CS759089A3 - Process for preparing 2-bromo-4.6-dinitroaniline - Google Patents
Process for preparing 2-bromo-4.6-dinitroaniline Download PDFInfo
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- CS759089A3 CS759089A3 CS897590A CS759089A CS759089A3 CS 759089 A3 CS759089 A3 CS 759089A3 CS 897590 A CS897590 A CS 897590A CS 759089 A CS759089 A CS 759089A CS 759089 A3 CS759089 A3 CS 759089A3
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- Prior art keywords
- bromo
- dinitroaniline
- dinitrochlorobenzene
- reaction
- ammonia
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- KWMDHCLJYMVBNS-UHFFFAOYSA-N 2-bromo-4,6-dinitroaniline Chemical compound NC1=C(Br)C=C([N+]([O-])=O)C=C1[N+]([O-])=O KWMDHCLJYMVBNS-UHFFFAOYSA-N 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- DWZNTFFZRWJFSU-UHFFFAOYSA-N 1-bromo-2-chloro-3,5-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC(Br)=C(Cl)C([N+]([O-])=O)=C1 DWZNTFFZRWJFSU-UHFFFAOYSA-N 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- KYDXWCHDUCDNGR-UHFFFAOYSA-N 1-chloro-2,3-dinitrobenzene Chemical class [O-][N+](=O)C1=CC=CC(Cl)=C1[N+]([O-])=O KYDXWCHDUCDNGR-UHFFFAOYSA-N 0.000 claims description 3
- 239000012736 aqueous medium Substances 0.000 claims description 3
- 239000002609 medium Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000005915 ammonolysis reaction Methods 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 239000012467 final product Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- -1 dinitrobenzene 2-bromo-4,6-dinitrochlorobenzene Chemical compound 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- LXQOQPGNCGEELI-UHFFFAOYSA-N 2,4-dinitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O LXQOQPGNCGEELI-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- DWHOIYXAMUMQTI-UHFFFAOYSA-L disodium;2-[(1-sulfonatonaphthalen-2-yl)methyl]naphthalene-1-sulfonate Chemical compound [Na+].[Na+].C1=CC2=CC=CC=C2C(S(=O)(=O)[O-])=C1CC1=CC=C(C=CC=C2)C2=C1S([O-])(=O)=O DWHOIYXAMUMQTI-UHFFFAOYSA-L 0.000 description 2
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 description 2
- TZZWIGRPBKTNGV-UHFFFAOYSA-N naphthalen-1-ylsulfonyloxymethyl naphthalene-1-sulfonate;sodium Chemical compound [Na].[Na].C1=CC=C2C(S(=O)(OCOS(=O)(=O)C=3C4=CC=CC=C4C=CC=3)=O)=CC=CC2=C1 TZZWIGRPBKTNGV-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- OLDMYNWXIGPOCI-UHFFFAOYSA-N 1-bromo-3,5-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC(Br)=CC([N+]([O-])=O)=C1 OLDMYNWXIGPOCI-UHFFFAOYSA-N 0.000 description 1
- KMAQZIILEGKYQZ-UHFFFAOYSA-N 1-chloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1 KMAQZIILEGKYQZ-UHFFFAOYSA-N 0.000 description 1
- LGAQVCNAUXQEJZ-UHFFFAOYSA-N 2-bromo-4,6-dinitrophenol Chemical compound OC1=C(Br)C=C([N+]([O-])=O)C=C1[N+]([O-])=O LGAQVCNAUXQEJZ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VYZAHLCBVHPDDF-UHFFFAOYSA-N Dinitrochlorobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 VYZAHLCBVHPDDF-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001513 alkali metal bromide Inorganic materials 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- XDLDASNSMGOEMX-UHFFFAOYSA-N benzene benzene Chemical compound C1=CC=CC=C1.C1=CC=CC=C1 XDLDASNSMGOEMX-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 150000005182 dinitrobenzenes Chemical class 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- VORRFUUQXVSQOQ-UHFFFAOYSA-N naphthalen-1-ylsulfonyloxymethyl naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(OCOS(=O)(=O)C=3C4=CC=CC=C4C=CC=3)=O)=CC=CC2=C1 VORRFUUQXVSQOQ-UHFFFAOYSA-N 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/52—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
-1- Předložený vynález se vztahuje k organické chemii a zejmé-na se týká způsobu výroby 2-brom-4,6-dinitroanilinu·The present invention relates to organic chemistry and more particularly to a process for producing 2-bromo-4,6-dinitroaniline.
Vynález najde široké uplatnění při výrobě disperzních barviv»V současné době jsou známy postupy výroby 2-brom-4,6-dinitroani-linu bromací 2,4-dinitroanilinu molekulárním bromem, která seprovádí podle čs» autorského osvědčení č. 152 605 v kyselině oc-tové za přítomnosti síry nebo podle německého spisu DE 5014972,ve vodném prostředí v přítomnosti peroxidu vodíku' nebo podleJournal fůr chemische Industrie, Kr0 11, 1986, str» 599 ve zře-děné kyselině chlorovodíkové za přítomnosti natriumhypochloritu.The present invention finds wide application in the production of disperse dyes. Currently, processes for the preparation of 2-bromo-4,6-dinitroaniline by bromination of 2,4-dinitroaniline with molecular bromine, which is carried out according to U.S. Patent No. 152,605, are known in the art. in the presence of sulfur or according to DE 5014972, in an aqueous medium in the presence of hydrogen peroxide or according to the journal Chemische Industrie, Kr 11, 1986, page 599 in dilute hydrochloric acid in the presence of sodium hypochlorite.
Ve všech těchto známých postupech, ve kterých nepředstavujeamonolýza poslední stupeň reakce, je v reakční směsi přítomen 2,4-dinitroanilin*In all of these known processes, in which the ammonolysis is not the last step of the reaction, 2,4-dinitroaniline * is present in the reaction mixture.
Je rovněž známa výroba 2-brom-4,6-dinitroanilinu amonolýzou2-brom-4,6-dinitrochlorbenzenu, která je prováděna tak, že seneche|plynný amoniak probublat suchým (nezředěným) alkoholem atento roztok je považován za výchozí sloučeninu (Journal Chemi-cal Society 125, 2482-84, 1324)., I přes získané vysoké výtěžky konečného produktu ( asi 85 % )nenalézá shora uvedený postup upotřebení ve velkém technickémměřítku a vdůsledku toho,byl prováděn pouze v měřítku laborator-ním, jelikož bylo nutné splnit komplikované technologické podmín- ky - plynný amoniak se musí nechat projít sloupcem hydroxidudraselného kvůli vysušení a alkohol musí být oddestilován» Výrobaplynného vysušeného amoniaku a bezvodého alkoholu vyžaduje ob- *1 -2- zvláště kategorické podmínky, které způsobují nerentabilnosttakovéto výroby.It is also known to produce 2-bromo-4,6-dinitroaniline by ammonolysis of 2-bromo-4,6-dinitrochlorobenzene, which is carried out by bubbling gaseous ammonia through dry (undiluted) alcohol and this solution is considered to be the starting compound (Journal Chemi- cal Society 125, 2482-84, 1324). Despite the high yields of the final product obtained (about 85%), the above procedure is not used on a large scale and as a result has been performed only on a laboratory scale since complicated technological conditions - ammonia gas must be allowed to pass through the potassium hydroxide column for drying and the alcohol has to be distilled off.
Známa je rovněž výroba 2-brom-4,β-dinitroanilinu amonolýzou2-4-dinitrochlorbenzenu s vodným amoniakem při teplotě 100 °C vautoklávu za následné bromace reakční směsi (US, A, 4581409). Výsledná reakční směs obsahuje jako příměsi 2-4-dinitroani-lin a sloučeniny, obsahující pryskyričnaté sloučeniny® Cílem předloženého vynálezu je vyvinout způsob výroby 2-brom--4,β-dinitroanilinu za podmínek, které umožňují přednostní sub- stituci volného atomu chloru před amineskupinou na benzenovémkruhu, což umožňuje získat čistý produkt. 'Tento úkol je vyřešen tím, že při způsobu výroby 2-brom-4,6-dinitroanilinu reakci dinitrobenzenu|derivátu s amoniakem zavyloučení konečného produktu se podle vynálezu použije jako de-rivátu dinitrobenzenu 2-brom-4,6-dinitrochlorbenzen a reakce samoniakem se provádí v přítomnosti anionaktivního dispergačníhočinidla ve vodném nebo vodně-alkalickém prostředí při teplotěS6 až 90 °C. Výtěžek konečného produktu činí 90 % teorie.It is also known to produce 2-bromo-4, β-dinitroaniline by ammonolysis of 2,4-dinitrochlorobenzene with aqueous ammonia at 100 ° C in an autoclave followed by bromination of the reaction mixture (US, A, 4581409). It is an object of the present invention to provide a process for the preparation of 2-bromo-4, β-dinitroaniline under conditions which allow the preferential substitution of free chlorine atom before an amine group on the benzene ring, allowing a pure product to be obtained. This object is achieved by the fact that in the process for the preparation of 2-bromo-4,6-dinitroaniline by reaction of the dinitrobenzene derivative with ammonia, the incorporation of the final product according to the invention is used as a derivative of the dinitrobenzene 2-bromo-4,6-dinitrochlorobenzene and the reaction by means of ammonia it is carried out in the presence of an anionic dispersing agent in aqueous or aqueous-alkaline medium at a temperature of from 6 to 90 ° C. The yield of the final product was 90% of theory.
Uako dispergační činidlo lze podle vynálezu použít dvojsod-ná sůl metylen-bis(naftalen-sulfonátu).As the dispersing agent, the disodium salt of methylene bis (naphthalene sulfonate) can be used according to the invention.
Další cíle a přednosti vynálezu jsou zřejmé z dále uvedené-ho podrobného popisu způsobu výroby 2-brom-4,6-dinitroanilinu az konkrétních příkladů provedení.Further objects and advantages of the invention will be apparent from the following detailed description of the process for the preparation of 2-bromo-4,6-dinitroaniline and from specific examples.
Způsob výroby 2-brom-4,6-dinitroanilinu podle vynálezu za-hrnuje amomolýzu 2-brom-4,6-dinitrochlorbenzenu. -τ- Výchozí sloučeninu 2-brom-4,6-dinitrobenzen je možno získatlibovolným známým způsobem, např» z chlorbenzenu, který se nej-dříve nechá reagovat se směsí kyseliny dusičné a kyseliny síro-vé nebo z jednotlivého o-, p-nitrobenzenu nebo z eutektické smě-si ο-, p—, m-nitrochlorbenzenu reakcí s bromem nebo bromidemalkalického kovu, s kyselinou dusičnou nebo dusičnanem alkalic-kého kovu a s kyselinou sírovou nebo oleem při těchto molárníchpoměrech reakčních složek (vztaženo na uvedenou aromatickou slou- čeninu halogenderivátu) : brom nebo bromid alkalického kovu : : kyselině sírové nebo oleu = 1,0 : 0,5 - 1,5 nebo 1,0 - '5,0 : : 2,0 - 4,0 nebo 2,5 - 5,0 : 6,0 - 70,0 při teplotě 20 až 120 °C.The process for the preparation of 2-bromo-4,6-dinitroaniline according to the invention comprises the amomolysis of 2-bromo-4,6-dinitrochlorobenzene. The starting compound 2-bromo-4,6-dinitrobenzene can be obtained in any known manner, for example from chlorobenzene, which is first reacted with a mixture of nitric acid and sulfuric acid or from a single o-, p-nitrobenzene or from the eutectic mixture of β-, β-, m -nitrochlorobenzene by reaction with bromine or bromide alkali metal, nitric acid or alkali metal nitrate and sulfuric acid or ole at these molar ratios of the reactants (based on the aromatic compound of the halogen derivative) ): alkali metal bromide or bromide:: sulfuric acid or oleum = 1.0: 0.5 - 1.5 or 1.0 - 5.0: 2.0 - 4.0 or 2.5 - 5, 0: 6.0-70.0 at 20-120 ° C.
Podle vynálezu se provádí amonolýza za mírných podmínek přiteplotě 86 až 90 °C ve vodném prostředí nebo v organickém rozpou-štědle, např, v chlorbenzenu, za přítomnosti anionaktivního dis-pergačního činidla,.According to the invention, ammonolysis is carried out under mild conditions at a temperature of 86-90 ° C in aqueous medium or in an organic solvent, e.g. chlorobenzene, in the presence of an anionic dispersing agent.
Amonolýza se provádí za použití 50% vodného roztoku amoniaku.Amonolysis is carried out using 50% aqueous ammonia solution.
Selektivní substituce atomu chloru za aminoskupinu a ne atomubromu nebo atomu chloru za atom bromu současně se uskutečnilaza přítomnosti libovolného anionaktivního dispergačního činidla,např. dvojsodné soli metylen-bis(naftalen-sulfonátu) nebo kon- ;;ϊγΛ'fy' VA»*. J\1 -: ·';? .. -. t.Selective substitution of the chlorine atom for the amino group and not the atomubroma or chloro atom for the bromine atom is simultaneously effected by the presence of any anionic dispersing agent, e.g. disodium methylenebis (naphthalene sulphonate) or conjugate; J 1 -: · '; .. -. t.
-J <Α -4- denzačního produktu kresol-formaldehydové pryskyřice s 2-6-na-triumnaftylsulfonátu s formaldehydem nebo natriumsulfitem.A densification product of cresol-formaldehyde resin with 2-6-na-triumnaphthyl sulfonate with formaldehyde or sodium sulfite.
Provedení amonolýzy za uvedených podmínek v přítomnostidispergačního činidla zabraňuje tomu, aby v konečném produktubyly rovněž přítomny příměsi s obsahem pryskyřičnatých láteka 2-brom-4,6-dinitrofenolu.The ammonolysis under these conditions in the presence of a dispersing agent prevents the addition of 2-bromo-4,6-dinitrophenol resinous ingredients in the final product.
Reakční směs, získaná způsobem amonolýzy podle vynálezuobsahuje jen konečný produkt s méně než 0,5 % bromchlordinitrebenzenu.The reaction mixture obtained by the ammonolysis process according to the invention contains only the final product with less than 0.5% bromochlorite nitrobenzene.
Pro lepší objasnění předloženého vynálezu jsou uvedeny ná-sledující příklady. Příklad 1 2,8 g 2-brom-4,6-dinitrochlorbenzenu se rozpustí ve 100 ml30% roztoku amoniaku, přidá se 0,28 g dvojsodné soli metylen-bis(naftalensulfonátu) a míchá se při teplotě 86 až 90 °C podobu 8 hodin.The following examples are provided to illustrate the present invention in greater detail. EXAMPLE 1 2.8 g of 2-bromo-4,6-dinitrochlorobenzene are dissolved in 100 ml of 30% ammonia solution, 0.28 g of disodium methylene bis (naphthalene sulfonate) is added and stirred at 86 to 90 DEG C. hours.
Ukončení reakce se zjišťuje chromatografií na tenké vrstvě.Reakční produkt se ochladí, sraženina 2-brom-4,6-dinitroanilinuse odfiltruje, promyje vodou a vysuší. Získá se 2,2 g 2-brom--4,β-dinitroanilinu ve výtěžku 85 % teorie, teplota tání je 149as 151 °C. i Příklad 2 2,3 g 2-brom~4,6-dinitrochlorbenzenu se míchá se 30 ml cl}ér·benzenu do rozpuštění, přidá se 100 ml 30% roztoku amoniaku s0,28 g dvojsodné soli metylen-bis-^naftalensulfonátu) a míchá -5- se při teplotě 88 až 90 °C po dobu 8 hodin. Po ukončení reakce,které sefstanoví chromatografií na tenké vrstvě, se přidá 30 mlvody a oddestiluje se chlorbenzen s vodou. Získá se 2,35 g 2--brom-4,β-dinitroanilin^Výtěžek činí 90 % teorie, teplota táníproduktu je 150 až lpi C. Příklad 3 28 g 2-brom-4,6-dinitrochlorbenzenu se smíchá s 300 ml 30%vodného roztoku amoniaku, přidají se 3 g dvojsodné soli metylen-bis-(naftalensulfonátu) a míchá se po dobu 8 hodin při teplotě86 až 90 °C. Ukončení reakce se stanoví chromatografií na tenkéVPStVŠ·The reaction was cooled, the precipitate of 2-bromo-4,6-dinitroaniline was filtered off, washed with water and dried. 2.2 g of 2-bromo-4, β-dinitroaniline are obtained in a yield of 85% of theory, m.p. 149 DEG-151 DEG. Example 2 2.3 g of 2-bromo-4,6-dinitrochlorobenzene are mixed with 30 ml of benzene benzene until dissolved, 100 ml of 30% ammonia solution with 0.28 g of disodium methylene-bis-naphthalenesulfonate salt are added. and stirring at 88-90 ° C for 8 hours. After completion of the reaction by thin layer chromatography, 30 ml of water are added and chlorobenzene is distilled off with water. 2.35 g of 2-bromo-4, β-dinitroaniline are obtained. Yield: 90% of theory, melting point 150 DEG-1 DEG C. EXAMPLE 3 28 g of 2-bromo-4,6-dinitrochlorobenzene are mixed with 300 ml. % aqueous ammonia solution, 3 g methylene bis (naphthalene sulfonate) disodium salt are added and stirred for 8 hours at 86-90 ° C. Termination of the reaction is determined by thin-layer chromatography.
Produkt se ochladí, sraženina 2-brom-4,6-dinitroanilinu seodfiltruje, promyje vodou a vysuší. Výtěžek činí 22,5 g ( 85 %)teorie. Příklad 4 28 g 2-brom--4, o-dinitrochlorbenzenu se vloží do 300 ml 30%roztoku amoniaku, přidají se 3 g kondenzačního produktu kresol--formaldehydové pryskyřice a 2,6-naftolsulfonátu sodného s for-maldehydem a sulfidem sodným a dále probíhá reakce tak, jak jepopsána v příkladu 3. Získá se 32 g 2-brom-4,β-dinitroanilinu v 85% výtěžku teorie.The product is cooled, the 2-bromo-4,6-dinitroaniline precipitate is filtered, washed with water and dried. The yield was 22.5 g (85%) of theory. EXAMPLE 4 28 g of 2-bromo-4, o-dinitrochlorobenzene are placed in 300 ml of a 30% ammonia solution, 3 g of the condensation product of cresol-formaldehyde resin and sodium 2,6-naphthol sulfonate with formaldehyde and sodium sulfide are added. the reaction proceeds as described in Example 3. 32 g of 2-bromo-4, β-dinitroaniline are obtained in 85% of theory yield.
Claims (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SU4622747 RU2007385C1 (en) | 1988-12-30 | 1988-12-30 | Method of 2-bromo-4,6-dinitroaniline synthesis |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS759089A3 true CS759089A3 (en) | 1992-01-15 |
Family
ID=21416276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS897590A CS759089A3 (en) | 1988-12-30 | 1989-12-29 | Process for preparing 2-bromo-4.6-dinitroaniline |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0402486A4 (en) |
| JP (1) | JPH03503173A (en) |
| CN (1) | CN1043933A (en) |
| CS (1) | CS759089A3 (en) |
| RU (1) | RU2007385C1 (en) |
| WO (1) | WO1990007489A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5292899A (en) * | 1991-11-27 | 1994-03-08 | Synthetic Technology Corporation | Synthesis of 11-nor-Δ-9-tetrahydrocannabinol-9-carboxylic acid glucuronide |
| GB9907458D0 (en) * | 1999-03-31 | 1999-05-26 | Rhone Poulenc Agrochimie | Processes for preparing pesticidal intermediates |
| RU2315749C1 (en) * | 2006-07-31 | 2008-01-27 | Федеральное государственное унитарное предприятие "Государственный научно-исследовательский институт "Кристалл" | Method for preparing 2,4,6-trichloro-3,5-dinitroaniline |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE3014972C2 (en) * | 1980-04-18 | 1984-11-22 | Chemische Fabrik Kalk GmbH, 5000 Köln | Process for the preparation of 2,4-dinitro-6-bromaniline |
-
1988
- 1988-12-30 RU SU4622747 patent/RU2007385C1/en active
-
1989
- 1989-12-22 JP JP90501831A patent/JPH03503173A/en active Pending
- 1989-12-22 EP EP19900901096 patent/EP0402486A4/en not_active Withdrawn
- 1989-12-22 WO PCT/SU1989/000332 patent/WO1990007489A1/en not_active Ceased
- 1989-12-29 CS CS897590A patent/CS759089A3/en unknown
- 1989-12-29 CN CN 89109829 patent/CN1043933A/en active Pending
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| Publication number | Publication date |
|---|---|
| JPH03503173A (en) | 1991-07-18 |
| EP0402486A4 (en) | 1991-06-05 |
| RU2007385C1 (en) | 1994-02-15 |
| CN1043933A (en) | 1990-07-18 |
| WO1990007489A1 (en) | 1990-07-12 |
| EP0402486A1 (en) | 1990-12-19 |
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