HRP940885A2 - Process for the preparation of n-phosphonomethyglycine - Google Patents
Process for the preparation of n-phosphonomethyglycine Download PDFInfo
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- HRP940885A2 HRP940885A2 HRP-2301/83A HRP940885A HRP940885A2 HR P940885 A2 HRP940885 A2 HR P940885A2 HR P940885 A HRP940885 A HR P940885A HR P940885 A2 HRP940885 A2 HR P940885A2
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- chlorine
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- 238000000034 method Methods 0.000 title claims description 21
- 238000002360 preparation method Methods 0.000 title description 10
- 238000006243 chemical reaction Methods 0.000 claims description 35
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 11
- -1 N-cyanomethyl-N-chloromethylamide acyl chloride Chemical class 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 7
- 150000001340 alkali metals Chemical group 0.000 claims description 6
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 4
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001263 acyl chlorides Chemical class 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 229910052700 potassium Chemical group 0.000 claims description 3
- 239000011591 potassium Chemical group 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000002346 iodo group Chemical group I* 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims 3
- 239000003377 acid catalyst Substances 0.000 claims 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- 239000011630 iodine Chemical group 0.000 claims 1
- 229910052740 iodine Chemical group 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- 239000000203 mixture Substances 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 239000002904 solvent Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 150000001266 acyl halides Chemical class 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- CTTRIWVSECLRDA-UHFFFAOYSA-N 2-[3,5-bis(cyanomethyl)-1,3,5-triazinan-1-yl]acetonitrile Chemical compound N#CCN1CN(CC#N)CN(CC#N)C1 CTTRIWVSECLRDA-UHFFFAOYSA-N 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000004009 herbicide Substances 0.000 description 3
- IBDQMQIFKZXODJ-UHFFFAOYSA-N n-(chloromethyl)-n-(cyanomethyl)acetamide Chemical compound CC(=O)N(CCl)CC#N IBDQMQIFKZXODJ-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- YPVUPNWBGXGHBB-UHFFFAOYSA-N 1,2-dichlorooct-1-ene Chemical compound CCCCCCC(Cl)=CCl YPVUPNWBGXGHBB-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- JGLMVXWAHNTPRF-CMDGGOBGSA-N CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O Chemical compound CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O JGLMVXWAHNTPRF-CMDGGOBGSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002015 acyclic group Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001334 alicyclic compounds Chemical class 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- UUYYJWFAHPQMJY-UHFFFAOYSA-N cyanomethoxy-oxido-oxophosphanium Chemical compound [O-][P+](=O)OCC#N UUYYJWFAHPQMJY-UHFFFAOYSA-N 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- NTNZTEQNFHNYBC-UHFFFAOYSA-N ethyl 2-aminoacetate Chemical compound CCOC(=O)CN NTNZTEQNFHNYBC-UHFFFAOYSA-N 0.000 description 1
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical class CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- OOUSUFKQKJONBC-UHFFFAOYSA-N n-(chloromethyl)acetamide Chemical compound CC(=O)NCCl OOUSUFKQKJONBC-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 229940093932 potassium hydroxide Drugs 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Područje izuma Field of invention
Ovaj izum je novi postupak za dobivanje N-fosfonometilglicina. This invention is a new process for obtaining N-phosphonomethylglycine.
Osnova izuma The basis of the invention
N-fosfonometilglicin i izvjesne soli su naročito efikasni kao herbicidi poslije nicanja. Komercijalni herbicid se prodaje kao formulacija koja sadrži izopropilaminsku sol N-fosfonometilglicina. N-phosphonomethylglycine and certain salts are particularly effective as post-emergence herbicides. The commercial herbicide is sold as a formulation containing the isopropylamine salt of N-phosphonomethylglycine.
N-fosfonometilglicin se može napraviti pomoću većeg broja postupka. Jedan takav postupak, kao što je opisan u U.S. Patentu 3,160,632 je reakcija N-fosfonometilglicina (glicin-metilenfosfonska kiseline) sa merkuri-kloridom u vodi na refluks temperaturi, i kasnije odvajanje reakcijskih proizvoda. Drugi postupci su fosfonometiliranje glicina i reakcija etil-glicinata sa formaldehidom. Posljednji postupak je opisan u U.S. Patent No. 3,868,407, 4,197,254 i 4,199,354. N-phosphonomethylglycine can be made using a number of processes. One such procedure, as described in U.S. Pat. Patent 3,160,632 deals with the reaction of N-phosphonomethylglycine (glycine-methylenephosphonic acid) with mercury chloride in water at reflux temperature, and the subsequent separation of the reaction products. Other procedures are phosphonomethylation of glycine and the reaction of ethyl glycinate with formaldehyde. The latter procedure is described in U.S. Patent No. 3,868,407, 4,197,254 and 4,199,354.
Srodna ranija znanost je u U.S. Patent 3,923,877 koji sugerira reakciju 1,3,5-tricijanometilheksahidro-1,3,5-triazina sa viškom disupstituiranog fosfita tako da se formira (RO)2P(O)CH2NHCH2CN (R je hidrikarbil ili supstituirani hidrokarbil) koji se hidrolizira tako da se dobiva N-fosfonometilglicin. Related earlier science is in the U.S. Patent 3,923,877 which suggests the reaction of 1,3,5-tricyanomethylhexahydro-1,3,5-triazine with excess disubstituted phosphite to form (RO)2P(O)CH2NHCH2CN (R is hydrocarbyl or substituted hydrocarbyl) which is hydrolyzed to give gets N-phosphonomethylglycine.
Zbog komercijalnog značaja N-fosfonometilglicina i izvjesnih soli kao herbicida, dragocjeni su poboljšani postupci za pripremu ovih spojeva. Because of the commercial importance of N-phosphonomethylglycine and certain salts as herbicides, improved procedures for the preparation of these compounds are valuable.
Kratak opis izuma Brief description of the invention
Ovaj izum odnosi se na postupak za prupremu N-fosfonometilglicina koji obuhvaća: This invention relates to a process for the preparation of N-phosphonomethylglycine, which includes:
(1) reakciju 1,3,5-tricijanometilheksahidro-1,3,5-triazina sa nekim acilhalogenidom, poželjno acilkloridom, tako da se formira N-cijanometil-N-halometilamid acil halogenida; (1) reaction of 1,3,5-tricyanomethylhexahydro-1,3,5-triazine with some acyl halide, preferably acyl chloride, so that N-cyanomethyl-N-halomethylamide acyl halide is formed;
(2) reakciju amida sa fosfitom tako da se formira N-acil-metil-N’cijanometilfosfonat; i (2) reaction of the amide with the phosphite to form N-acyl-methyl-N'cyanomethylphosphonate; and
(3) hidrolizu ovog fosfonata tako da se dobiva N-(fosfono-metil)-glicin. (3) hydrolysis of this phosphonate to yield N-(phosphono-methyl)-glycine.
Detaljan opis izuma Detailed description of the invention
Postupak iz ovog izuma može se ilustrirati slijedećom reakcijskom shemom: The process of this invention can be illustrated by the following reaction scheme:
[image] [image]
gdje je R alifatična ili aromatična grupa kao što je ovdje definirana kasnije, poželjno C1-4 alikl, najpoželjnije metil ili etil i X je klor, brom ili jod, poželjno klor. where R is an aliphatic or aromatic group as defined hereinbelow, preferably C1-4 alkyl, most preferably methyl or ethyl and X is chlorine, bromine or iodo, preferably chlorine.
[image] [image]
gdje su R i X definirani kao gore a R1 i R2 su oba aromatične grupe ili oba alifatične grupe, poželjno su R1 i R2 C1-C6 alkil, još poželjnije C1-4 alkil ili je R3 alkalni metal (M) poželjno natrij ili kalij. where R and X are defined as above and R1 and R2 are both aromatic groups or both aliphatic groups, preferably R1 and R2 are C1-C6 alkyl, more preferably C1-4 alkyl or R3 is an alkali metal (M) preferably sodium or potassium.
[image] [image]
gdje su R, R1 i R2 kao što je definirano gore i H+ je takva jaka kiselina kao što su klorovodična, bromovodična, jodovodična, dušična, sumporna, fosfonska ili klorooctena kiselina i OH- je takva jaka baza kao što su natrij-hidroksid ili kali-hidroksid, poželjno u vodenoj, vodeno-alkoholnoj ili alkoholnoj otopini. Poželjno se hidroliza vrši u prisustvu jake kiseline. where R, R1 and R2 are as defined above and H+ is such a strong acid as hydrochloric, hydrobromic, hydroiodic, nitric, sulfuric, phosphonic or chloroacetic acid and OH- is such a strong base as sodium hydroxide or potassium -hydroxide, preferably in an aqueous, aqueous-alcoholic or alcoholic solution. The hydrolysis is preferably carried out in the presence of a strong acid.
U gornjoj reakcijskoj shemi grupa R nije direktno uključena u reakcijskoj fazi (a) između 1,3,5-tricijanometilheksahidro-1,3,5-triazina i acilklorida. Grupe R, R1 ili R2 nisu direktno uključene u reakcijsku fazu (b) između N-cijanometil-N-kloro-metilamida reakcijskog proizvoda uz faze (a) i fosfita. Grupe R, R1 i R2 se odvajaju u reakcijskoj fazi (c) kada se fosfonat reakcijski proizvod iz reakcijske faze (b) podvrgne hidrolizi. Zato, prirodna grupa R, R1 i R2 nije kritična, premda se treba izbjegavati grupa koju će ometati reakcijska faza (a) i (b). In the above reaction scheme, the group R is not directly involved in the reaction phase (a) between 1,3,5-tricyanomethylhexahydro-1,3,5-triazine and acyl chloride. The groups R, R1 or R2 are not directly involved in the reaction phase (b) between N-cyanomethyl-N-chloro-methylamide of the reaction product in addition to phases (a) and phosphite. The groups R, R1 and R2 are separated in reaction step (c) when the phosphonate reaction product from reaction step (b) is subjected to hydrolysis. Therefore, the natural group R, R 1 and R 2 are not critical, although the group that will interfere with the reaction phase (a) and (b) should be avoided.
Grupa “C1-4 alkil” obuhvaća metil, etil, n-propil, izopropil n-butil, izobutil, sek-butil i terc-butil. Grupa “C1-4 alkil obuhvaća iste radikale kao C1-4 alkil plus 6 pentila i 16 heksila. The group "C1-4 alkyl" includes methyl, ethyl, n-propyl, isopropyl n-butyl, isobutyl, sec-butyl and tert-butyl. The group "C1-4 alkyl includes the same radicals as C1-4 alkyl plus 6 pentyl and 16 hexyl.
Termin “alifatična grupa” koristi se u širokom smislu da prikaže veliku klasu organskih grupa koje se karakteriziraju time što su izvedene iz (1) serija acikličnih (struktura otvorenog niza) parafinskih, olefinskih i acetilenskih ugljikovodika i njihovih derivata ili (2) alicikličnih spojeva. Alifatična grupa može imati od 1 do 10 ugljenikovih atoma. The term "aliphatic group" is used in a broad sense to denote a large class of organic groups characterized by being derived from (1) series of acyclic (open chain structure) paraffinic, olefinic and acetylenic hydrocarbons and their derivatives or (2) alicyclic compounds. An aliphatic group can have from 1 to 10 carbon atoms.
Termin “aromatična grupa” koristi se u širokom smislu da se razlikuje od alifatične grupe i uključuje grupu izvedenu iz (1) spojeva koji imaju 6 do 20 ugljikovih atoma, a karakterizira se prisustvom najmanje jednog benzolovog prstena, uključujući monociklične, biciklične, i policiklične ugljikovodike i njihove derivate i (2) heterocikličnih spojeva koji imaju 5 do 19 ugljikovih atoma koja su slična po strukturi i koja se karakteriziraju time što imaju nezasićenu prstenastu strukturu koja sadrži namanje jedan atom koji se razlikuje od ugljika kao što su dušik, sumpor i kisik i derivati ovih heterocikličnih spojeva. The term "aromatic group" is used in a broad sense to distinguish it from an aliphatic group and includes a group derived from (1) compounds having 6 to 20 carbon atoms and characterized by the presence of at least one benzene ring, including monocyclic, bicyclic, and polycyclic hydrocarbons and their derivatives and (2) heterocyclic compounds having 5 to 19 carbon atoms which are similar in structure and which are characterized by having an unsaturated ring structure containing at least one atom different from carbon such as nitrogen, sulfur and oxygen and derivatives of these heterocyclic compounds.
Reakcijska faza (a) poželjno se vrši na temperaturi između 0°C do oko 150°C, poželjnije između 40°C do oko 110°C i najpoželjnije između 75°C do oko 85°C. Ova reakcijska vaza može se vršiti na atmosferskom, sub-atmosferskom ili super-atmosferskom tlaku, poželjno na atmosferskom tlaku. Poželjno je da se reakcija vrši u nekom otapalu za acilhalogenih, kao što su etilendiklorid, metilenklorid, tetrahidroguran ili teluol. Reaction phase (a) is preferably carried out at a temperature between 0°C to about 150°C, more preferably between 40°C to about 110°C and most preferably between 75°C to about 85°C. This reaction vessel can be operated at atmospheric, sub-atmospheric or super-atmospheric pressure, preferably at atmospheric pressure. It is preferable that the reaction is carried out in a solvent for acylhalogens, such as ethylene dichloride, methylene chloride, tetrahydrofuran or telulol.
Potrebno je tri mola acilhalogenida za reakciju sa jednim molom 1,3,5-tricijanometilheksahidro-1,3,5-triazinom. Može se koristiti višak acilhalogenida za osiguranje kompletne reakcije sa triazinom. Veliki višak acilhalogenida može služiti kao otapalo u ovoj reakcijskoj fazi. Otapalo ili bilo koji višak acilhalogenida može se odvojiti radi izoliranja N-cijanometil-N-klorometilamida acilhalogenida u visokim prinosima. Međutim ovaj amid se brzo termički degradira i pomoću hidrolize i treba se držati u internoj atmosferi ako je izoliran. Three moles of acyl halides are required to react with one mole of 1,3,5-tricyanomethylhexahydro-1,3,5-triazine. An excess of acyl halide can be used to ensure complete reaction with the triazine. A large excess of acyl halide can serve as a solvent in this reaction phase. The solvent or any excess acyl halide can be removed to isolate the N-cyanomethyl-N-chloromethylamide acyl halide in high yields. However, this amide rapidly degrades thermally and by hydrolysis and should be kept in an internal atmosphere if isolated.
Najpoželjnije se ne koristi višak acilhalogenida i otapalo koje se koristi u reakcijskoj fazi (a) također se koristi kao otapalo u reakcijskoj fazi (b). Tako se otapalo ne mora odvajati poslije kompletiranja faze (a) i koristi se u reakcijskoj fazi (b). Most preferably, no excess acyl halide is used and the solvent used in reaction step (a) is also used as a solvent in reaction step (b). Thus, the solvent does not have to be separated after the completion of phase (a) and is used in the reaction phase (b).
U reakcijskoj fazi (b), najpoželjnije reagiraju oko jednake molske količine N-cijanometil-N-halometilamida acilhalogenida i fosfina. Manje poželjno mogu se koristiti do 2 molska viška i najmanje poželjno do 10 molova viška. In the reaction phase (b), approximately equal molar amounts of N-cyanomethyl-N-halomethylamide acyl halide and phosphine react most preferably. Less preferably, up to 2 molar excess and least preferably up to 10 molar excess can be used.
Reakcija je egzotermna i može se vršiti na temperaturi između 0 do 150°C., poželjnije između 40°C do oko 100°C, najpoželjnije između 75°C do oko 85°C. The reaction is exothermic and can be carried out at a temperature between 0 to 150°C, preferably between 40°C to about 100°C, most preferably between 75°C to about 85°C.
Nije potrebno otapalo za reakciju, međutim, može se koristiti bilo koje interno otapalo, poželjno otapalo koje ima točku ključanja između 40°C do oko 100°C. Primjeri takvih otapala su etilenklorid, metilenklorid, tetrahidrofuran i toluol. Korištenje internog otapala pomaže rasipanje reakcijske topline. Najpoželjnije je otapalo ono koje se koristi u reakcijskoj fazi (a). Bilo koje otapalo koje se koristi u ovoj reakcijskoj fazi bit će odvojeno poslije kompletiranja reakcijske faze (c), tako da je poželjno ono koje se može odvojiti isparavanjem. No solvent is required for the reaction, however, any internal solvent can be used, preferably a solvent having a boiling point between 40°C to about 100°C. Examples of such solvents are ethylene chloride, methylene chloride, tetrahydrofuran and toluene. Using an internal solvent helps dissipate the heat of reaction. The most preferred solvent is the one used in reaction step (a). Any solvent used in this reaction step will be separated after completion of reaction step (c), so one that can be separated by evaporation is preferred.
Alkalnometalni fosfiti koji imaju formulu: Alkali metal phosphites having the formula:
[image] [image]
gdje su R1 i R2 kao što je definirano, a R3 je alkalni metal oni reagiraju sa N-cijanometil-N-halometilamidom pod takvom internom atmosferom kao što je dušik. Alkalnometalni fosfit se može napraviti reakcijom alkoksida alkalnog metala, hidrida alkalnog metala ili alkalnog metala sa jednakom molskom količinom disupstituiranog fosfita formule: wherein R 1 and R 2 are as defined and R 3 is an alkali metal they react with N-cyanomethyl-N-halomethylamide under such an internal atmosphere as nitrogen. An alkali metal phosphite can be made by reacting an alkali metal alkoxide, an alkali metal hydride, or an alkali metal with an equal molar amount of a disubstituted phosphite of the formula:
[image] [image]
u kojoj su R1 i R2 kao što je definirano. Ova reakcija se vrši u takvoj internoj atmosferi kao što je dušik. in which R1 and R2 are as defined. This reaction is carried out in such an internal atmosphere as nitrogen.
Alkalnometalni fosfiti formule Alkali metal phosphites of the formula
[image] [image]
u kojoj su R1 i R2 i M kao što je definirano, zbog tautomerije imaju slijedeću dopunsku strukturnu formulu in which R1 and R2 and M are as defined, due to tautomerism have the following complementary structural formula
[image] [image]
gdje su R1 i R2 kao što je definirano a M je alkalni metal. where R1 and R2 are as defined and M is an alkali metal.
U reakcijskoj fazi (c), mol fosfonatnog reakcijskog proizvoda iz reakcijske faze (b) hidrolizira se sa 5 molova vode. Hidroliza se vrši u prisustvu jake kiseline ili baze kao što je definirano gore. Poželjna je hidroliza kiselo katalizirana, poželjna sa nekom neoragnskom kiselinom i najpoželjnija sa klorovodičnom ili bromovodičnom kiselinom. Hidroliza daje željeni N-fosfonometilglicin. Poželjno se koristi najmanje 2 mola kiseline. Najpoželjnije, koristi se veliki višak iznad 2 mola. Poželjno se klorovodična ili bromovodična kiselina može koristiti u koncentriranom ili vodenom obliku. In reaction phase (c), a mole of phosphonate reaction product from reaction phase (b) is hydrolyzed with 5 moles of water. Hydrolysis is carried out in the presence of a strong acid or base as defined above. Acid-catalyzed hydrolysis is preferred, preferably with some non-aronic acid and most preferably with hydrochloric or hydrobromic acid. Hydrolysis gives the desired N-phosphonomethylglycine. Preferably, at least 2 moles of acid are used. Most preferably, a large excess above 2 moles is used. Hydrochloric or hydrobromic acid can preferably be used in concentrated or aqueous form.
Posljednja reakcijska faza se vrši na temperaturi između 0 do oko 200°C, poželjno između 50°C do oko 125°C, i najpoželjnije između 100°C do oko 125°C. The last reaction phase is carried out at a temperature between 0 to about 200°C, preferably between 50°C to about 125°C, and most preferably between 100°C to about 125°C.
Mogu se koristiti atmosferski, sub-atmosferski ili super-atmosferski tlakovi. Poželjno se za vrijeme hidrolize koristi atmosferski tlak. Atmospheric, sub-atmospheric or super-atmospheric pressures can be used. Atmospheric pressure is preferably used during hydrolysis.
Krut N-fosfonometilglicin može se regenerirati konvencionalnim tehnikama u reakcijskoj fazi (c). Isparljivi tekući proizvodi kao što su alkoholi (metanol), kloridi (metilklorid), kiseline (octena kiselina), voda i višak kiseline mogu se odvojiti standardnim tehnikama za odvajanje. @eljeni N-fosfonometilglicin regenerira se visoko čist otapanjem u vodi. Prilagođavanje pH otopine na između 1 i 2, dozvoljavanjem da kristalizira iz otopine i odvajanjem filtracijom. Solid N-phosphonomethylglycine can be regenerated by conventional techniques in reaction step (c). Volatile liquid products such as alcohols (methanol), chlorides (methyl chloride), acids (acetic acid), water, and excess acid can be separated using standard separation techniques. The desired N-phosphonomethylglycine is regenerated in high purity by dissolving it in water. Adjusting the pH of the solution to between 1 and 2 by allowing it to crystallize from the solution and separating it by filtration.
Postupak iz ovog izuma može se bolje shvatiti imajući za referencu slijedeće specifične primjere. The process of the present invention can be better understood by reference to the following specific examples.
Primjer 1 Example 1
Dobivanje N-cijanometil-N-klorometilacetamida Preparation of N-cyanomethyl-N-chloromethylacetamide
[image] [image]
17 grama (g) (0.0835 mola) 1,3,5-tricijanometilheksahidro-1,3,5-triazina suspendira se u balonu sa okruglim dnom sa 150 mililitara (nl) 1,2-diklorooctena. Doda se odjednom 40 ml (0.563 mola) acetilklorida i reakcijska smjesa se refleksira 3 sata, tada se ispari pod smanjenim tlakom tako da se dobiva 26.9 g (79.85%) N-cijanometil-N-klorometilacetamida. Struktura je potvrđena uobičajenim analitičkim postupcima (infracrvena, protonska nuklearna magnetna rezonancija i masena spektroskopija). 17 grams (g) (0.0835 mole) of 1,3,5-tricyanomethylhexahydro-1,3,5-triazine is suspended in a round bottom flask with 150 milliliters (nl) of 1,2-dichloroacetone. 40 ml (0.563 mol) of acetyl chloride was added at once and the reaction mixture was refluxed for 3 hours, then it was evaporated under reduced pressure so that 26.9 g (79.85%) of N-cyanomethyl-N-chloromethylacetamide were obtained. The structure was confirmed by the usual analytical methods (infrared, proton nuclear magnetic resonance and mass spectroscopy).
Primjer 2 Example 2
Dobivanje 0,0-dimetil-N-cijanometil-N-acetilaminometilfosfona Preparation of 0,0-dimethyl-N-cyanomethyl-N-acetylaminomethylphosphone
[image] [image]
Amidni spoj napravljen u Primjeru 1 (26.9 g, 0.3 mola) razrijedi se sa 75 ml diklorometana. Doda se trimetilfosfit (25.5 g, 0.206 mola) i smjesa se miješa na sobnoj temperaturi preko noći, refleksira se 0.5 sati i ispari se pod smanjenim tlakom tako da se dobiva 43.9 g (79.32%) željenog proizvoda. Struktura je potvrđena pomoću infracrvene (ir), protonske nuklearne magnetne rezonancije (nmr) i masene spektroskopije (ms). The amide compound made in Example 1 (26.9 g, 0.3 mol) is diluted with 75 ml of dichloromethane. Trimethylphosphite (25.5 g, 0.206 mol) was added and the mixture was stirred at room temperature overnight, refluxed for 0.5 h and evaporated under reduced pressure to give 43.9 g (79.32%) of the desired product. The structure was confirmed using infrared (ir), proton nuclear magnetic resonance (nmr) and mass spectroscopy (ms).
Primjer 3 Example 3
Dobivanje N-fosfonometilglicina Preparation of N-phosphonomethylglycine
[image] [image]
Fosfonatni reakcijski proizvod iz Primjera 2 (19.5 g, 0.09 mola) kombinira se sa 100 ml (1.21 mola) koncentrirane klorovodične kiseline, refleksira se 3 sata i ispari se pod smanjenim tlakom. Poslije otapanja ostataka u 30 ml vode, pH se podesi na 10 sa 50% natrij-hidroksidom, smjesa se ispari pod smanjenim tlakom. Proizvod se ponovno otopi u 30 ml vode i pH se podesi na 1 sa koncentriranom klorovodičnom kiselinom. Smjesa se drži u hladnjaku preko noći i slijedeće jutro izolira se filtracijom 5.4 g (98.3% čistoća po težini) željenog proizvoda (35.49% prinos). Struktura je potvrđena pomoću ir spektroskopije, nmr i tekuće kromatografije (1c). The phosphonate reaction product from Example 2 (19.5 g, 0.09 mol) is combined with 100 ml (1.21 mol) of concentrated hydrochloric acid, refluxed for 3 hours and evaporated under reduced pressure. After dissolving the residues in 30 ml of water, the pH is adjusted to 10 with 50% sodium hydroxide, the mixture is evaporated under reduced pressure. The product is redissolved in 30 ml of water and the pH is adjusted to 1 with concentrated hydrochloric acid. The mixture is kept in the refrigerator overnight and the next morning, 5.4 g (98.3% purity by weight) of the desired product (35.49% yield) is isolated by filtration. The structure was confirmed by IR spectroscopy, nmr and liquid chromatography (1c).
Primjer 4 Example 4
Dobivanje N-fosfonometilglicina Preparation of N-phosphonomethylglycine
50 ml. 1,2-dikloroctena zagrijava se na refluksu u balonu sa okruglim dnom od 50 ml. Dodaje se istovremeno acetilklorid (5.5 ml, 0.077 mola) i 3.4 g (0.0167 mola) 1,3,5-tricijanometilheksahidro-1,3,5-triazina tijekom 10 minuta uz održavanje viška acetilhalogenida u reakcijskoj posudi. Smjesa se refleksira 0.5 sati pošto je dodavanje završeno i tada se ispari pod smanjenim tlakom. 50 ml. 1,2-dichlorooctene is heated at reflux in a 50 ml round-bottomed flask. Acetyl chloride (5.5 ml, 0.077 mol) and 3.4 g (0.0167 mol) of 1,3,5-tricyanomethylhexahydro-1,3,5-triazine are added simultaneously over 10 minutes while maintaining an excess of acetyl halide in the reaction vessel. The mixture is refluxed for 0.5 hours after the addition is complete and then evaporated under reduced pressure.
Dodaju se 5 ml toluola i 6.6 ml (0.05 mola) trimetilfosfita na ostatak i ova smjesa se reflektira 15 minuta, mješa se na sobnoj temperaturi 2 sata i ispari se pod smanjenim tlakom. Doda se 30 ml koncentrirane (0.36 mola) klorovodične kiseline na ostatak i smjesa se reflektira 3 sata i odvoji se pod smanjenim tlakom tako da se dobiva 11.3 g krutih tvari koje sadrže 47.9% tež. željenog N-fosfonometilglicina kao što je određeno pomoću 1c. Struktura je potvrđena pomoću C13 i protonske nmr. Ukupan prinos N-fosfonometilglicina bio je 64%. 5 ml of toluene and 6.6 ml (0.05 mol) of trimethylphosphite are added to the residue and this mixture is refluxed for 15 minutes, stirred at room temperature for 2 hours and evaporated under reduced pressure. 30 ml of concentrated (0.36 mol) hydrochloric acid is added to the residue and the mixture is refluxed for 3 hours and separated under reduced pressure so that 11.3 g of solids containing 47.9% by weight are obtained. of the desired N-phosphonomethylglycine as determined by 1c. The structure was confirmed by C13 and proton nmr. The total yield of N-phosphonomethylglycine was 64%.
Primjer 5 Example 5
Dobivanje 0.0-dimetil N-cijanoetil-N-karboetoksiaminometilfosfonata Preparation of 0.0-dimethyl N-cyanoethyl-N-carboethoxyaminomethylphosphonate
[image] [image]
Etilkloroformijat (8 ml., 0.083 mola) otopljen je u 8 ml metilenklorida i 3.4 g 1,3,5-tricijanometilheksahidro-1,3,5-triazina (0.0167 mola) se kombiniraju u balonu sa okruglim dnom od 50 ml koji je opremljen sa mješalicom i refluks kondenzatorom. Smjesa se refleksira 1 sat i ispari se pod smanjenim tlakom. Ostatak se otopi u 5 ml metilenklorida. Doda se trimetilfosfit (5 ml, 0.042 mola) otopljen u 15 ml metilenklorida. Reakcijska smjesa se reflektira 1 sat Ohlađenoj smjesi doda se 50 ml vode. Smjesa se ekstrahira tri puta sa 50 ml metilenklorida. Organski djelovi se spoje i suše sa magnezij-sulfatom i ispare se pod vakumom tako da se dobiva 6.9 g željenog proizvoda što je 50 postotni prinos. Struktura je potvrđena pomoću ir, nmr i ms. Ethyl chloroformate (8 ml., 0.083 mol) was dissolved in 8 ml of methylene chloride and 3.4 g of 1,3,5-tricyanomethylhexahydro-1,3,5-triazine (0.0167 mol) were combined in a 50 ml round bottom flask equipped with with mixer and reflux condenser. The mixture is refluxed for 1 hour and evaporated under reduced pressure. The residue is dissolved in 5 ml of methylene chloride. Trimethylphosphite (5 ml, 0.042 mol) dissolved in 15 ml of methylene chloride was added. The reaction mixture is stirred for 1 hour. 50 ml of water is added to the cooled mixture. The mixture is extracted three times with 50 ml of methylene chloride. The organic parts are combined and dried with magnesium sulfate and evaporated under vacuum so that 6.9 g of the desired product is obtained, which is a 50 percent yield. The structure was confirmed by ir, nmr and ms.
Primjer 6 Example 6
Dobivanje N-fosfonometilglicina Preparation of N-phosphonomethylglycine
Fosfonatni reakcijski proizvod iz Primjera 5 (4.9 g, 0.02 mola) se kombinira sa 20 ml (0.24 mola) koncentrirane klorovodične kiseline, refleksira se 3 sata i ispari se pod smanjenim pritiskom. Poslije otapanja ostataksa u 30 ml vode, pH se podesi na 10 sa 50% natrij-hidroksidom i smjesa se ispari pod smanjenim pritiskom. Proizvod se ponovno otopi u oko 5 ml vode. Struktura je potvrđena pomoću nmr i tekuće kromatografije (1c). The phosphonate reaction product from Example 5 (4.9 g, 0.02 mol) is combined with 20 ml (0.24 mol) of concentrated hydrochloric acid, refluxed for 3 hours and evaporated under reduced pressure. After dissolving the residues in 30 ml of water, the pH is adjusted to 10 with 50% sodium hydroxide and the mixture is evaporated under reduced pressure. The product is re-dissolved in about 5 ml of water. The structure was confirmed by nmr and liquid chromatography (1c).
Primjer 7 Example 7
Dobivanje 0,0-dimetil-N-cijanometil-N-acetilaminometilfosfonata Preparation of 0,0-dimethyl-N-cyanomethyl-N-acetylaminomethylphosphonate
[image] [image]
5.6 g (0.05 m) kalij-t-butoksida suspendira se u balonu sa okruglim dnom sa 25 ml tetrahidrofurana (sušen preko molekulskih sita) i suspenzija se ohladi u vodenoj kupaonici. Dalje se dodaje ukapavanjem 6.44 ml (0.05 m) dietilfosfita na suspenziju tijekom 5 minuta, pod dušikom. Smjesa se ohladi na ledenoj kupaonici i dodaje se ukapavanjem tijekom 15 minuta 7.33 g (0.05 m) 5.6 g (0.05 m) of potassium t-butoxide is suspended in a round-bottom flask with 25 ml of tetrahydrofuran (dried over molecular sieves) and the suspension is cooled in a water bath. Next, 6.44 ml (0.05 m) of diethylphosphite is added dropwise to the suspension over 5 minutes, under nitrogen. The mixture is cooled in an ice bath and 7.33 g (0.05 m) is added dropwise over 15 minutes.
N-cijanomet N-klorometilacetamida razrijeđenog sa 50 ml tetrahidrofurana. Smjesa se pusti da se zagrije na sobnu temperaturu i miješa se 3 sata. Smjesa se filtrira preko dikalita i tetrahidrofuran se ispari pod smanjenim tlakom tako da se dobiva 9.0 g željenog proizvoda. Struktura je potvrđena pomoću ir, nmr, ms, C-13 nmr. N-cyanometh of N-chloromethylacetamide diluted with 50 ml of tetrahydrofuran. The mixture is allowed to warm to room temperature and stirred for 3 hours. The mixture is filtered over dicalite and the tetrahydrofuran is evaporated under reduced pressure to give 9.0 g of the desired product. The structure was confirmed by ir, nmr, ms, C-13 nmr.
Primjer 8 Example 8
Dobivanje fosfonometilglicina Obtaining phosphonomethylglycine
[image] [image]
5.4 g (0.022 m) spoja napravljenog u Primjeru 7 kombinira se sa 30 ml (0.363 m) koncentriran Hcl, reflektira 3 sata i tada ispari pod smanjenim tlakom tako da se dobiva željeni proizvod polusmeđa kruta tvar. Struktura je potvrđena pomoću ir. C-13 nmr i 1c tehnika. 5.4 g (0.022 m) of the compound made in Example 7 was combined with 30 ml (0.363 m) of concentrated HCl, refluxed for 3 hours and then evaporated under reduced pressure to give the desired product as a semi-brown solid. The structure was confirmed using ir. C-13 nmr and 1c technique.
Primjer 9 Example 9
Dobivanje 0,0-dimetil-N-cijanometil-N-aoetilaminometilfosfonata Obtaining 0,0-dimethyl-N-cyanomethyl-N-aoethylaminomethylphosphonate
[image] [image]
1.44 g (0.06 m) natrij-hidrida suspendira se sa 25 ml tetrahidrofurana (sušenog preko molekulskih sita) pod suhim dušikom. Dodaje se ukapavanjem tijekom 15 minuta 6.4 ml (0.05 m) dimetilfosfata. Kada je sav plinoviti vodenik razvijen smjesa se ohladi na ledenoj kupki i dodaje se ukapavanjem tijekom 15 minuta 7.33 g. (0.05 m) N-cijanometil-N-klorometilacetamida, razrijeđenog sa 50 ml suhog tetrahidrofurana. Smjesa se mješa preko noći, fultrira se i ispari pod smanjenim tlakom tako da se dobiva 11.5 g željenog proizvoda, kao žuto ulje. 1.44 g (0.06 m) of sodium hydride is suspended with 25 ml of tetrahydrofuran (dried over molecular sieves) under dry nitrogen. 6.4 ml (0.05 ml) of dimethyl phosphate is added dropwise over 15 minutes. When all hydrogen gas has evolved, the mixture is cooled in an ice bath and 7.33 g (0.05 m) of N-cyanomethyl-N-chloromethylacetamide, diluted with 50 ml of dry tetrahydrofuran, is added dropwise over 15 minutes. The mixture is stirred overnight, filtered and evaporated under reduced pressure to give 11.5 g of the desired product as a yellow oil.
Struktura je potvrđena pomoću ir, nmr, ms, C-13 nmr i gplc tehnika. The structure was confirmed by ir, nmr, ms, C-13 nmr and gplc techniques.
Spoj iz primjera 9 može se hidrolizirati u fosfonometilglicin prema učenju iz Primjera 3. The compound from Example 9 can be hydrolyzed to phosphonomethylglycine according to the teachings of Example 3.
Claims (15)
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US06/465,931 US4427599A (en) | 1982-06-22 | 1983-02-14 | Method for preparation of N-phosphonomethylglycine |
YU230183A YU44390B (en) | 1983-02-14 | 1983-11-22 | Process for making n-phosphonomethylglycine |
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