SE194128C1

SE194128C1 -

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Publication number: SE194128C1
Authority: SE
Publication date: 1964-01-01

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Uppfinnare: F Ackermann, A-E Siegrist och M Diinnenberger Prioritet begard fain den 17 juni 1955 (Schweiz) Foreliggande uppfinning avser ett forfarande for framstallning av nya dikarbonsyradiamider med formeln: • (1) van X betecknar on vdteatom, en kloratom eller en alkylgrupp med 1-4 kolatomer, Y betecknar en vateatom eller en metylgrupp och R betecknar resten —CH = CH—, resten —/\— eller resten HC—CH IIII —c C — / 0 vilket fOrfarande kannetecknas darav, att man kondenserar dikarbonsyradihalogenider med formeln halogen—CO—R—CO—halogen van i R har angiven betydelse, i molekylforhallandet 1: 2 i narvaro av inerta organiska losningsmedel vid temperaturer mellan 100 och 200° C med primara arylaminer med formeln (2) van i X och Y har angiven betydelse. Sasom clikarbonsyradihalogenider anvander man exempelvis dikarbonsyradibromider eller foretradesvis dikarbonsyradiklorider, sasom fumarsyradiklorid, tereftalsyradiklorid eller furan-2,5-dikarbonsyradiklorid. Lampliga primara arylaminer med f or-mein (2) aro exempelvis 1-amino-2-oxibensen 1-amino-2-o3d-5-metyl-bensen 1-amino-2-oxi-4-metyl-bensen 1-amino-2-oxi-3,5-dimetyl-bensen 1-amino-2-o3d-5-tert.-butyl-bensen 1-amino-2-oxi-5-klor-bensen. Inventors: F Ackermann, AE Siegrist and M Diinnenberger Priority as found on June 17, 1955 (Switzerland). -4 carbon atoms, Y represents a hydrogen atom or a methyl group and R represents the residue -CH = CH-, the residue - / \ - or the residue HC-CH IIII -c C - / 0 which process can be characterized by condensing dicarboxylic acid dihalides of the formula halogen —CO — R — CO —halogen van in R has the meaning given, in the molecular ratio 1: 2 in the presence of inert organic solvents at temperatures between 100 and 200 ° C with primary arylamines of formula (2) van in X and Y have the meaning given . As clicarboxylic acid dihalides, for example, dicarboxylic acid dibromides or, preferably, dicarboxylic acid dichlorides, such as fumaric acid dichloride, terephthalic acid dichloride or furan-2,5-dicarboxylic acid dichloride are used. Suitable primary arylamines of form (2) are, for example, 1-amino-2-oxybenzene 1-amino-2-o3d-5-methyl-benzene 1-amino-2-oxy-4-methyl-benzene 2-oxy-3,5-dimethyl-benzene 1-amino-2-o3d-5-tert-butyl-benzene 1-amino-2-oxy-5-chloro-benzene.

Kondensationen ager rum i narvaro av ett inert organiskt losningsmedel. Hrtil1 kan man anvanda de mest olika liisningsmedel, i vilka bada utgangsmaterialen aro bestandiga. Goda resultat uppnas exempelvis med over 100° C kokande losningsmodel av bensenserien, sasom toluen, xylener, kumen, klorbensen, di- eller triklorobensener eller nitrobensen. Kondensationsreaktionen genomMires vid temperaturer mellan 100 och 200° C Efter avslutad omsattning kunna dikarbonsyradiamiderna isoleras ur reaktionsblandningen pa i och for sig kant Att. I manga fall aro de sá svarlosliga i det anvanda losningsmedlet, aft de eventuellt efter kylning av blandningen utfalla i mycket gott utbyte och med hog renhetsgrad. The condensation takes place in the presence of an inert organic solvent. For this purpose, one can use the most diverse solvents in which both starting materials are resistant. Good results are obtained, for example, with a solution model of the benzene series boiling above 100 ° C, such as toluene, xylenes, cumene, chlorobenzene, di- or trichlorobenzene or nitrobenzene. The condensation reaction is carried out by mixing at temperatures between 100 and 200 ° C. After completion of the reaction, the dicarboxylic acid diamides can be isolated from the reaction mixture per se. In many cases they are so unresponsive in the solvent used, that they may precipitate in a very good yield and with a high degree of purity after cooling the mixture.

FOreningarna med formeln (1) Oro vardefulla mellanprodukter, vilka exempelvis kunna anvandas for framstallning av fargamnen, foretradesvis emellertid for framstallning av optiska vithetsforstarkande medel. De kunna exempelvis med hjalp av vattenavspjalkande medel overfOras till heterocykliska foreningar (oxazoler), vilka kunna framstallas vasentligt lattare och i renare form On enligt kanda forfaranden, t. ex. genom upphettning av wdaminoarylforeningar med dikar- 00 IIII NH — C —R —C —HN HO Dupl. kI. 12 p: 3 2— — bonsyror av samma slag som barnstenssyra och foljande dehydrering. The compounds of formula (1) However, valuable intermediates which can be used, for example, for the preparation of the dyes, are preferably for the preparation of optical brightness enhancers. They can be transferred, for example, with the aid of water-repellent agents to heterocyclic compounds (oxazoles), which can be prepared substantially lighter and in a purer form On according to known procedures, e.g. by heating wdaminoaryl compounds with dicar- 00 IIII NH - C —R —C —HN HO Dupl. kI. 12 p: 3 2— - bonic acids of the same kind as succinic acid and subsequent dehydration.

I foljande exempel beteckna delar, savida joke nagot annat angives, viktdelar och procent viktpro cent. In the following examples denote parts, savida joke something else is stated, parts by weight and percent weight percent.

Exempel 1. En losning av 123 delar 1-amino-2- oxi-5-metylbensen i 1200 delar monoklorbensen forsattes droppvis under °untiring och utestangande av luften vid 125-130° C Mom 1 timme med 76,5 delar fumarsyradiklorid och blandningen kokas sedan fOrsiktigt ytterligare 6 timmar. Man later blandningen svalna, franfiltrerar kondensationsprodukten och tvattar den med klorbensen, alkohol och vatten. Det filtrerade materialet loses vid 0° C i utspadd natriumhydroxid, losningen filtreras och den gula kondensationsprodukten utMlles med utspadd saltsyra, franfiltreras, tvattas med vatten och torkas. Example 1. A solution of 123 parts of 1-amino-2-oxy-5-methylbenzene in 1200 parts of monochlorobenzene was continued dropwise during untiring and expelling the air at 125-130 ° C for 1 hour with 76.5 parts of fumaric acid dichloride and the mixture was boiled. then gently for another 6 hours. The mixture is allowed to cool, the condensation product is filtered off and washed with chlorobenzene, alcohol and water. The filtered material is dissolved at 0 ° C in dilute sodium hydroxide, the solution is filtered and the yellow condensation product is eluted with dilute hydrochloric acid, filtered off, washed with water and dried.

Det erhallna, gula pulvret med formeln OHHO H-CO-CH=CH-CO - N H smaller vid 255° C efter omkristallisering ur vattenhaltig dimetylformamid. Kondensationen kan -aven genomforas i m-xylen. The resulting yellow powder of the formula OHHO H-CO-CH = CH-CO - N H narrows at 255 ° C after recrystallization from aqueous dimethylformamide. The condensation can also be carried out in m-xylene.

Om man ersatter de 123 delarna 1-amino-2- ,oxi-5-metylbensen med ekvimolekylara mangder 1-amino-2-oxi-3,5-dimetylbensen, erhaller man fOreningen med formeln i form av ett ljust pulver med liknande egenskaper. If one replaces the 123 parts of 1-amino-2-, oxy-5-methylbenzene with equimolecular amounts of 1-amino-2-oxy-3,5-dimethylbenzene, the compound of the formula is obtained in the form of a light powder with similar properties.

Om man ersatter de 123 delarna 1-amino-2- oxi-5-metylbensen med den ekvimolekylara mangden 1-amino-2-oxi-5-klorbensen, erhaller man foreningen med formeln OHHO CNH-C-CH=C H-C-HN If 00 Kondensationen kan aven genomforas i isattika. Replacing the 123 parts of 1-amino-2-oxy-5-methylbenzene with the equimolecular amount of 1-amino-2-oxy-5-chlorobenzene gives the compound of the formula OHHO CNH-C-CH = C HC-HN If The condensation can also be carried out in glacial acetic acid.

Exempel 2. En suspension av 58 delar fumarsyra 11000 delar o-diklorbensen forsattes droppvis vid 160-165° C Mom 4-6 timmar under god omrering med 131 delar tionylklorid. Man erhailer en losning, fran vilkeri eventuellt fortfarande narvarande tionylklorid kan avlagsnas genom omroring vid ungefar 1° C. Under utestangande av luft avkyler man till ungefar 110° C, .tillsatter 109 delar 1-amino-2-oxibensen och omrer 8 timmar vid 140-150° C, varvid den grOn skiftande gula, fasta kondensationsprodukten med formeln OHHO NH -C-CH=C H-O-N H IIII 00 utfalles till storre delen. o-diklorbensenen avdestilleras med anga, aterstoden franfiltreras, tvattas med varmt vatten och torkas. Example 2. A suspension of 58 parts of fumaric acid 11000 parts of o-dichlorobenzene was continued dropwise at 160-165 ° C for 4-6 hours with good stirring with 131 parts of thionyl chloride. A solution is obtained, from which any still present thionyl chloride can be removed by stirring at about 1 ° C. While expelling air, it is cooled to about 110 ° C, 109 parts of 1-amino-2-oxybenzene are added and the mixture is stirred for 8 hours at 140 ° C. -150 ° C, whereby the green-shifting yellow solid condensation product of the formula OHHO NH -C-CH = C HON H IIII 00 precipitates for the most part. The o-dichlorobenzene is distilled off with steam, the residue is filtered off, washed with hot water and dried.

Kondensationsprodukten med ovanstaende formel utgor ett grongult pulver, som ar lbsligt i utspadd natriumhydroxidlOsning och kan aterutfallas med syra. Den nya produkten smalter vid 262° C. The condensation product of the above formula is a green-yellow powder which is soluble in dilute sodium hydroxide solution and can be reprecipitated with acid. The new product melts at 262 ° C.

Exempel 3. 109 delar 1-amino-2-oxibensen i 800 delar klorbensen forsattes droppvis vid 125130° C Mom 1 timme med en losning av 101,5 delar tereftalsyradiklorid i 200 delar klorbensen och blandningen kokas forsiktigt y tierligare 6 timmar. Example 3. 109 parts of 1-amino-2-oxybenzene in 800 parts of chlorobenzene were added dropwise at 125130 ° C for 1 hour with a solution of 101.5 parts of terephthalic acid dichloride in 200 parts of chlorobenzene and the mixture was boiled gently for another 6 hours.

Man later blandningen svalna, franfiltrerar den utfallda kondensationsprodukten, tvattar den med klorbensen och alkohol och torkar den. The mixture is allowed to cool, the precipitated condensation product is filtered off, washed with chlorobenzene and alcohol and dried.

Den erhallna pro dukten med formeln OH NH- C 0 utgor ett gulaktigt pulver, som är losligt i vattenhaltiga alkalier och kan omfallas med syra. The product obtained with the formula OH NH-C 0 constitutes a yellowish powder, which is soluble in aqueous alkalis and can be reacted with acid.

Exempel 4. En losning av 109 delar 1-amino-2- oxibensen i 1200 delar klorbensen forsattes droppvis under omroring och utestangande av luft vid 125-130° C inom 1 timme med 67 delar fumarsyradiklorid och Mlles under Mt kokning ytterligare 6 timmar. Man later blandningen svalna, franfiltrerar kondensationsprodukten och tvattar den med klorbensen, alkohol och vatten. Det filt- rerade materialet loses vid 0° C i utspadd natriumhydroxid, losningen filtreras och den gula kondensationsprodukt, som utfalles med utspadd saltsyra, tvattas neutral med vatten och torkas. Example 4. A solution of 109 parts of 1-amino-2-oxybenzene in 1200 parts of chlorobenzene was continued dropwise with stirring and quenching of air at 125-130 ° C within 1 hour with 67 parts of fumaric acid dichloride and Mlles under Mt boiling for another 6 hours. The mixture is allowed to cool, the condensation product is filtered off and washed with chlorobenzene, alcohol and water. The filtered material is dissolved at 0 ° C in dilute sodium hydroxide, the solution is filtered and the yellow condensation product, which precipitates with dilute hydrochloric acid, is washed neutral with water and dried.

Det erhallna gula pulvret med formeln OHHO NH-CO-CH=C H-C 0-H N smalter efter kristallisering ur vattenhaltig dimetylformamid vid 262° C. Kondensationen kan aven genomforas i m-xylen. The resulting yellow powder of the formula OHHO NH-CO-CH = C H-C O-H N melts after crystallization from aqueous dimethylformamide at 262 ° C. The condensation can also be carried out in m-xylene.

Om man ersatter de 109 delarna 1-amino-2- oxibensen med ekvimolekylara mangder 1-amino2-oxi-5-klorbensen erhaller man foreningen med foljande formel och med liknande egenskaper: OHHO NH-CO-CH=CH-00-HN CH3 OHHO H-CO-CFK H-CO-NH H3C C — HN 0 HO Cl Cl - -3 Exempel 5. Pa i exempel 4 angivet salt erhdller man 24,6 delar 1-amino-2-oxi-5-metylbensen, 19,3 delar furan-2,5-dikarbonsyrarliklorid och 300 delar monoklorbensen foreningen med formeln OHHC —CHHO 1111 H3CH-CO - C C - CO-HN \c/ i form av ett ljust pulver med smaltpunkten 272° C, vilket har liknande egenskaper. Replacing the 109 parts of 1-amino-2-oxybenzene with equimolecular amounts of 1-amino2-oxy-5-chlorobenzene gives the compound of the following formula and having similar properties: OHHO NH-CO-CH = CH-00-HN CH3 OHHO H-CO-CFK H-CO-NH H3C C - HN 0 HO Cl Cl - -3 Example 5. On the salt given in Example 4, 24.6 parts of 1-amino-2-oxy-5-methylbenzene are obtained, 19, 3 parts of furan-2,5-dicarboxylic acid chloride and 300 parts of the monochlorobenzene compound of the formula OHHC -CHHO 1111 H3CH-CO - CC - CO-HN \ c / in the form of a light powder with a melting point of 272 ° C, which has similar properties.

Exempel 6. En losning av 16,5 delar p-tertidr butyl-o-aminofenol i 80 delar klorbensen fOrsattes droppvis under omroring och utestangande av luft vid 125-130° C inom 10 minuter med 7,6 delar fumarsyradiklorid, som är utspadd med 20 delar klorbensen. Darefter kokas blandningen 4 timrnar under dterflddskylning, lamnas att svalna och filtreras. Den gula kondensationsprodukten med formeln van i X betecknar en vateatom, en kloratom eller en alkylgrupp med 1-4 kolatomer, Y betecknar en vdteatom eller en metylgrupp och R betecknar resten -CH = CH-, resteneller resten kannetecknat ddrav, att dikarbonsyradihalogenider med formeln halogen-CO-R-CO-halogen van i R har angiven betydelse, i molforhallandet 1: 2 kondenseras med primdra arylaminer med formeln H3C HC-C HC OHHO /CH3 NH-C-CH=CH-C-HNC-CH3 \CH3 smatter after omkristallisering vid 140-143° C.Example 6. A solution of 16.5 parts of p-tetidr butyl-o-aminophenol in 80 parts of chlorobenzene was proceeded dropwise with stirring and quenching of air at 125-130 ° C within 10 minutes with 7.6 parts of fumaric acid dichloride diluted with 20 parts chlorobenzene. The mixture is then boiled for 4 hours under continuous cooling, left to cool and filtered. The yellow condensation product of the formula van in X represents a hydrogen atom, a chlorine atom or an alkyl group having 1-4 carbon atoms, Y represents a hydrogen atom or a methyl group and R represents the radical -CH = CH-, the radical or the radical may denote that -CO-R-CO-halogen van in R has the indicated meaning, in the molar ratio 1: 2 is condensed with primary arylamines of the formula H3C HC-C HC OHHO / CH3 NH-C-CH = CH-C-HNC-CH3 \ CH3 smatter after recrystallization at 140-143 ° C.

Claims

Patent claim: Process for the preparation of new dicarboxylic acid diamides of the formula 0 0 IIII NH- C - RC -HN OHHO used in X and Y have the stated meaning, in the presence of inert organic solvents at temperatures between 100 and 200 ° C. Request publications: Patents! Real France 848 386.