NO752505L - - Google Patents
Info
- Publication number
- NO752505L NO752505L NO752505A NO752505A NO752505L NO 752505 L NO752505 L NO 752505L NO 752505 A NO752505 A NO 752505A NO 752505 A NO752505 A NO 752505A NO 752505 L NO752505 L NO 752505L
- Authority
- NO
- Norway
- Prior art keywords
- formula
- carbamate
- alkyl
- phenyl
- compound
- Prior art date
Links
- 238000000034 method Methods 0.000 claims description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000004480 active ingredient Substances 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 2
- 239000000969 carrier Substances 0.000 claims description 2
- 239000012876 carrier material Substances 0.000 claims description 2
- KCLZXXMMEDEBMF-UHFFFAOYSA-N ethyl n-(3-hydroxyphenyl)carbamate Chemical compound CCOC(=O)NC1=CC=CC(O)=C1 KCLZXXMMEDEBMF-UHFFFAOYSA-N 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims description 2
- 230000002363 herbicidal effect Effects 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- FFQQCJGNKKIRMD-UHFFFAOYSA-N methyl n-(3-hydroxyphenyl)carbamate Chemical compound COC(=O)NC1=CC=CC(O)=C1 FFQQCJGNKKIRMD-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 125000005270 trialkylamine group Chemical group 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 2
- 239000007787 solid Substances 0.000 claims 2
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 claims 1
- LFXBHRAIYSPAOR-UHFFFAOYSA-N (3-methylphenyl)-(2,3,4,5,6-pentachlorophenyl)carbamic acid Chemical compound CC1=CC(=CC=C1)N(C2=C(C(=C(C(=C2Cl)Cl)Cl)Cl)Cl)C(=O)O LFXBHRAIYSPAOR-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229940125797 compound 12 Drugs 0.000 claims 1
- 239000003995 emulsifying agent Substances 0.000 claims 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- -1 monochlorophenyl Chemical group 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- SIZKDIQMNFWPBD-UHFFFAOYSA-N hydroxy(phenyl)carbamic acid Chemical compound OC(=O)N(O)C1=CC=CC=C1 SIZKDIQMNFWPBD-UHFFFAOYSA-N 0.000 description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005917 acylation reaction Methods 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- RDEOOHIDOFXZGU-UHFFFAOYSA-N (2,3,4,5,6-pentachlorophenyl)-phenylcarbamic acid Chemical compound ClC=1C(Cl)=C(Cl)C(Cl)=C(Cl)C=1N(C(=O)O)C1=CC=CC=C1 RDEOOHIDOFXZGU-UHFFFAOYSA-N 0.000 description 2
- CKDWPUIZGOQOOM-UHFFFAOYSA-N Carbamyl chloride Chemical compound NC(Cl)=O CKDWPUIZGOQOOM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000010933 acylation Effects 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical compound ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- AURJXZJUNOGUEO-UHFFFAOYSA-N (2-carbamoyloxyphenyl)carbamic acid Chemical class NC(=O)OC1=CC=CC=C1NC(O)=O AURJXZJUNOGUEO-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical class CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 230000006181 N-acylation Effects 0.000 description 1
- 125000005118 N-alkylcarbamoyl group Chemical group 0.000 description 1
- 230000006179 O-acylation Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229940112021 centrally acting muscle relaxants carbamic acid ester Drugs 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- BSCCSDNZEIHXOK-UHFFFAOYSA-N phenyl carbamate Chemical class NC(=O)OC1=CC=CC=C1 BSCCSDNZEIHXOK-UHFFFAOYSA-N 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/26—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
- C07C271/28—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a non-condensed six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/04—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from amines with formation of carbamate groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C271/12—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C271/16—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/40—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings
- C07C271/42—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C271/44—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
Foreliggende oppfinnelse vedrorer en fremgangsmåte for fremstilling av N-(karbamoyl-oksy-fenyl)-karbamater, som er anvendbare som herbicider. The present invention relates to a method for the production of N-(carbamoyl-oxy-phenyl)-carbamates, which can be used as herbicides.
Ifolge foreliggende oppfinnelse er det oppnådd en fremstillings-måte for fremstilling av forbindelser av formel I According to the present invention, a production method for the production of compounds of formula I has been achieved
(hvori R"<*>" står for alkyl, cykloalkyl eller eventuelt halogen-eller alkylsubstituert aryl, (where R"<*>" stands for alkyl, cycloalkyl or optionally halogen- or alkyl-substituted aryl,
2 2
R er hydrogen eller alkyl,R is hydrogen or alkyl,
R<3>er alkyl)R<3>is alkyl)
som omfatter reaksjonen mellom en karbamat av formel III which comprises the reaction between a carbamate of formula III
(hvori R3 har samme betydning som ovenfor nevnt) (wherein R3 has the same meaning as mentioned above)
og en ester av formel IIand an ester of formula II
: 1 : 1
1 2 1 2
hvori R og R har ovenfor nevnte betydning og A betyr en fenylgruppe med minst to elektrone- in which R and R have the above meaning and A means a phenyl group with at least two electron-
tiltrekkende substituenter)attracting substituents)
i nærvær ' av en base.in the presence ' of a base.
Uttrykket "alkyl" referer seg til rette eller forgrenede mettede alifatiske hydrokarboksylgrupperingen med 1-7 karbonatomer ( f.eks. metyl, etyl, n-propyl, isopropyl, n-butyl etc). Cykloalkylgruppene inneholder 3-7 karbonatomer ( f.eks. cyklopropyl, cyklopentyl, cykloheksyl etc). Det eventuelt halogensubstituerte eller alkylsubstituerte arylgruppene kan fortrinnsvis være en f enyl-, monoklorf enyi-, monobromfenyl-eller metylfenylgruppe, fortrinnsvis en m-tolyl- eller fenylgruppe). The term "alkyl" refers to the straight or branched saturated aliphatic hydrocarboxyl group of 1-7 carbon atoms (eg methyl, ethyl, n-propyl, isopropyl, n-butyl etc). The cycloalkyl groups contain 3-7 carbon atoms (e.g. cyclopropyl, cyclopentyl, cyclohexyl etc). The optionally halogen-substituted or alkyl-substituted aryl groups can preferably be a phenyl, monochlorophenyl, monobromophenyl or methylphenyl group, preferably a m-tolyl or phenyl group).
Symbolet A representerer fortrinnsvis en fenylgruppe substituert med minst to halogenatomer, fortrinnsvis kloratomer. Som en egnet representant for A kan nevnes pentaklorfenylgruppen. The symbol A preferably represents a phenyl group substituted with at least two halogen atoms, preferably chlorine atoms. As a suitable representative of A, the pentachlorophenyl group can be mentioned.
Fremgangsmåten for foreliggende oppfinnelse er spesielt egnet for fremstilling av de folgende forbindelser av formelen I: metyl-N-3-/N1 -(31 -metyl-fenyl)-karbamoyl7-fenyl-karbamat, etyl-N-3-/N~' - (f enyl) -karbamoyl7-f enyl-karbamat. The method of the present invention is particularly suitable for the preparation of the following compounds of the formula I: methyl-N-3-/N1 -(31-methyl-phenyl)-carbamoyl7-phenyl-carbamate, ethyl-N-3-/N~' - (phenyl)-carbamoyl7-phenylcarbamate.
Karbamater av formelen I kan fremstilles ved forskjellige metoder. Karakteristisk for de nevnte kjente metoder er acylering av den sure hydroksylgruppen i det tilsvarende N-hydroksy-fenyl-karbamat ved hjelp av reaktive karbonsyre-derivater. Carbamates of the formula I can be prepared by various methods. Characteristic of the aforementioned known methods is acylation of the acidic hydroxyl group in the corresponding N-hydroxy-phenyl-carbamate by means of reactive carbonic acid derivatives.
Ved anvendelse av isocyanat kan forbindelsene av formel I fremstilles i en-trinns addisjons-reaksjon i nærvær av en basisk katalysator (J. Org. Chem. 28, 658 (1963), By using isocyanate, the compounds of formula I can be prepared in a one-step addition reaction in the presence of a basic catalyst (J. Org. Chem. 28, 658 (1963),
jHelv. Chim. Acta 48, 2oo5 (1965), ungarsk patent nr. 154.o47) . jHell. Chim. Acta 48, 2oo5 (1965), Hungarian Patent No. 154.o47).
Sluttproduktene av formel I kan videre fremstilles ved en Isubstitusjons-reaksjon-fosgenering- i to trinn, hvor forst det tilsvarende klor-formiatet oppstår og deretter omsettes med det tilsvarende amin, eller hvor karbaminsyrekloridet dannes forut utfra aminet og deretter omsettes med det tilsvarende N-hydroksy-fenyl-karbamatet (Meth. der Org. Chem. The end products of formula I can further be prepared by an I-substitution-reaction-phosgenation- in two steps, where first the corresponding chloroformate is formed and then reacted with the corresponding amine, or where the carbamic acid chloride is first formed from the amine and then reacted with the corresponding N- hydroxy-phenyl-carbamate (Meth. der Org. Chem.
8, loi (1952), Chem. Pharm. Bull. 15, 2ol5 (1967)., ungarske patenter nr. 154.o47 og 157.o44. 8, 11 (1952), Chem. Pharm. Bull. 15, 2ol5 (1967)., Hungarian Patent Nos. 154.o47 and 157.o44.
Forbindelsene av formel I kan også fremstilles ved substitusjons-reaksjon uten forutgående fremstilling av klorformiatet eller karbaminsyrekloridet ved samtidig reaksjon mellom fosgen, det tilsvarende N-hydroksy-fenyl-karbamatet og den tilsvarende amin (ungarsk patent nr. 154.o44). The compounds of formula I can also be prepared by substitution reaction without prior preparation of the chloroformate or carbamic acid chloride by simultaneous reaction between phosgene, the corresponding N-hydroxy-phenyl-carbamate and the corresponding amine (Hungarian patent no. 154.o44).
Anvendelsen av såkalte aktiverte karbaminsyreestere somThe use of so-called activated carbamic acid esters such as
acylerende hjelpemidler er kjent fra peptidkjemien (fransk patent nr. 872.92o, Nature 175, 685 (1955). acylating auxiliaries are known from peptide chemistry (French patent no. 872.920, Nature 175, 685 (1955).
Det er videre kjent at sterkt reaktive fenylestere av karbamin-syre kan anvendes for N-acylering (ungarsk patent nr. 162.382). It is also known that highly reactive phenyl esters of carbamic acid can be used for N-acylation (Hungarian patent no. 162,382).
Ifolge fremstillingsmåten i foreliggende oppfinnelse anvendes aktive N-aryl-karbaminsyreestere til O-acylering av fenol-derivater som bærer primært substituerte grupper som substituenter. According to the method of preparation in the present invention, active N-aryl carbamic acid esters are used for O-acylation of phenol derivatives which carry primarily substituted groups as substituents.
Ved å studere acyleringsreaksjoner for N-hydroksyfenyl-iBy studying acylation reactions for N-hydroxyphenyl-i
karbamater har man funnet at forbindelser med formel I kan fremstilles ved hjelp av en kjemisk ny prosess i enhetlig og meget ren form gjennom anvendelse av aktive karbaminsyre-fenylestere. Denne fremgangsmåten er mer fordelaktig både fra kvantitativ og kvalitativt synspunkt enn acyleringen utfort med fosgen, isocyanater eller aktive N-alkyl-karbamoylestere. carbamates, it has been found that compounds of formula I can be prepared by means of a new chemical process in uniform and very pure form through the use of active carbamic acid phenyl esters. This method is more advantageous both from a quantitative and qualitative point of view than the acylation carried out with phosgene, isocyanates or active N-alkyl carbamoyl esters.
Men således ifolge kjente metoder O-karbamoylering av N-hydroksy-fenyl-karbamater har vært utfort ved hjelp av en addisjonsreaksjon (isocyanat) eller en to-trinns substitusjons-reaks jon (fosgen), presenterer den foreliggende oppfinnelse en en-trinns substitusjons-reaksjon for gjennomforing av O-karbamoylering. However, according to known methods O-carbamoylation of N-hydroxy-phenyl-carbamates has been carried out by means of an addition reaction (isocyanate) or a two-step substitution reaction (phosgene), the present invention presents a one-step substitution reaction for carrying out O-carbamoylation.
I . • I I . • I
Reaksjonen utfores fortrinnsvis i et organisk opplosningsmiddel I i nærvær av en base. For dette formål kan anvendes uorganiske i baser eller tertiære aminer, fortrinnsvis trialkylaminer (f.eks. trietylamin) eller pyridin. The reaction is preferably carried out in an organic solvent I in the presence of a base. For this purpose, inorganic bases or tertiary amines can be used, preferably trialkylamines (eg triethylamine) or pyridine.
Reaksjonen kan fortrinnsvis utfores i et organisk opplosningsmiddel. Det foretrekkes anvendt et organisk opplosningsmiddel hvor to av utgangsmaterialene ( basen er også inkludert) The reaction can preferably be carried out in an organic solvent. It is preferred to use an organic solvent where two of the starting materials (the base is also included)
er opploslige og hvor forbindelsen som dannes er enten uopp-loselig eller kan isoleres ved felling av fraksjonert krystalli-sering i ren tilstand, mens forurensninger forblir i opplosningen. Man kan med fordel anvende aromatiske hydrokarboner ( f.eks. tolyen), lavere ketoner ( f.eks. acetoner), estere ( f.eks. etylacetat), etere ( f.eks. dioksan), klorérte hydrokarboner (f.eks. kloroform).Når uorganiske baser benyttes,kan reaksjons-produktet renses - om nodvendig - ved suspensjon i vann. are soluble and where the compound formed is either insoluble or can be isolated by precipitation of fractional crystallization in a pure state, while impurities remain in the solution. Aromatic hydrocarbons (e.g. toluene), lower ketones (e.g. acetones), esters (e.g. ethyl acetate), ethers (e.g. dioxane), chlorinated hydrocarbons (e.g. chloroform).When inorganic bases are used, the reaction product can be purified - if necessary - by suspension in water.
_De karbamylerende midler av formel II kan fremstilles gjennom kjente metoder som anvendes for fremstilling av fenyl- eller tiofenylestere ( J. Org. Chem. 28, 658 (1963). _The carbamylating agents of formula II can be prepared through known methods used for the preparation of phenyl or thiophenyl esters (J. Org. Chem. 28, 658 (1963).
Saltet av den fenoliske bestanddelen av den aktive esterThe salt of the phenolic component of the active ester
som dannes i reaksjonen kan greit atskilles fra reaksjonsblandingen og tilbakefores i fremstillingen slik at det kan anvendes ved fremstillingen av den aktive ester, f.eks. som folger: Moderluten rores med et overskudd på lo% ( i forhold til feholkompontdelen) av en lo% natriumhydroksydopplosning. which is formed in the reaction can easily be separated from the reaction mixture and fed back into the preparation so that it can be used in the preparation of the active ester, e.g. as follows: The mother liquor is stirred with an excess of 10% (in relation to the fehol component part) of a 10% sodium hydroxide solution.
Etter atskillelse av de "to fasene,blir den vandige fasen surgjort med 1:1 fortynnet saltsyre til pH 1, det utfelte fenolet blir filtrert fra, vasket og torket. After separation of the two phases, the aqueous phase is acidified with 1:1 dilute hydrochloric acid to pH 1, the precipitated phenol is filtered off, washed and dried.
Gjenvinningsgrad 9o%.Recovery rate 9o%.
Det tertiære aminet kan gjenvinnes som hydrokloridsalt ved inndamping eller etter alkalisering ved hjelp av destillasjon. Den enkle og okonomiske gjenvinningsmetoden i tillegg til renheten av produktet og de hoye utbyttene gjor fremstillingen meget okonomisk. The tertiary amine can be recovered as the hydrochloride salt by evaporation or after alkalization by means of distillation. The simple and economical recycling method, in addition to the purity of the product and the high yields, make the production very economical.
Forbindelsene av formel I fremstilt ifolge fremgangsmåten for I foreliggende oppfinnelse kan omdannes til herbicide sammensetninger ved tidligere kjente metoder. Den aktive bestanddel blir fortrinnsvis formulert som en pulverblanding eller stabilisert emulsjon. Emulsjonene kan fremstilles ved å blande ' den aktive bestanddel med et egnet løsningsmiddel og, om onsket, The compounds of formula I produced according to the method of the present invention can be converted into herbicidal compositions by previously known methods. The active ingredient is preferably formulated as a powder mixture or stabilized emulsion. The emulsions can be prepared by mixing the active ingredient with a suitable solvent and, if desired,
med en eller flere emulsjonsdannende substanser. Mengden av tilsetningen av opplosningsmidlet,tilsetningens type og kar.akter og bærematerialet og den prosentuelle andel av den virksomme ingrediens velges ut fra betraktningen av de gitte omstendigheter og anvendelsens krav. De vanlige bærere og tilsetningsmidler anvendes etter bruk av kjente formulerings-metoder for fremstilling av pesticider. Innholdet av aktiv bestanddel kan variere over et vidt område og kan generelt ligge fra o,ool% - ca. 95%. with one or more emulsion-forming substances. The quantity of the addition of the solvent, the type and nature of the addition and the carrier material and the percentage of the active ingredient are selected based on consideration of the given circumstances and the requirements of the application. The usual carriers and additives are used after using known formulation methods for the production of pesticides. The content of active ingredient can vary over a wide range and can generally range from o.ool% - approx. 95%.
Ytterligere detaljer om den foreliggende oppfinnelse kanFurther details of the present invention can
finnes i eksemplene.found in the examples.
EKSEMPEL 1EXAMPLE 1
Til 5o ml kloroform ble 8,0g (o,o2 mol) pentaklorfenyl n-(m-tolyl)-karbamat og 3,34 g (o,o2 mol) metyl-N-(3-hydroksy-fenyl)karbamat tilsatt. Ved 25°C ble 2,1 g (o,o2o5 mol) trietylamin tilsatt og reaksjonsblandingen omrort ved 25°C i 5 timer. To 50 ml of chloroform, 8.0 g (0.02 mol) of pentachlorophenyl n-(m-tolyl)-carbamate and 3.34 g (0.02 mol) of methyl N-(3-hydroxy-phenyl) carbamate were added. At 25°C, 2.1 g (0.0205 mol) of triethylamine was added and the reaction mixture stirred at 25°C for 5 hours.
Det presipiterte produkt ble filtrert, vasket med kloroformThe precipitated product was filtered, washed with chloroform
og torket. Således erholdes 4,8 g metyl-N-3-/N1 -(3'-metyl-fenyl)-karbamoyl7-fenyl-karbamat. Smp. 146-148°C. and dried. 4.8 g of methyl-N-3-(N1-(3'-methyl-phenyl)-carbamoyl-7-phenyl-carbamate are thus obtained. Temp. 146-148°C.
EKSEMPEL 2EXAMPLE 2
Fremgangsmåten ifolge eksempel 1 ble utfort, bortsett fra atThe procedure according to example 1 was carried out, except that
som reaksjonsmedium ble det anvendt 5o ml klorbenzen og at det presipiterte produktet ble vasket med klorbenzen. 50 ml of chlorobenzene was used as reaction medium and that the precipitated product was washed with chlorobenzene.
Utbytte: 4,8 g, smp. 146-148°C.Yield: 4.8 g, m.p. 146-148°C.
EKSEMPEL 3EXAMPLE 3
Fremgangsmåten ifolge eksempel 1 ble utfort, bortsett fra atThe procedure according to example 1 was carried out, except that
som reaksjonsmedium ble anvendt 5o ml etylacetat. Etter omroring av reaksjonsblandingen ved 25°C i 5 timer, ble opplosningen inndampet, resten ble suspendert i toluen, produktet ble filtrert ifra, vasket med vann og torket. 50 ml ethyl acetate was used as reaction medium. After stirring the reaction mixture at 25°C for 5 hours, the solution was evaporated, the residue was suspended in toluene, the product was filtered off, washed with water and dried.
Utbytte: 5,o g, smp. 146-148°C.Yield: 5.o g, m.p. 146-148°C.
I IN
l l
EKSEMPEL 4EXAMPLE 4
15,43 g (o,o4 mol) pentaklorf enyl-N-f enyl-rkarbamat og 7,24 g (o,o4 mol) etyl-N-(3-hydroksyfenyl)-karbamat ble tilsatt til loo ml etylacetat. Etter tilsetning av 4,2 g (o,oo41 mol) trietylamin, ble reaksjonsblandingen omrort i 5 timer ved 25°C. Opplosningsmidelt ble fradestillert og resterende oljen blir opplost i loo ml varm benzen. Ved avkjoling blir de presipiterte krystaller filtrert fra, vasket med benzen og torket. Således erholdes 11 g etyl-N-,/^(N'-fenyl)-karbamoyl7-fenyl-karbamat. Utbytte 91,8%, smp. 146-148°C. 15.43 g (0.04 mol) of pentachlorophenyl-N-phenyl-carbamate and 7.24 g (0.04 mol) of ethyl-N-(3-hydroxyphenyl)-carbamate were added to 100 ml of ethyl acetate. After addition of 4.2 g (0.oo41 mol) of triethylamine, the reaction mixture was stirred for 5 hours at 25°C. The solvent was distilled off and the remaining oil was dissolved in 10 ml of hot benzene. On cooling, the precipitated crystals are filtered off, washed with benzene and dried. Thus, 11 g of ethyl N-,/^(N'-phenyl)-carbamoyl-7-phenyl-carbamate are obtained. Yield 91.8%, m.p. 146-148°C.
Utgangsmaterialet kan. fremstilles på fSigende måte:The starting material can. produced in the following manner:
Til en blanding av 27 g (o,l mol) pentaklorfenol, 13,1 g (o,ll mol) fenyl-isocyanat og Ibo ml toluen ble o,8 ml trietylamin tilsatt ved 25°C. Reaksjonsblandingen blir omrort under avkjoling med isvann i 3 timer ved 25°, hvoretter the presipiterte produktet blir filtrert fra, vasket og torket. Således erholdes 35,1 g pentaklorfenyl-N-fenyl-karbamat. Utbytte: 9o,5%. To a mixture of 27 g (0.1 mol) of pentachlorophenol, 13.1 g (0.1 mol) of phenyl isocyanate and 10 ml of toluene, 0.8 ml of triethylamine was added at 25°C. The reaction mixture is stirred while cooling with ice water for 3 hours at 25°, after which the precipitated product is filtered off, washed and dried. 35.1 g of pentachlorophenyl-N-phenyl-carbamate are thus obtained. Dividend: 9o.5%.
Claims (6)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HUCI1490A HU170115B (en) | 1974-07-12 | 1974-07-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO752505L true NO752505L (en) | 1976-01-13 |
Family
ID=10994526
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO752505A NO752505L (en) | 1974-07-12 | 1975-07-11 |
Country Status (23)
| Country | Link |
|---|---|
| JP (1) | JPS5132542A (en) |
| AR (1) | AR222621A1 (en) |
| BE (1) | BE831262A (en) |
| CA (1) | CA1064048A (en) |
| CH (1) | CH618584A5 (en) |
| CS (1) | CS194721B2 (en) |
| DD (1) | DD121512A2 (en) |
| DE (1) | DE2530521B2 (en) |
| DK (1) | DK139027B (en) |
| EG (1) | EG11800A (en) |
| ES (1) | ES439294A1 (en) |
| FI (1) | FI61873C (en) |
| FR (1) | FR2277816A1 (en) |
| GB (1) | GB1479250A (en) |
| HU (1) | HU170115B (en) |
| IL (1) | IL47668A (en) |
| IN (1) | IN140842B (en) |
| MX (1) | MX3678E (en) |
| NL (1) | NL7508245A (en) |
| NO (1) | NO752505L (en) |
| PL (1) | PL104534B1 (en) |
| SE (1) | SE420088B (en) |
| SU (1) | SU886738A3 (en) |
-
1974
- 1974-07-12 HU HUCI1490A patent/HU170115B/hu unknown
-
1975
- 1975-07-08 IL IL47668A patent/IL47668A/en unknown
- 1975-07-09 DE DE2530521A patent/DE2530521B2/en not_active Ceased
- 1975-07-09 EG EG401/75A patent/EG11800A/en active
- 1975-07-10 FI FI752008A patent/FI61873C/en not_active IP Right Cessation
- 1975-07-10 ES ES439294A patent/ES439294A1/en not_active Expired
- 1975-07-10 FR FR7521688A patent/FR2277816A1/en active Granted
- 1975-07-10 NL NL7508245A patent/NL7508245A/en not_active Application Discontinuation
- 1975-07-10 IN IN1349/CAL/1975A patent/IN140842B/en unknown
- 1975-07-10 SE SE7507951A patent/SE420088B/en unknown
- 1975-07-11 AR AR259528A patent/AR222621A1/en active
- 1975-07-11 DK DK318175AA patent/DK139027B/en not_active IP Right Cessation
- 1975-07-11 GB GB29290/75A patent/GB1479250A/en not_active Expired
- 1975-07-11 CH CH912775A patent/CH618584A5/en not_active IP Right Cessation
- 1975-07-11 CA CA231,284A patent/CA1064048A/en not_active Expired
- 1975-07-11 JP JP50084566A patent/JPS5132542A/en active Pending
- 1975-07-11 SU SU752153655A patent/SU886738A3/en active
- 1975-07-11 DD DD187258A patent/DD121512A2/xx unknown
- 1975-07-11 CS CS754932A patent/CS194721B2/en unknown
- 1975-07-11 NO NO752505A patent/NO752505L/no unknown
- 1975-07-11 BE BE158200A patent/BE831262A/en not_active IP Right Cessation
- 1975-07-12 PL PL1975182043A patent/PL104534B1/en unknown
- 1975-07-14 MX MX75100304U patent/MX3678E/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EG11800A (en) | 1979-03-31 |
| BE831262A (en) | 1975-11-03 |
| DE2530521B2 (en) | 1978-03-16 |
| IL47668A (en) | 1978-03-10 |
| SE420088B (en) | 1981-09-14 |
| FI61873C (en) | 1982-10-11 |
| ES439294A1 (en) | 1977-03-01 |
| SU886738A3 (en) | 1981-11-30 |
| DE2530521A1 (en) | 1976-01-29 |
| JPS5132542A (en) | 1976-03-19 |
| DK139027C (en) | 1979-05-07 |
| CA1064048A (en) | 1979-10-09 |
| NL7508245A (en) | 1976-01-14 |
| DK139027B (en) | 1978-12-04 |
| FI61873B (en) | 1982-06-30 |
| AR222621A1 (en) | 1981-06-15 |
| FR2277816A1 (en) | 1976-02-06 |
| FR2277816B1 (en) | 1982-07-30 |
| SE7507951L (en) | 1976-01-13 |
| CH618584A5 (en) | 1980-08-15 |
| HU170115B (en) | 1977-04-28 |
| GB1479250A (en) | 1977-07-06 |
| CS194721B2 (en) | 1979-12-31 |
| AU8296275A (en) | 1977-01-13 |
| IL47668A0 (en) | 1975-10-15 |
| DD121512A2 (en) | 1976-08-05 |
| IN140842B (en) | 1976-12-25 |
| FI752008A (en) | 1976-01-13 |
| MX3678E (en) | 1981-04-23 |
| PL104534B1 (en) | 1979-08-31 |
| DK318175A (en) | 1976-01-13 |
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