 g Alamine-a® 336 (1.5 ekvivalenta) u 55 ml toluola i 25 ml amilalkohola. Ova smjesa se snažno miješa i sa nastavljenim miješanjem otopi se sav fosfonometilglicin. A round-bottomed flask is taken and to that flask is added 8.62 grams (g) of 98.1% phosphonomethylglycine (0.05 mol) suspended in 12 milliliters (ml) of water and to this is added 7.7 g of a 72.9% aqueous solution of trimethylsulfonium chloride (5.63 g, 0.05 mol) and 29.4 g of Alamine® 336 (1.5 equivalents) in 55 ml of toluene and 25 ml of amyl alcohol. This mixture is stirred vigorously and with continued stirring all the phosphonomethylglycine dissolves.
Tada se odvoje faze smjese i vodena (donja) faza (23.7 g) se tada koncentrira pod smanjenim pritiskom dajući 18.75 g proizvoda koji je bio vodena otopina za koju je nađeno da je 65% tež. sulfonij sol fosfonometilglicina. The mixture phases were then separated and the aqueous (lower) phase (23.7 g) was then concentrated under reduced pressure to give 18.75 g of product which was an aqueous solution found to be 65% by weight. sulfonium salt of phosphonomethylglycine.
Izvršeni su dodatni eksperimenti, u kojima su otapalo i kloridni spoj varirani prema Tablici I. niže. U Tablici I. polazni spoj, otapala i razni drugi konstituenti prikazani su zajedno sa reakcionim uvjetima i prinosom proizvoda. Additional experiments were performed, in which the solvent and chloride compound were varied according to Table I below. In Table I, the starting compound, solvents and various other constituents are shown together with the reaction conditions and product yield.
TABLICA I. TABLE I.
IZVOD IZ EKSPERIMENATA EXTRACT FROM EXPERIMENTS
[image] [image]
* PMG -fosfonometilglicin * PMG -phosphonomethylglycine
U postupku iz izuma, kao što je prikazano gore, N-fosfonometilglicin i trimetilsulfonijklorid se prvo miješaju u vodi sa aminom, sve u prisustvu otapala koje se ne miješa sa vodom. Aminklorhidrat, formiran prema formuli 1, se ekstrahira u organsku fazu na osnovu svoje niske topljivosti u vodi, tako da zaostaje krajnji proizvod, trialkilsulfonij ili sulfoksonij soli N-fosfonometilglicina ili druge organske soli u vodenoj fazi bez kontaminacije sa stranim ionima. In the process of the invention, as shown above, N-phosphonomethylglycine and trimethylsulfonium chloride are first mixed in water with the amine, all in the presence of a water-immiscible solvent. Amine hydrochloride, formed according to formula 1, is extracted into the organic phase on the basis of its low solubility in water, so that the final product remains, trialkylsulfonium or sulfoxonium salts of N-phosphonomethylglycine or other organic salts in the aqueous phase without contamination with foreign ions.
Postupak kao što je opisan gore je pogodan u odnosu na druge, koji zahtijevaju formiran intermedijarnih spojeva koji sami po sebi moraju odvajati u cilju provođenja raznih faza postupaka. The process as described above is convenient compared to others, which require the formation of intermediate compounds that must separate themselves in order to carry out various stages of the process.
Stručnjacima će biti jasno da se mogu vršiti varijacije u količinama reaktanata, korištenim temperaturama, korištenim molskim odnosima i reakcionom vremenu u postupku iz izuma, bez odstupanja od duha i obima pridodanih Zahtjeva. It will be clear to those skilled in the art that variations can be made in the amounts of reactants, the temperatures used, the mole ratios used and the reaction time in the process of the invention, without deviating from the spirit and scope of the appended Claims.
Claims (9)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/457,812 US4431594A (en) | 1983-01-13 | 1983-01-13 | Method for preparation of salts of N-phosphonomethylglycine |
| YU2299/83A YU43199B (en) | 1983-01-13 | 1983-11-22 | Process for obtaining n-phosphonomethyl glycine salts |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| HRP940884A2 true HRP940884A2 (en) | 1997-06-30 |
| HRP940884B1 HRP940884B1 (en) | 1998-12-31 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| HRP940884 HRP940884B1 (en) | 1983-01-13 | 1994-10-28 | Method for preparation of salts of n-phosphonomethylglycine |
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| Country | Link |
|---|---|
| HR (1) | HRP940884B1 (en) |
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| HRP940884B1 (en) | 1998-12-31 |
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