SE194131C1 - - Google Patents

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SE194131C1
SE194131C1 SE194131DA SE194131C1 SE 194131 C1 SE194131 C1 SE 194131C1 SE 194131D A SE194131D A SE 194131DA SE 194131 C1 SE194131 C1 SE 194131C1
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parts
formula
water
compounds
amino
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60—Optical bleaching or brightening
    • D06L4/657—Optical bleaching or brightening combined with other treatments, e.g. finishing, bleaching, softening, dyeing or pigment printing
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D249/22—Naphthotriazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/62—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems having two or more ring systems containing condensed 1,3-oxazole rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
    • C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
    • C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
    • C07D279/16—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
    • C09B35/02—Disazo dyes
    • C09B35/039—Disazo dyes characterised by the tetrazo component
    • C09B35/34—Disazo dyes characterised by the tetrazo component the tetrazo component being heterocyclic
    • D06L3/1257—

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Description

Uppfinnare: F Ackermann, A-E Siegrist och M Dannenberger Prioritet begard frail. den 17 juni 1955 (Schweiz) Det liar visat sig, att heterocykliska foreningar av samma typ som den i och for sig kanda Ibensoxazoly1-(2)1-etylenen pa lampligt satt kunna framstallas, om acylfbreningar med formeln: eller med formeln X NH X\\/ 2 Z \ 0—C—R—C-0/\XZ (la) 00 van i X betecknar en vateatom, en kloratom eller en alkylgrupp med 1-4 kolatomer, Z betecknar en vateatom eller en metylgrupp och R resten —CH = CH—, resten\ eller resten HC—CH —C C- \ / 0 behandlas med sadana medel, som ha formaga att ur angivna acylforeningar avspjalka vatten och eventuellt infora sulfonsyragrupper, varvid bildas foreningar med formeln: XX\/1\T\ /N\/> Man erhaller de har sasom utgangsamnen tjanande foreningarna med formlerna (1) eller (la), om man kondenserar dikarbonsyradihalogenider med formeln: halogen—CO—R---CO—halogen, van i R liar angiven betydelse, i molekylfiirhallandet 1 : 2 med en lamplig primar aminobensen, som i o-stallning till aminogruppen uppvisar en oxigrupp. Sasom dikarbonsyradihalogenider anvander man exempelvis dikarbonsyradibromid eller foretradesvis dikarbonsyradiklorid, sasom fumarsyradiklorid, tereftalsyradiklorid eller furan-2,5- dikarbonsyradiklorid. Lampliga primara aminobensener, som o-stallning till aminogruppen uppvisar en oxigrupp, aro exempelvis 1-amino-2- oxibensen, 1-amino-2-oxi-5-metyl-bensen, 1-amino-2-oxi-4-metyl-bensen, 1-amino-2-oxi-3,5-dimetyl-bensen, 1-amino-2-oxi-5-tert-butylbensen, 1- amino-2-oxi-5-klor-b ensen. Inventors: F Ackermann, A-E Siegrist and M Dannenberger Priority requested frail. June 17, 1955 (Switzerland) It has been found that heterocyclic compounds of the same type as the per se known Ibensoxazoly1- (2) 1-ethylene can be conveniently prepared if acyl compounds of the formula: or of the formula X NH X Z 2 represents a hydrogen atom, a chlorine atom or an alkyl group having 1-4 carbon atoms, Z represents a hydrogen atom or a methyl group and R the radical —CH = CH-, the residue \ or the residue HC — CH —C C T h / N , in the molecular ratio 1: 2 with a suitable primer aminobenzene, which in the o-position to the amino group has an oxy group. As dicarboxylic acid dihalides, for example, dicarboxylic acid dibromide or, preferably, dicarboxylic acid dichloride, such as fumaric acid dichloride, terephthalic acid dichloride or furan-2,5-dicarboxylic acid dichloride are used. Suitable primary aminobenzenes, which o-form to the amino group have an oxy group, are, for example, 1-amino-2-oxybenzene, 1-amino-2-oxy-5-methylbenzene, 1-amino-2-oxy-4-methylbenzene. benzene, 1-amino-2-oxy-3,5-dimethyl-benzene, 1-amino-2-oxy-5-tert-butylbenzene, 1-amino-2-oxy-5-chloro-benzene.

Kondensationen sker i narvaro av ett inert, organiskt lOsningsmedel. Man kan harvid anvanda losningsmedel av skilda slag, i vilka bada utga.ngsamnena aro bestandiga. Alltefter reaktionsbetingelserna kunna karbonsyrahalogeniderna antingen reagera med1-10-grupperna eller H,N-grupperna i aminobensenerna. Den forsta reaktionen in-trader foretradesvis vid milda, sura reaktionsbetingelser under det att vid kraftigare betingelser aminogrupperna i regel acyleras. De vid milda och sura betingelser framstallbara estrarna omlagra sig la.tt till acylaminer, t. ex. vid uppvarmning organiska losningsmedel eller genom behandling med baser. For omedelbar framstallning av de senare anvander man lampligen losningsmedel med forhallandevis hog kokpunkt, t. ex. hogre an 100° C. Goda resultat erhallas exempelvis med Over 100° C kokande losningsmedel ur bensenserien, sasom toluen, xylener, ldorbensen, di- eller X \\/ NH—C—R—C—NHX I\ 0 0 (1) I-12N 2— — triklorbensener eller nitrobensen. Für att icke fOrlanga reaktionstiden for mycket är det lampligt att arbeta vid temperaturer Over 100° C men i allmanhet bor den icke overstiga 200° C. The condensation takes place in the presence of an inert, organic solvent. It is possible to use solvents of various kinds, in which both starting materials are resistant. Depending on the reaction conditions, the carbonic acid halides can react either with the 1-10 groups or the H, N groups in the aminobenzenes. The first reaction preferably occurs under mild, acidic reaction conditions while under more severe conditions the amino groups are usually acylated. The esters which can be prepared under mild and acidic conditions are readily rearranged into acylamines, e.g. when heating organic solvents or by treatment with bases. For immediate production of the latter, solvents with a relatively high boiling point are suitably used, e.g. higher than 100 ° C. Good results are obtained, for example, with Boilers from the benzene series boiling above 100 ° C, such as toluene, xylenes, chlorobenzene, di- or X I-12N 2— - trichlorobenzenes or nitrobenzene. In order not to prolong the reaction time too much, it is convenient to work at temperatures above 100 ° C, but in general it should not exceed 200 ° C.

Efter fullbordad omsattning kunna acylf Oreningarna isoleras pa vanligt, i och for sig kant satt ur reaktionsblandningen. I manga fall aro de sa svarlosliga i det anvanda losningsmedlet att de, eventuellt efter avkylning av blandningen, utfalla i mycket gott utbyte och i mycket ren form. After completion of the reaction, the acylph impurities can be isolated in the usual manner, per se set out of the reaction mixture. In many cases they are so unresponsive in the solvent used that, possibly after cooling the mixture, they precipitate in very good yield and in very pure form.

De salunda framstallbara acylforeningarna med formeln (1) eller (la) behandlas nu med vattenavspjalkande medel. Man kan som vattenavspjalkande medel exempelvis anvanda svaveltrioxid fOretradesvis i form av oleum. Harvid sker forutom ringslutningen aven en sulfonering. Sarskilt lamplig har anvandningen av zinkkIorid visat sig vara. Genom behandling av acylforeningarna i en zinkkloridsmalta, som fore upphettningen med ftirdel forsattes med en liten mangd vatten, kan vattenavspjalkningen °eh armed ringslutningen till bisoxazolylforeningen genomforas pa enkelt salt och med gott resultat. Lampliga ternperaturer for vattenavspjalkningen medelst zinkklorid aro exempelvis temperaturer mellan 140 och 180° C, foretradesvis ungefar 160° C. Efter \ —OH av- slutad omsattning kunna pro dukterna erhallas pa enkelt satt genom tillsats av vatten till smaltan och surgoring av den utfallda blandningen och franskilj as genom filtrering. For vidare rening kan man omkristallisera dem ur lampliga organiska losningsmedel. The acyl compounds of formula (1) or (Ia) which can thus be prepared are now treated with water-repellent agents. Sulfur trioxide can be used, for example, as a water-repellent agent, preferably in the form of an oleum. In addition to the ring closure, a sulfonation also takes place. The use of zinc chloride has proved to be particularly appropriate. By treating the acyl compounds in a zinc chloride malt, which was preheated with a small amount of water before heating, the water cleavage and the armed cyclization to the bisoxazolyl compound can be carried out on simple salt and with good results. Suitable temperatures for the water splitting off with zinc chloride are, for example, temperatures between 140 and 180 ° C, preferably about 160 ° C. franskilj as by filtration. For further purification, they can be recrystallized from suitable organic solvents.

Bis-oxazoly1fOreningarna kunna enligt foreliggande forfarande framstallas vasentligt lattare och i renare form an enligt det kanda forfarandet genom upphettning av oxiforeningar med dikarbonsyror av samma slag som barnstenssyra och f0Ijande dehydrering. The bis-oxazolyl compounds can be prepared in the present process substantially lighter and in a purer form than in the known process by heating oxy compounds with dicarboxylic acids of the same kind as succinic acid and subsequent dehydration.

Foreningarna med formeln (2) kunna utom for de nedan namnda anvandningsandamalen aven anvandas for optisk vithetsforstarkning av lacker och massor, t. ex. nitrocellulosalacker eller filmer av acetylcellulosa och giva harvid Overraskande goda vithetsforstarkande effekter. The compounds of formula (2) can, in addition to the uses mentioned below, also be used for optical whitening reinforcement of lacquers and pulps, e.g. nitrocellulose lacquers or films of acetylcellulose and give surprisingly good whitening-enhancing effects.

I foljande exempel beteckna delar, savida icke nagot annat anmarkes, viktdelar och procent viktprocent. Temperaturerna aro angivna i celsiusgrader. In the following examples, parts, unless otherwise indicated, denote parts by weight and percent by weight. The temperatures are given in degrees Celsius.

Exempel 1. En smalta av 10 delar etylenglykol och 150 delar zinkklorid forsattes vid 155-160° mom ungefar 1/4 timme med 30 delar av acylaminoforeningen med formeln H,C—\/ —NH—C—CH=CH—C—HN—\/—CH, 00 och omrores ytterligare 10 timmar vid 160-165°. Man tillsatter droppvis 600 delar kallt vatten, varvid temperaturen far sjunka. Darefter tillsdtter man koneentrerad saltsyra till sur reaktion. Man omrtir ytterligare 1 timme vid ungefar ^/0 C—CH H,C i form av ljusa kristaller, vilka smalta vid 183184°. Losningen i dioxan fluorescerar blaaktigt. Om man ersatter de 30 delarna av den ovan- H,C \—OH 60°, franfiltrerar den utfallda pro dukten, tvattar den med vatten, tills filtratet reagerar neutralt och kiistalliserar den eventuellt ur dioxan. Man erhailer a,fl-di45-metylbensoxazoly1-(2)J-etylen med formeln =CH—C N namnda acylforeningen med foreningen med formeln CH, H0—/\ H,CNr-NH—C—CH=CH—C—HN— —CH, 00 erhaller man a,fl-di-[5,7-dimetylbensoxazoly1-(2)1-etylen med formeln CH,CH, J\ 0 %\// C—CH=CH—C som liar liknande egenskaper. '1\1 — —3 De harvid som utgangsamnen anyanda acylforeningarna kunna framstdllas pa foljande sdtt: En lOsning av 123 delar 1-amino-2-oxi-5-metylbensen i 1200 delar klorbensen forsattes droppvis under omroring och utestangande av luft vid 125-130° inom 1 timme med 76,5 delar fumarsyradiklorid och Mlles latt kokande i ytterligare 6 timmar. Man later blandningen svalna, franfiltrerar kondensationsprodukten och tvattar denna med klorbensen, alkohol och vatten. Det filtrerade materialet loses vidi utspadd nat- 143C riumhydroxidlosning, losningen filtreras och den gula kondensationsprodukten utfalles med atspadd saltsyra, franfiltreras, tvdttas med vatten och torkas. Kristalliserad ur vattenhaltig dimetylformamid smdlter den vid 255°. Kondensationen kan dven genomforas i m-xylen. Example 1. A melt of 10 parts of ethylene glycol and 150 parts of zinc chloride was continued at 155 DEG-160 DEG C. for about 1/4 hour with 30 parts of the acylamino compound of the formula H, C - \ / - CH .00 and stirred for a further 10 hours at 160-165 °. 600 parts of cold water are added dropwise, whereby the temperature is allowed to drop. Concentrated hydrochloric acid is then added to the acidic reaction. The mixture is stirred for a further 1 hour at about C The solution in dioxane fluoresces bluish. If one replaces the 30 parts of the above H, C There is obtained α, β-di45-methylbenzoxazolyl- (2) J-ethylene of the formula = CH-CN named acyl compound with the compound of the formula CH, HO - / —CH The starting materials as the other acyl compounds can be prepared as follows: A solution of 123 parts of 1-amino-2-oxy-5-methylbenzene in 1200 parts of chlorobenzene was continued dropwise with stirring and expelling air at 125 DEG. 130 ° within 1 hour with 76.5 parts of fumaric acid dichloride and Mlles lightly 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 in dilute sodium hydroxide solution, the solution is filtered and the yellow condensation product is precipitated with dilute hydrochloric acid, filtered off, washed with water and dried. Crystallized from aqueous dimethylformamide, it melts at 255 °. The condensation can then also be carried out in m-xylene.

Ora man ersatter de 123 delarna 1-amino-2-oxi5-metylbensen med den ekvimolekyldra mangden 1-amino-2-oxi-3,5-dimetylbensen, erhaller man foreningen med formeln: CH3 Ho-)\ OH TLC—/ —NH—C—CH= CH C HN \ \/ 0 CH3 Kondensationen kan aven genomforas i isattika. Exempel 2. 90 delar av foreningen med formeln "OHHO /—NH—C—CH= CH— C—FIN- \/ 0Oil skttas till en 160-168' varm smdlta av 30 delar vatten och 450 delar zinkklorid inom 1/4 till 1/2 timme och omriiras sedan ytterligare 6 timmar vid denna temperatur. Darefter tillfor man droppvis 450 delar vatten, varvid temperaturen far sjunka, och omror vid 90-100°, tills en homogen laming bildas, och hailer denna losning vid 50-70° till 900 delar vatten och 60 delar koncentrerad saltsyra. Man omror 1 timme, filtrerar, tvdttar med varmt vatten, tills filtratet är fdrglost och neutralt, samt torkar vid 90-100°. Man erhaller den kdnda a-9-[bensoxazoly1-(2)1-etylenen med formeln: C—CH=CH—C \/\17\N/ som after omkristallisering ur dioxan smaller vid 246-247° och lost i alkohol fluorescerar starkt blaaktigt i ultraviolett ljus. By replacing the 123 parts of 1-amino-2-oxy-5-methylbenzene with the equimolecular amount of 1-amino-2-oxy-3,5-dimethylbenzene, the compound of the formula is obtained: CH3 Ho -) \ OH TLC— / —NH —C — CH = CH C HN \ \ / 0 CH3 The condensation can also be carried out in glacial acetic acid. Example 2. 90 parts of the compound of the formula "OHHO / —NH — C — CH = CH— C — FIN- 1/2 hour and then stirred for a further 6 hours at this temperature, then 450 parts of water are added dropwise, the temperature is allowed to drop, and stirred at 90-100 °, until a homogeneous laming is formed, and this solution is heated at 50-70 ° to 900 parts of water and 60 parts of concentrated hydrochloric acid, stirring for 1 hour, filtering, washing with warm water until the filtrate is completely neutral, and drying at 90 DEG-100 DEG C. The cated a-9- [benzoxazoly1- ) 1-ethylene of the formula: C-CH = CH-C

Om man ersdtter utgangsprodukterna med an-given formel med acylforeningen med formeln: OH /\ NH—CO CH=CHCO FIN- erhaller man dibensoxazolen med formeln: \ 0 \ /\v/r0 IC—CH =CH—C(1) —NH—C—CH=CH—C—NH- \/IIil\/ 00 kan framstdllas pa foljande Ott: En suspension av 58 delar fumarsyra i 600 delar o-diklorbensen forsdttes droppvis vid 160-165° inom 3-4 timmar och under god omroring med 131 delar tionylklorid. Man erhaller en losning, ur Aiken eventuellt fortfarande narvarande tionylklorid avldgsnas genom omroring vid ungefdr 150°. Under utestangande av luft avkyler man till ungefar 110°, tillsdtter 104 delar 1-amino-2-oxibensen och °milk 8 timmar vid 140-150°, varvid den gronskiftande gula, fasta kondensationsproduk ten utfalles till storre delen. o-diklorbensen avdestilleras med anga, aterstoden franfiltreras, tvattas med varmt vatten och torkas. Kondensationsprodukten utgor ett gronskiftande gult pulver, som är losligt i utspddd natriumhydroxidlosning och kan omfdllas med syra. Den nya produkten smdlter vid 262°. Replacing the starting materials of the indicated formula with the acyl compound of the formula: OH / \ NH-CO CH = CHCO FIN- gives the dibenzoxazole of the formula: \ 0 \ / \ v / r0 IC-CH = CH-C (1) - NH-C-CH = CH-C-NH- good stirring with 131 parts of thionyl chloride. A solution is obtained, from which even the thionyl chloride still present is removed by stirring at about 150 °. With the exclusion of air, it is cooled to about 110 °, 104 parts of 1-amino-2-oxybenzene and milk are added for 8 hours at 140-150 °, the greenish-yellow solid condensation product precipitating out for the most part. The o-dichlorobenzene is distilled off with steam, the residue is filtered off, washed with hot water and dried. The condensation product is a greenish yellow powder which is soluble in dilute sodium hydroxide solution and can be filled with acid. The new product melts at 262 °.

Pa analogt satt kan den som utgangsamne anvanda acylforeningen (I) framstallas. In an analogous manner, the starting material using the acyl compound (I) can be prepared.

I N •/\C1 som har liknande egenskaper. In N • / \ C1 which have similar properties.

Den som utgangsamne anvanda acylfOreningen med formeln 4— — Exempel 3. Man f &far sasom beskrivits i exempel 1 men anvander 30 delar av foreningen med formeln —CO—HN- \% eller 30 delar av foreningen med formeln r"—OH HC--CH HO—/Ni IIII1I 1-13C— II—NH—C O—C C—C 0 —HN\,/ -4 I—CH, \/ \ / 0 De salunda erhallna foreningarna med formlerna "70 \/0 \ C—N/ \c \/\Ni ha liknande egenskaper som de i fOregaende exempel beskrivna dioxazolforeningarna. The starting material using the acyl compound of formula 4 - Example 3. The procedure is as described in Example 1 but using 30 parts of the compound of the formula -CO-HN- \% or 30 parts of the compound of the formula r CH HO— / Ni IIII1I 1-13C— II — NH — CO — CC — C 0 —HN \, / -4 I — CH, \ / \ / 0 N / \ c \ / \ You have similar properties to the dioxazole compounds described in the above examples.

De som utgangsamnen anvanda acylforeningarna kunna framstallas pa foljande Ott: 109 delar 1-amino-2-oxibensen resp. 123 delar 1-amino-2-oxi-5-metylbensen i 1200 delar klorbensen fOrsattas droppvis vid 125-130° Mom en timme med en losning av 101,5 delar tereftalsyra- CH—CH 0 och /\i/°[ ! C—C C—C diklorid resp. 96,5 delar furandikarbonsyraklorid i 200 delar klorbensen och kokas darefter forsiktigt ytterligare 6 timmar. The acyl compounds used as starting materials can be prepared as follows: 109 parts of 1-amino-2-oxybenzene resp. 123 parts of 1-amino-2-oxy-5-methylbenzene in 1200 parts of chlorobenzene are added dropwise at 125-130 ° Mom for one hour with a solution of 101.5 parts of terephthalic acid-CH-CH 2 and / C-C C-C dichloride resp. 96.5 parts of furandicarboxylic acid chloride in 200 parts of chlorobenzene and then boil 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.

Exempel 4. 10 delar av foreningen med formeln .1 CH,C--NH-0C—CH=CH-0C—HN—„— H, sattas under kylning till 100 delar 21-procentig oleum, upphettas Mom ungefar 2 timmar till 115° och halles 3 timmar vid 115-120°. Example 4. 10 parts of the compound of the formula .1 CH, C - NH-OC-CH = CH-OC-HN - ° and kept for 3 hours at 115-120 °.

Efter avkylning hailer man blandningen i isvatten, tillsatter natriumklorid, filtrerar den utfallda sulfonsyran och tvattar den med natriumkloridlosning. After cooling, the mixture is soaked in ice water, sodium chloride is added, the precipitated sulfonic acid is filtered off and washed with sodium chloride solution.

Det filtrerade materialet omrores med vatten vid 60-80°, neutraliseras med natriumhydrmdd och filtreras eventuellt fran en ringa mangd fasta fororeningar. Filtratet indunstas till torrhet. The filtered material is stirred with water at 60-80 °, neutralized with sodium hydride and optionally filtered from a small amount of solid impurities. The filtrate is evaporated to dryness.

Det erhallna natriumsaltet av a4-di-[metyl bensoxazoly1-(2)-etylendisulfonsyra är losligt i vatten med blaaktig fluorescens. The resulting sodium salt of α4-di- [methylbenzoxazolyl- (2) -ethylenedisulfonic acid is soluble in water with a bluish fluorescence.

Man erhaller en likaledes fluorescerande sullensyra, am man som utgangsamne i stallet for acylforeningen med den ovannamnda formeln anvander fiireningen med formeln N/2—NH-0C—CH=CH—CO—HN Exempel 5. 12,6 delar av diacylfareningen med formeln "\—OHHO—" H,C \/CH, H,C—C j—NH-0C—CH=CH—CO—HN-1„—C—CH, / \/N/ \ HC'CH2 sattas till en till 160-170° uppvarmd smalta av 4 delar zinkklorid och omrores 3 timmar vid denna temperatur. Vid 100° tillsatter man darefter 60 delar vatten och omror, tills en homogen losning bildas. Darefter installer man lasningen pa kongosur reaktion med koncentrerad saltsyra och mitr vidare en. halvtimme vid 50°, filtrerar, tvattar med vatten av 50°, tills filtratet reagerar neutralt, och torkar. Efter omkristallisering ur dioxanvatten smaller den gula kondensationsprodukten med formeln: — — /o\/\ H,CCH, C—CH =CH—C H3C—C—,-C-CH3 H,C/ \/\/N\CH, vid 157-158°. A similarly fluorescent sulfuric acid is obtained, starting from the compound of the formula N / 2 -NH-OC-CH = CH-CO-HN as the starting material instead of the acyl compound of the above formula. Example 5. 12.6 parts of the diacyl compound of the formula " \ —OHHO— "H, C \ / CH, H, C — C to 160-170 ° heated melt of 4 parts of zinc chloride and stir for 3 hours at this temperature. At 100 °, 60 parts of water and stirrer are then added until a homogeneous solution is formed. The installation is then installed on the congo acid reaction with concentrated hydrochloric acid and further measured. half an hour at 50 °, filter, wash with water of 50 °, until the filtrate reacts neutrally, and dries. After recrystallization from dioxane water, the yellow condensation product of the formula: - - / o \ / \ H, CCH, C — CH = CH — C H3C — C at 157-158 °.

Den som utgangsamne anvanda diacylforeningen kan framstallas pa foljande salt: En lOsning av 16,5 delar 1-amino-2-oxi-5- tertiarbutylbensen i 80 delar klorbensen forsattes droppvis under omroring och utestangande av luft vid 125-10 inom 10 minuter med en lbsning av 7,6 delar fumarsyradiklorid i 20 delar klor bensen. Darefter kokar man 4 timmar under itierflodskylning, later blandningen svalna och filtrerar. Den gula kondensationsprodukten smalter efter omkristallisering vid 140-143°. The starting material using the diacyl compound can be prepared on the following salt: A solution of 16.5 parts of 1-amino-2-oxy-5-tertiarbutylbenzene in 80 parts of chlorobenzene was added dropwise with stirring and quenching of air at 125-10 within 10 minutes with a Dissolution of 7.6 parts of fumaric acid dichloride in 20 parts of chlorine benzene. Then boil for 4 hours under itier river cooling, allow the mixture to cool and filter. The yellow condensation product melts after recrystallization at 140-143 °.

Exempel 6. En smalta av 150 delar zinkklorid och 10 delar vatten fOrsattes vid 155-1600 under en kvarts timme med 27 delar av acylforeningen med formeln 0 0 H,N—\/—CH, 2 HCI och omrores 8 timmar vid samma temperatur. Darefter tillsatter man droppvis 250 delar vatten, varunder temperaturen far sjunka till 100°, och installer losningen darefter pa kongosur reaktion vid 50° med koncentrerad saltsyra. Darefter omrores ytterligare 1 timme vid 50-60°, filtreras och tvattas till neutral reaktion. Man erhaller pa sa satt a,13-di-{5-mety1bensoxazo1y1-(2)}-etylen. Den ur metylenklorid-metanol omkristalliserade produkten smalter vid 182-183°. Example 6. A melt of 150 parts of zinc chloride and 10 parts of water was added at 155-1600 for a quarter of an hour with 27 parts of the acyl compound of the formula 0 H, N - / CH - 2 HCl and stirred for 8 hours at the same temperature. Then 250 parts of water are added dropwise, during which the temperature is allowed to drop to 100 °, and the solution is then installed on a congo acid reaction at 50 ° with concentrated hydrochloric acid. It is then stirred for a further 1 hour at 50-60 °, filtered and washed until neutral. There is thus obtained a, 13-di- {5-methylbenzoxazolyl- (2)} -ethylene. The product recrystallized from methylene chloride-methanol melts at 182-183 °.

Den som utgangsamne anyanda estern med ovansthende formel kan framstallas pa folj ande satt: En uppslamning av 12,3 delar 1-amino-2-oxi-5- metylbensen i 100 delar bensen forsattes droppvis under omroring vid rumstemperatur under 2 minuter med 7,6 delar fumarsyradiklorid. Efter 10 minuter franfiltreras fanning, tvattas den med 30 delar bensen och torkas. Den ljusgula kondensationsprodukten smalter vid 218°. The starting ester of the above formula can be prepared as follows: A slurry of 12.3 parts of 1-amino-2-oxy-5-methylbenzene in 100 parts of benzene was added dropwise with stirring at room temperature for 2 minutes with 7.6 parts of fumaric acid dichloride. After 10 minutes, the fanning is filtered off, washed with 30 parts of benzene and dried. The light yellow condensation product melts at 218 °.

Exempel 7. 10 delar av acylfOreningen med for-mein H0—/\ />—CO—HN- -NH-0C— / omrOras vid 170-17° med 100 delar o-diklorbensen. Darefter tillsattes 0,1 del p-toluensulfonsyra och det hela Mlles ungef Sr 12 timmar vid en temperatur av 170-175°, varvid en losning bildas efter hand. Man later blandningen svalna, franfiltrerar bildad 1,4-digbensoxazoly1-(2')Fbensen, tvattar densamma med diklorbensen, alkohol och vatten och torkar den. Example 7. 10 parts of the acyl compound with the form H0- / Then 0.1 part of p-toluenesulfonic acid and the whole of Mlles were added for about 12 hours at a temperature of 170-175 °, whereby a solution formed gradually. The mixture is allowed to cool, the 1,4-digbenzoxazolyl- (2 ') benzene formed is filtered off, washed with dichlorobenzene, alcohol and water and dried.

Pa liknande salt kan man av acylforeningen med formeln HO /\ H2C—N/—NH-0C—CH=CH—00—HN—/ —CH, N erhalla a„8-di-[5-metylbensoxazoly1-(2)J-etylen. On a similar salt one can obtain from the acyl compound of the formula HO / -ethylene.

Claims (2)

Patentanspra.k:Patentanspra.k: 1. Forfarande I Or framstallning av heterocykEska foreningar, kannetecknat &ray, att acylforeningar med formeln: 0 0 I!II N/NH—C—R—C—NH /XX \(1) II 0 0 van i X betecknar en vateatom, en kloratom eller en alkylgrupp med 1-4 kolatomer, Z betecknar en vateatom eller en metylgrupp och R betecknar resten —CH = CH—, resten\— eller HO/\ eller med formeln: XX\ NH, H,N\ /X zX/\ on/\ (la) 6— — resten HC-- CH, behandlas med sadana medel, \ / 0 som ha formdga att ur angivna acylfbreningar avspjfilka vatten och eventuellt infora sulfonsyragrupper, varvid bildas foreningar med formeln: X \y,N\ \/X N X C—R—C(2) YX/\ 0/ van i X och R ha angiven betydelse och Y betecknar en vdteatom, en metylgrupp eller en sulfonsyragrupp.1. Process I In the preparation of heterocyclic compounds, it can be characterized in that acyl compounds of the formula: N / NH-C — R — C — NH / XX \ (1) II 0 0 van i X represent a hydrogen atom, a chlorine atom or an alkyl group having 1-4 carbon atoms, Z represents a hydrogen atom or a methyl group and R represents the radical -CH = CH-, the radical \ - or HO / \ or of the formula: XX \ NH, H, N \ / X zX / \ on / \ (la) 6— - the residue HC-- CH, are treated with such agents, \ / 0 which are capable of reflecting water from the indicated acyl compounds and possibly introducing sulfonic acid groups, whereby compounds of the formula: X \ y, N are formed. (2) YX / \ 0 / van in X and R have the indicated meaning and Y represents a hydrogen atom, a methyl group or a sulfonic acid group. 2. FOrfarande enligt patentansprdket 1, kalinetecknat ddrav, att man sasom vattenavspjalkande medel anvander zinkklorid. Anfiirda publikationer:2. A process according to claim 1, characterized in that zinc chloride is used as the water-repellent agent. Cited publications:
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