CS257059B1 - Process for preparing derivatives of 2,1,3-benzotiadiazin-4-on-2,2-dioxide - Google Patents
Process for preparing derivatives of 2,1,3-benzotiadiazin-4-on-2,2-dioxide Download PDFInfo
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- CS257059B1 CS257059B1 CS865948A CS594886A CS257059B1 CS 257059 B1 CS257059 B1 CS 257059B1 CS 865948 A CS865948 A CS 865948A CS 594886 A CS594886 A CS 594886A CS 257059 B1 CS257059 B1 CS 257059B1
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- Prior art keywords
- organic
- separated
- methylpyridine
- acid
- dioxide
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- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims abstract description 58
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002585 base Substances 0.000 claims abstract description 19
- 150000007530 organic bases Chemical class 0.000 claims abstract description 14
- 238000000605 extraction Methods 0.000 claims abstract description 11
- 238000004821 distillation Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000010533 azeotropic distillation Methods 0.000 claims abstract description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound 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 abstract description 7
- 239000011734 sodium Substances 0.000 claims abstract description 7
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 7
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000012074 organic phase Substances 0.000 claims abstract description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 3
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 3
- 150000004820 halides Chemical class 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 10
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 238000007363 ring formation reaction Methods 0.000 claims description 8
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical class NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 5
- 239000008346 aqueous phase Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- MQZXGMYANOJYIY-UHFFFAOYSA-N 2,2-dioxo-1h-2$l^{6},1,3-benzothiadiazin-4-one Chemical class C1=CC=C2C(=O)NS(=O)(=O)NC2=C1 MQZXGMYANOJYIY-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000003916 acid precipitation Methods 0.000 claims description 2
- HHSPVTKDOHQBKF-UHFFFAOYSA-J calcium;magnesium;dicarbonate Chemical compound [Mg+2].[Ca+2].[O-]C([O-])=O.[O-]C([O-])=O HHSPVTKDOHQBKF-UHFFFAOYSA-J 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- 239000011591 potassium Chemical group 0.000 claims description 2
- 229910052700 potassium Chemical group 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims 1
- 150000008064 anhydrides Chemical class 0.000 claims 1
- 230000007420 reactivation Effects 0.000 claims 1
- ZOMSMJKLGFBRBS-UHFFFAOYSA-N bentazone Chemical compound C1=CC=C2NS(=O)(=O)N(C(C)C)C(=O)C2=C1 ZOMSMJKLGFBRBS-UHFFFAOYSA-N 0.000 abstract description 14
- 239000005476 Bentazone Substances 0.000 abstract description 10
- CNBGNNVCVSKAQZ-UHFFFAOYSA-N benzidamine Natural products C12=CC=CC=C2C(OCCCN(C)C)=NN1CC1=CC=CC=C1 CNBGNNVCVSKAQZ-UHFFFAOYSA-N 0.000 abstract description 10
- -1 (isopropylamide) anthranilic acid pyridine Chemical compound 0.000 abstract description 4
- 150000008065 acid anhydrides Chemical class 0.000 abstract description 2
- 239000004009 herbicide Substances 0.000 abstract description 2
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012071 phase Substances 0.000 abstract 2
- FLDAUVOWVUHPRM-UHFFFAOYSA-N 3-propan-2-yl-2H-1,2,3-benzothiadiazin-4-one Chemical compound C(C)(C)N1NSC2=C(C1=O)C=CC=C2 FLDAUVOWVUHPRM-UHFFFAOYSA-N 0.000 abstract 1
- 239000012043 crude product Substances 0.000 abstract 1
- 230000002363 herbicidal effect Effects 0.000 abstract 1
- 239000012450 pharmaceutical intermediate Substances 0.000 abstract 1
- 239000002689 soil Substances 0.000 abstract 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 12
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 8
- 239000012044 organic layer Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000010410 layer Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OTTDACPMYLDVTL-UHFFFAOYSA-N ethyl quinoline-3-carboxylate Chemical compound C1=CC=CC2=CC(C(=O)OCC)=CN=C21 OTTDACPMYLDVTL-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- XUWVIABDWDTJRZ-UHFFFAOYSA-N propan-2-ylazanide Chemical compound CC(C)[NH-] XUWVIABDWDTJRZ-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical class [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- MXZDMUOYQBHOCH-UHFFFAOYSA-N 2-amino-n-butylbenzamide Chemical compound CCCCNC(=O)C1=CC=CC=C1N MXZDMUOYQBHOCH-UHFFFAOYSA-N 0.000 description 1
- FWQYJOPJMIEKHZ-UHFFFAOYSA-N 2-amino-n-propan-2-ylbenzamide Chemical compound CC(C)NC(=O)C1=CC=CC=C1N FWQYJOPJMIEKHZ-UHFFFAOYSA-N 0.000 description 1
- WIFSDCDETBPLOR-UHFFFAOYSA-N 2-aminobenzoic acid Chemical compound NC1=CC=CC=C1C(O)=O.NC1=CC=CC=C1C(O)=O WIFSDCDETBPLOR-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- HTLZVHNRZJPSMI-UHFFFAOYSA-N N-ethylpiperidine Chemical compound CCN1CCCCC1 HTLZVHNRZJPSMI-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical class [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- OENLEHTYJXMVBG-UHFFFAOYSA-N pyridine;hydrate Chemical compound [OH-].C1=CC=[NH+]C=C1 OENLEHTYJXMVBG-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- Plural Heterocyclic Compounds (AREA)
Abstract
Spósob výroby uvedených derivátov, zvlášt 3-izopropylbenzotiadiazín-4-on~2,2- -dioxidu (bentazonu) sa uskutočňuje z alkylamidu (izopropylamidu) kyseliny antranilovej, aduktu pyridinovéj bázy (2-metylpyridínu) s oxidom sírovým, ktoré reagujú za tvorby soli sulfámovej kyseliny. Tá sa dehydratačne cyklizuje pósobením halogenidov a/alebo anhydridov kyselin (hlavně POCI3), pričom sa surový produkt hydrolyzuje vodou s následným oddělením ťažšej organickej a lahšej vodnej fáze. Z organickej fázy sa pósobením hydroxidu alkalického kovu oddělí sodná alebo draselná sol bentazonu. tahšia vodná fáza sa neutralizuje najmenej jedným oxidom, hydroxidom alebo uhličitanom alkalického kovu alebo zeminy, pričom uvolněná báza (2-metylpyridin) sa oddělí azeotropickou destiláciou a následným destilačným alebo extrakčným delením sa regeneruje organická báza a rozpúšťadlo, ktoré sa recyklujú a destilačný zvyšok sa separuje alebo deponuje. Ide o prakticky bezodpadová technológiu výroby herbicidu alebo medziproduktu farmaceutík.Method of producing said derivatives, especially 3-isopropylbenzothiadiazin-4-one ~ 2,2- Dioxide (bentazone) is carried out from the alkylamide (isopropylamide) anthranilic acid pyridine base adduct (2-methylpyridine) with sulfur trioxide, which react to form sulfamic acid salts. It is dehydrated cyclizes by the action of halides and / or acid anhydrides (mainly POCl 3), with the crude product hydrolyses with water followed by separating heavier organic and lighter water phase. From the organic phase with hydroxide the alkali metal separates the sodium or bentazone potassium salt. thicker water phase is neutralized with at least one oxide, alkali metal hydroxide or carbonate or soil, with the liberated base (2-methylpyridine) is separated by azeotropic distillation followed by distillation or extraction separating the organic base and solvent, which are recycled and distilled the residue is separated or deposited. It's practically waste-free herbicide production technology or a pharmaceutical intermediate.
Description
Vynález sa týká spósobu výroby derivátov 2,1,3-benzotiadiazín-4-on-2,2-dioxidu, ako 3-izopropyl-2,1,3-benzotiadiazín-4~on-2,2-dioxidu (bentazonu) z izopropylamidu kyseliny antranilovej i2-amínobenzoovej), jeho sulfonáciou aduktom oxidu mírového s 2-metylpyridínom v dichlóretáne a cyklizáciou soli 1-(izopropylamidokarbonylS-fenylsulfámovej kyseliny s 2-metylpyridínom pósobením oxychloridu fosforečného a hydrolýzou vzniknutej zložitej zmesi s následnou technicky jednoduchou regeneráciou aspoň podstatných množstiev pomocných látok.The present invention relates to a process for the preparation of 2,1,3-benzothiadiazin-4-one-2,2-dioxide derivatives such as 3-isopropyl-2,1,3-benzothiadiazin-4-one 2,2-dioxide (bentazone) from isopropylamide of anthranilic acid (2-aminobenzoic acid), by its sulfonation with an adduct of peaceful oxide with 2-methylpyridine in dichloroethane, and cyclization of the 1- (isopropylamidocarbonylS-phenylsulfamic acid) with 2-methylpyridine salt by treatment with phosphorus oxychloride and hydrolysis resulting from substances.
Deriváty 2,1,3-benzotiadiazín-4-on-2,2-dioxidu, hlavně však 3-izopropyl-2,1,3-benzotiadiazín-4-on~2,2-dioxid, sú významné hlavně z hladiska farmaceutickéj výroby, ale tiež výroby pesticídov a z nich najmá herbicídov. Najčastejšie sa vyrábajú z derivátov kyseliny antranilovej (2-amínobenzoovej), napr. 2-sulfamidobenzoových kyselin cyklizáciou fosgénom (USA pat.2,1,3-Benzothiadiazin-4-one-2,2-dioxide derivatives, but mainly 3-isopropyl-2,1,3-benzothiadiazin-4-one-2,2-dioxide, are of particular importance for pharmaceutical production. but also the production of pesticides and especially herbicides. They are most often produced from anthranilic acid (2-aminobenzoic) derivatives, e.g. Of 2-sulfamidobenzoic acids by phosgene cyclization (U.S. Pat.
822 257), obvykle za přítomnosti organických báz, ako pyridinu a jeho alkylderivátov, N,N-dimetylanilínu, N-etyl-piperidínu, N-metylpyrolidónu, imidazolov ap. Ďalej cyklizácia 2-sulf-amidoesterov kyseliny benzoovej sa móže uskutočniť. aj pósobením oxychloridu fosforečného alebo tionylchloridu (Belgický pat. 702 877)! „ Okrem toho, zavedenie skupiny SO2 do molekuly sa uskutočňuje (pat. ČSSR 204 023; Europ. pat. přihláška 0 070 467) tak, že sa vychádza z esterov kyseliny antranilovej, ktoré sa sulfonujú na jej amínoskupine komplexom pyridinových báz, připravených z bázy a kyseliny chlórsulfónovej.822 257), usually in the presence of organic bases such as pyridine and its alkyl derivatives, N, N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidone, imidazoles and the like. Further, the cyclization of the 2-sulfo-amidoesters of benzoic acid can be carried out. also by the action of phosphorus oxychloride or thionyl chloride (Belgian Pat. 702 877)! "In addition, the introduction of the SO 2 group into the molecule is effected (U.S. Pat. No. 204,023; European Pat. Application 0 070 467) starting from anthranilic acid esters which are sulfonated on its amino group with a pyridine base complex prepared from base and chlorosulfonic acid.
Pre technické riešenie v priemyselnom meradle je však zapotreby regenerácia inertných rozpúšťadiel (dichlóretán), hlavně však reaktívnych rozpúšťadiel, ako je 2-metylpyridín, ktorého aduktom s oxidom sírovým sa sulfonuje.However, for an industrial solution on an industrial scale, the regeneration of inert solvents (dichloroethane), especially reactive solvents such as 2-methylpyridine, whose sulfur trioxide adduct is sulfonated, is required.
Pri cyklizácii 2-sulfamidobenzoových kyselin oxychloridom fosforečným za přítomnosti pyridinových báz dochádza po dehydratácii za súčasnej cyklizácie k vzniku rozpadných produktov dehydratačného činidla (HCI, H^PO^), ktoré sa za přítomnosti hydrolyzačnej vody viažu na pyridinová bázu. Preto za přítomnosti inertného rozpúšťadla je nutné zásadité ako aj inertně rozpúšťadlo regenerovat.Cyclization of 2-sulfamidobenzoic acids with phosphorous oxychloride in the presence of pyridine bases results in dehydration products (HCl, H 2 PO 4) which bind to pyridine base in the presence of hydrolyzing water after dehydration with simultaneous cyclization. Therefore, in the presence of an inert solvent, both basic and inert solvents need to be regenerated.
Podlá předloženého vynálezu spósob výroby derivátov 2,1,3-benzodiazín-4-on-2,2-dioxidu obecného vzorcaAccording to the present invention, a process for the preparation of 2,1,3-benzodiazin-4-one-2,2-dioxide derivatives of the general formula
II !O v ktorom R' je vodík alebo alkyl až Cg, X je vodík, sodík alebo draslík, ž derivátov kyseliny antranilovej obecného vzorca .CONHR’ kde R' má vyššie uvedený význam, ktoré reagujú s oxidom sírovým a/alebo s kyselinou chlórsulfonovou v přítomnosti najmenej jednej organickej bázy alebo s aduktom oxidu sírového na organickú bázu alebo bázy za vzniku odpovedajúcich solí sulfámovej kyseliny, ktoré samotné a/alebo volné sulfámové kyseliny sa dehydratačne cyklizujů pósobením halogenidov a/alebo anhydridov kyselin, s výhodou oxychloridom fosforečným, sa uskutočňuje tak, že po dehydratačnej cyklizácii sa surový reakčný produkt hydrolyzuje vodou a oddělí sa ťažšia organická a lahšia vodná fáza, z organickej fázy, s výhodou za miešania, sa pósobením vodného roztoku alespoň jedného hydroxidu alkalického kovu, s výhodou hydroxidu sodného, oddělí sodná a/alebo draselná sol 3-alkyl-2,],3-tiadiazín-4-on-2,2-dioxidu vo formě prevážne vodného roztoku, z ktorého sa 3-alkyl-2,1,4-tiadiazín-4-on-2,2-dioxid izoluje po prezrážaní kyselinou s následnou separáciou. Potom sa lahšia vodná fáza neutralizuje najmenej jedným oxidom, hydroxidom alebo uhličitanom alkalického kovu alebo zeminy, s výhodou uhličitanom vápenatým a/alebo uhličitanom horečnatovápenatým, pričom uvolněná báza alebo bázy, s výhodou 2-metylpyridín, sa oddelia azeotropickou destiláciou s vodou a/alebo extrakčnou reaktifikáciou s 1,2-dichlóretanom a následným extrakčným a/alebo destilačným delením sa regeneruje báza alebo organické bázy a rozpúšťadlo, pričom zvyšky vody sa oddelia, s výhodou extrakčnou destiláciou. Organická báza alebo bázy a rozpúšťadlá sa spravidla vracajú do stupňa přípravy aduktu, pričom destilačný zvyšok z azeotropickej destilácie a/alebo extrakčnej rektifikácie sa deponuje a/alebo separuje, s výhodou filtráciou alebo odstredovaním anorganického podielu.II ! Wherein R 'is hydrogen or alkyl to C8, X is hydrogen, sodium or potassium, anthranilic acid derivatives of the formula .CONHR' wherein R 'is as defined above, which react with sulfur trioxide and / or chlorosulfonic acid in the presence of at least one organic base or an adduct of sulfur trioxide to the organic base or bases to form the corresponding sulfamic acid salts, which alone and / or the free sulfamic acids are cyclized dehydrating by treatment with halides and / or acid anhydrides, preferably phosphorus oxychloride, such that after dehydration cyclization, the crude reaction product is hydrolyzed with water and the heavier organic and lighter aqueous phase is separated from the organic phase, preferably with stirring, by separating the aqueous solution of at least one alkali metal hydroxide, preferably sodium hydroxide, the sodium and / or potassium salts 3-alkyl-2,1,3-thiadiazin-4-one 2,2-dioxide in the form of pre of a serious aqueous solution from which the 3-alkyl-2,1,4-thiadiazin-4-one 2,2-dioxide is isolated after acid precipitation followed by separation. Thereafter, the lighter aqueous phase is neutralized with at least one alkali metal or earth carbonate, hydroxide or carbonate, preferably calcium carbonate and / or calcium magnesium carbonate, the liberated base or bases, preferably 2-methylpyridine, separated by azeotropic distillation with water and / or extractive by reacting with 1,2-dichloroethane followed by extraction and / or distillation separation, the base or organic bases and the solvent are recovered, the residual water being separated, preferably by extraction distillation. The organic base or bases and solvents are generally returned to the adduct preparation stage, wherein the distillation residue from azeotropic distillation and / or extraction rectification is deposited and / or separated, preferably by filtration or by centrifugation of the inorganic fraction.
Výhodou spósobu výroby podlá vynálezu je komplexně spracovanie surovin a regenerácia cenných rozpúšťadiel tak, že ide prakticky o bezodpadový proces s pozitívnymi i ekologickými dósledkami a nájdenie vhodných reagentov umožňujúcich recykláciu pomocných látok a technicky poměrně jednoducho výrazné znížiť spotřebu surovin.The advantage of the production method according to the invention is the complex processing of raw materials and the recovery of valuable solvents so that it is practically a waste-free process with positive and ecological consequences and finding suitable reagents enabling recycling of auxiliaries and technically quite simply reducing the consumption of raw materials.
Postup syntézy možno vyjádřit takto:The synthesis procedure can be expressed as follows:
1. Příprava aduktu oxidu sírového (z oxidu sírového a/alebo kyseliny chlórsulfónovej) s derivátom pyridinu, napr. 2-metylpyridínom1. Preparation of an adduct of sulfur trioxide (from sulfur trioxide and / or chlorosulfonic acid) with a pyridine derivative, e.g. 2-methylpyridine
šo3 ve]šo 3 ve]
2. Sulfonácia alkylamidu kyseliny antranilovej, napr. izopropylamidu kyseliny antraniloconhch(ch3), conhch(ch3)2 + CK’ <2. Sulfonation of anthranilic acid alkylamide, e.g. isopropylamide of anthraniloconhch (ch 3 ), conhch (ch 3 ) 2 + CK '<
so,so,
CH, nhso3h.CH, nhso 3 hr.
CH,CH,
3. Cyklizáoia pósobením oxychloridu fosforečného conhch(ch3)2 Nhso3h. p3. Cyclization with phosphorus oxychloride conhch (ch 3 ) 2 N h 50 3 h. p
CH, +· poci3 a:CH, + · position 3 and:
oabout
NH/ ^0 n-ch(ch3)2 NH / 0 ^ N-CH (CH3) 2
CCc„, bentazon + NaOH (+KOH)CCc ', bentazone + NaOH (+ KOH)
HqPOd * sodná alebo draselná sol bentazonuHqPOd * sodium or potassium salt of bentazone
Uvolňeniet2-metylpyridínu před recyklováním, napr. pósobením uhličitanu vápenatého:Release of 2-methylpyridine prior to recycling, e.g. by calcium carbonate:
HCI !CKCHj + HCI ! CK CH +
HCI r |) + CaCI2 + co2 + h2o ch3 HCl (R) + CaCl 2 + co 2 + h 2 o 3
+ CaCO3 -5- (^j)_CH+ Ca(H2PO4)2 + H2O + CO2 + CaCO 3 -5- (R) - CH + Ca (H 2 PO 4 ) 2 + H 2 O + CO 2
•ch3 + CaCOg• ch 3 + CaCO 3
4- CaHPO^ 4· H2O + CO24- CaHPO ^ 4 · H2O + CO2
Pri izolácii pyridinu alebo jeho derivátov podía vynálezu, za účelom hlavně jeho recyklovania, sa kyslé zložky z vodnej fázy viažu oxidmi, resp. produktami ich hydratácie, zvlášť hydroxidmi, alebo uhličitanmi kovov I. a/alebo II. skupiny Meitdelejevovej tabulky, najlepšie sodíka alebo vápníka a/alebo horčíka.In the isolation of pyridine or its derivatives according to the invention, for the purpose of recycling it in particular, the acidic components from the aqueous phase are bound by oxides or oxides. hydration products thereof, in particular metal hydroxides or carbonates of I. and / or II. of a Meitdelejev group, preferably sodium or calcium and / or magnesium.
Přidáním oxidov, hydroxidov a/alebo uhličitanov, ako napr. uhličitanu vápenatého alebo hydroxidu vápenatého do kvapalnej zmesi voda - pyridinová báza - kyselina trihydrogénfosforečná··- kyselina chlorovodíková vznikají hlavně fosforečnany vápenaté a chlorid vápenatý. Fosforečnany vápenaté sa obvykle v podstatnej miere vylúčia ako tuhá fáza a chlorid vápenatý zostáva v kvapalnej fáze.The addition of oxides, hydroxides and / or carbonates, such as e.g. Calcium carbonate or calcium hydroxide in a liquid mixture of water - pyridine base - trihydrogenphosphoric acid ·· - hydrochloric acid is mainly produced by calcium phosphates and calcium chloride. Calcium phosphates are usually largely eliminated as a solid phase and calcium chloride remains in the liquid phase.
Takto po neutralizácii kyslých komponentov v uvedenej zmesi sa pyridin, 2-metylpyridín, připadne iná použitá pyridinová báza oddělí azeotropickou destiláciou. Destilát obsahujúci najčastejšie 50 až 70 % vody a 30 až 50 % pyridínovej bázy sa vyextrahuje vhodným chlórovaným uhlovodíkom, napr. 1,2-dichlóretánom. Organická vrstva obsahujúca najčastejšie do 3 % hmot. vody sa oddělí ako azeotropická zmes s dichlóretánom.Thus, after neutralization of the acidic components in said mixture, pyridine, 2-methylpyridine, or any other pyridine base used, is separated by azeotropic distillation. The distillate containing most often 50-70% water and 30-50% pyridine base is extracted with a suitable chlorinated hydrocarbon, e.g. 1,2-dichloroethane. An organic layer containing up to 3 wt. water is separated as an azeotropic mixture with dichloroethane.
Organická vrstva pozostávajúca zo zmesi dichlóretán-2-metylpyridín sa použije na přípravu sulfonačného činidla - aduktu 2-metylpyridínu s oxidom sírovým (oxid sírový pochádza bu3 zo samotného oxidu sírového, připadne oddělený z olea alebo kyseliny chlórsulfónovej), pričom dichlóretán slúži ako rozpúšťadlo bázy.The organic layer consisting of a mixture of dichloroethane-2-methylpyridine is used to prepare the sulfonating agent-adduct of 2-methylpyridine with sulfur trioxide (sulfur trioxide comes either from sulfur trioxide alone, optionally separated from oleate or chlorosulfonic acid), with dichloroethane serving as the base solvent.
Niektoré podrobnejšie údaje o uskutočnení spósobu podlá vynálezu, ako aj Salšie výhody, sú zřejmé z príkladov.Some of the more detailed details of an embodiment of the method of the invention, as well as the more substantial advantages, are evident from the examples.
Příklad 1Example 1
Příprava 3-izopropyl-2,1,3-benzotiadiazín-4-on-2,2-dioxidu (bentazónu) z izopropylamidu kyseliny antranilovej sa uskutočňuje tak, že do zmesi bezvodých rozpúšťadiel - 1,2-dichlóretánu a 2-metylpyridínu (obsah 11,3 % hmot.) sa počas 30 min pri teplote 0 °C přidá 52,1 hmot. častí oxidu sírového. Po člalších 20 min sa přidá 92,7 hmot. častí izopropylamidu kyseliny antranilovej a zmes sa mieša počas 1 h pri teplote 20 °C.Preparation of 3-isopropyl-2,1,3-benzothiadiazin-4-one-2,2-dioxide (bentazone) from anthranilic acid isopropylamide is carried out by adding to the mixture of anhydrous solvents 1,2-dichloroethane and 2-methylpyridine (content of 11.3% by weight) is added over a period of 30 min at 0 ° C to 52.1% by weight. parts of sulfur trioxide. After another 20 min, 92.7 wt. of anthranilic acid isopropylamide and the mixture was stirred at 20 ° C for 1 h.
K vzniknutéj suspenzii 2-metylpyridínovej soli kyseliny 1-(izopropylamidokarbonyl>ťfenýlsulfámovej kyseliny sa přidá pri teplote miestnosti počas 5 min'í54,2 hmot. častí oxychloridu fosforečného (POCl^ř a reakční zmes sa pod spátným chladičom zahřeje do varu. Po 2 h zohrievaní a vychladnutí sa reakčná zmes hydrolyzuje 416 hmot. časťami vody a extrahuje .300 hmot. časťami vodného roztoku hydroxidu sodného o koncentrácii 8,5 % hmot.To the resulting suspension of the 2-methylpyridine salt of 1- (isopropylamidocarbonylphenylsulfamic acid) was added, at room temperature, 54.2 parts by weight of phosphorus oxychloride (POCl 2) at room temperature over 5 minutes, and the reaction mixture was heated to reflux under reflux. by heating and cooling, the reaction mixture is hydrolyzed with 416 parts by weight of water and extracted with 300 parts by weight of an aqueous solution of sodium hydroxide at a concentration of 8.5% by weight.
Organická fáza sa opSť premyje 240 hmot. časťami vody. Spojené alkalické extrakty sa okyslia zriedenou kyselinou sírovou v množstve 66,6 hmot. častí o koncentrácii 50 % hmot. Vzniknutá zrazenina sa odfiltruje a vysuší. Získá sa 112 hmot, častí 3-izopropyl-2,l,3-benzotiadiazín-4-on-2,2-dioxidu (bentazónu) o teplote tavenia 130-134 °C.The organic phase is again washed with 240 wt. parts of water. The combined alkaline extracts were acidified with dilute sulfuric acid in an amount of 66.6 wt. % by weight of 50 wt. The resulting precipitate was filtered off and dried. 112 parts by weight of parts of 3-isopropyl-2,1,3-benzothiadiazin-4-one 2,2-dioxide (bentazone) with a melting point of 130-134 ° C are obtained.
Ďalej sa spracovávajú hydrolyzačné vody tak, aby sa z nich izolovali a recyklovali cenné zložky, hlavně 2-metylpyridín. Tak k 610 hmot. častiam hydrolyzačnýoh vód s obsahom 108 hmot. častí 2-metylpyridínu (17,7 % hmot) viazaného vo formě soli s anorganickou kyselinou (kyselina sírová, kyselina chlorovodíková, kyselina trihydrogénfosforečnáj, sa přidá 119 hmot. častí uhličitanu vápenatého a zmes sa mieša pri teplote miestnosti počas 30 min.Further, the hydrolysis waters are treated to recover and recycle valuable components, especially 2-methylpyridine. So to 610 mass. parts of hydrolysis water containing 108 wt. parts of 2-methylpyridine (17.7% by weight) bound in the form of a salt with an inorganic acid (sulfuric acid, hydrochloric acid, phosphoric acid) were added 119 parts by weight of calcium carbonate and the mixture was stirred at room temperature for 30 min.
Uvolněný 2-metylpyridín sa oddestiluje v azeotropickej zmesi, obsahujúcej v 250 hmot. častiach azeotropickej zmesi 308 hmot. častí 2-metylpyridínu. Destilačný zvyšok sa odfiltruje, premyje vodou, vysuší a anorganická hmota sa deponuje.The released 2-methylpyridine is distilled off in an azeotropic mixture containing 250 wt. parts of the azeotropic mixture 308 wt. parts of 2-methylpyridine. The distillation residue is filtered off, washed with water, dried and the inorganic mass is deposited.
Získaná azeotropická zmes sa spracuje extrakciou 1,2-dichlóretánom tak, že sa 250 hmot. častí azeotropickej zmesi extrahuje dvakrát po 190 hmot. časťami 1,2-dichlóretánu. Potom organická vrstva obsahuje 380 hmot. časti dichlóretánu, 108 hmot. častí 2-metylpyridínu a 6 hmot. častí vody. Vodná vrstva pozostáva zo 138 hmot. častí vody a 2 hmot. častí dichlčretánu. Z organickej vrstvy (494 hmot. častí) sa oddestiluje voda (6 hmot. častí vody a 34 hmot. častí dichlóretánu). Destilačný zvyšok obsahuje 1,2-dichlóretán a 2-metylpyridín (346 a 108 hmot. častí). Po úpravě zloženia (na 12,5 % hmot. 2-metylpyridínu) sa táto zmes znova použije na přípravu aduktu oxidu sírového s 2-metylpyridínom, ktorý je sulfonačným činidlom izopropylamidu kyseliny antranilovej.The azeotropic mixture obtained is treated with extraction with 1,2-dichloroethane so that 250 wt. parts of the azeotropic mixture are extracted twice by 190 wt. parts of 1,2-dichloroethane. Then the organic layer contains 380 wt. parts of dichloroethane, 108 wt. parts of 2-methylpyridine and 6 wt. parts of water. The aqueous layer consists of 138 wt. parts of water and 2 wt. parts of dichloromethane. Water (6 parts by weight of water and 34 parts by weight of dichloroethane) was distilled off from the organic layer (494 parts by weight). The distillation residue contains 1,2-dichloroethane and 2-methylpyridine (346 and 108 parts by weight). After adjusting the composition (to 12.5% by weight of 2-methylpyridine), this mixture is reused to prepare an adduct of sulfur trioxide with 2-methylpyridine, which is the sulfonating agent of anthranilic acid isopropylamide.
Příklad 2Example 2
Postupuje sa podobné ako v přiklade 1, len miesto kyseliny sirovéj sa na okyslenie alkalických extraktov použije mólove rovnaké množství kyseliny trihydrogénfosforečnej a potom získaná anorganická hmota sa hedeponuje, lebo obsahuje prevážne vodorozpustné vápenaté hydrogénsoli kyseliny fosforečnéj, ktoré sa primiešavajú do priemyselných hnojiv.The procedure is similar to that of Example 1, except that instead of sulfuric acid, a molar equal amount of trihydrogenphosphoric acid is used to acidify the alkaline extracts, and then the inorganic mass obtained is hedeponated as it contains predominantly water-soluble calcium hydrogen phosphates mixed in industrial fertilizers.
Příklad 3Example 3
Příprava bentazónu sa uskutočňuje podlá postupu, ktorý je uvedený v příklade 1, len s tým rozdielom, že namiesto uhličitanu vápenatého sa použije bezvodý uhličitan sódny. Organická vrstva po azeotropickej destilácii obsahuje 346 hmot. častí 1,2-dichlóretánu a 106 hmot. častí 2-metylpyridínu. Po extrakcii destilátu dichlóretánom vo vodnej vrstvě ostávajú 2 hmot. časti 2-metylpyridínu. Regenerovaná zmes dichlóretán s 2-metylpyridínom sa použije pre přípravu aduktu s oxidom sírovým.The preparation of bentazone is carried out according to the procedure described in Example 1, except that anhydrous sodium carbonate is used instead of calcium carbonate. The organic layer after azeotropic distillation contains 346 wt. parts of 1,2-dichloroethane and 106 wt. parts of 2-methylpyridine. After extraction of the distillate with dichloroethane in the aqueous layer, 2 wt. parts of 2-methylpyridine. The recovered mixture of dichloroethane with 2-methylpyridine is used to prepare the sulfur trioxide adduct.
Příklad 4Example 4
Příprava bentazónu sa uskutočňuje podlá příkladu 1, ale s tým rozdielom, že na neutralizáciu kyslých solí 2-metylpyridínu sa použije hydroxid sodný. Organická vrstva (destilačný zvyšok)1 po azeotropickej destilácii obsahuje 343 hmot. častí dichlóretánu, 100 hmot. častí 2-metylpyridínu; 8 hmot. častí 2-metylpyridínu zostáva vo vodnej vrstvě po extrakcii destilátu (azeotropická zmes) dichlóretánom.The preparation of the bentazone is carried out according to Example 1, except that sodium hydroxide is used to neutralize the acid salts of 2-methylpyridine. The organic layer (distillation residue) 1 after azeotropic distillation contains 343 wt. parts by weight of dichloroethane, 100 wt. portions of 2-methylpyridine; 8 wt. parts of 2-methylpyridine remain in the aqueous layer after the distillate (azeotropic mixture) is extracted with dichloroethane.
Příklad 5Example 5
Postup přípravy bentazónu sa uskutočňuje podlá přikladu 1, ale s tým rozdielom, že na neutralizáciu kyslých solí 2-metylpyridínu sa použije 1 100 hmot. častí vápenného mlieka (obsah 8 % hmot. hydroxidu vápenatého). Organická vrstva obsahuje 325 hmot. častí dichlóretánu, hmot. častí 2-metylpyridínu. Vodná vrstva po extrakcii dichlóretánom obsahuje 14 hmot. častí 2-metylpyridínu.The preparation of bentazone is carried out according to Example 1, but with the difference that 1,100% by weight are used to neutralize the acid salts of 2-methylpyridine. parts of lime milk (8% by weight of calcium hydroxide). The organic layer contains 325 wt. parts by weight of dichloroethane; parts of 2-methylpyridine. The aqueous layer after extraction with dichloroethane contains 14 wt. parts of 2-methylpyridine.
Příklad 6Example 6
Postupuje sa podobné ako v příklade 1, len miesto izopropylamidu kyseliny antranilovej sa použije rovnaké molové množstvo sek. butylamidu kyseliny antranilovej. Získá sa 123,5 hmot. častí 3-sek.butyl-2,1,3-benzotiadiazín-4-on-2,2-dioxidu o teplote tavenia 153-154 °C.The procedure is similar to that of Example 1 except that the same molar amount of sec is used instead of anthranilic isopropylamide. anthranilic acid butylamide. 123.5 wt. parts of 3-sec-butyl-2,1,3-benzothiadiazin-4-one 2,2-dioxide having a melting point of 153-154 ° C.
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CN107417545B (en) * | 2017-04-20 | 2019-08-16 | 浙江中山化工集团股份有限公司 | The aftertreatment technology of condensation liquid in a kind of Bentazon preparation process |
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