NO121015B - - Google Patents
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- NO121015B NO121015B NO169775A NO16977567A NO121015B NO 121015 B NO121015 B NO 121015B NO 169775 A NO169775 A NO 169775A NO 16977567 A NO16977567 A NO 16977567A NO 121015 B NO121015 B NO 121015B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 18
- 125000004442 acylamino group Chemical group 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000007858 starting material Substances 0.000 claims description 10
- 239000011592 zinc chloride Substances 0.000 claims description 9
- 235000005074 zinc chloride Nutrition 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 150000002790 naphthalenes Chemical class 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 238000004061 bleaching Methods 0.000 claims description 2
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 150000003855 acyl compounds Chemical class 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000000155 melt Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 238000001953 recrystallisation Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000007859 condensation product Substances 0.000 description 6
- 150000004982 aromatic amines Chemical class 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- -1 aliphatic dicarboxylic acids Chemical class 0.000 description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 230000007717 exclusion Effects 0.000 description 4
- 239000001630 malic acid Substances 0.000 description 4
- 235000011090 malic acid Nutrition 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000006798 ring closing metathesis reaction Methods 0.000 description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000005001 aminoaryl group Chemical group 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical class ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- RNHDAKUGFHSZEV-UHFFFAOYSA-N 1,4-dioxane;hydrate Chemical compound O.C1COCCO1 RNHDAKUGFHSZEV-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- FHHZOYXKOICLGH-UHFFFAOYSA-N dichloromethane;ethanol Chemical compound CCO.ClCCl FHHZOYXKOICLGH-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Substances [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 238000009994 optical bleaching Methods 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B7/00—Roofs; Roof construction with regard to insulation
- E04B7/08—Vaulted roofs
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
- E04C3/00—Structural elongated elements designed for load-supporting
- E04C3/38—Arched girders or portal frames
- E04C3/40—Arched girders or portal frames of metal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24149—Honeycomb-like
- Y10T428/24157—Filled honeycomb cells [e.g., solid substance in cavities, etc.]
Description
Framgangsmåte til framstilling av optisk blekende heterocykliske forbindelser. Process for the preparation of optically bleaching heterocyclic compounds.
Det ble funnet at optiske blekende It was found that optical bleaching
heterocykliske forbindelser, f. eks. slike som heterocyclic compounds, e.g. such as
det i og for seg kjente a, /?-[benzoksazolyl-(2)]-etylen, eller generelt forbindelser med the per se known a, /?-[benzoxazolyl-(2)]-ethylene, or generally compounds with
sammensetningen the composition
hvori Rq og R2 hver betyr en på den angitte måte med heteroringen kondensert arylrest og R3 betyr et broledd, hvor begge kullstoffatomer i heteroringen er forbundet med hverandre ved hjelp av en alifatisk - C = C-binding kan framstilles på fordelaktig måte når man behandler acylaminoforbindelser med formelen hvori R, og R2 hver betyr en arylrest og - OC - R i - CO - resten av en alifatisk oksydikarbonsyre hvis - CO-grupper er sammenknyttet med hverandre over en bro med to kullstoffatomer av hvilke minst ett er bundet til en oksygruppe og HO-grup-pene hver står i nabostilling til - NH-gruppen, med vannavspaltende midler. Man kommer til de her som utgangsstoffer tjenende forbindelser med formel (1) når man kondenserer alifatiske dikarbonsyrer, hvis karbonsyregrupper er forbundet med hverandre ved hjelp av en gruppe av to kullstoffatomer av hvilke minst ett er bundet til en oksygruppe, ved begge karbonsyregrupper med primære arylaminer, som i nabostilling til aminogruppen inneholder en oksygruppe. Som dikarbonsyrer av den omtalte sammensetning kommer f. eks. vinsyre, men særlig eplesyre, i betraktning, og av disse syrer får man således acylaminoforbindelser av den ovenfor angitte sammensetning, hvis rest - R4 - tilsvarer formelen in which Rq and R2 each mean an aryl residue fused with the heteroring in the indicated manner and R3 means a bridge link, where both carbon atoms in the heteroring are connected to each other by means of an aliphatic - C = C bond can be produced advantageously when treating acylamino compounds with the formula in which R, and R2 each means an aryl residue and - OC - R i - CO - the residue of an aliphatic oxydicarboxylic acid whose - CO groups are connected to each other via a bridge of two carbon atoms of which at least one is bonded to an oxy group and The HO groups each stand in a neighboring position to the - NH group, with water splitting agents. The compounds of formula (1) used here as starting materials are obtained when condensing aliphatic dicarboxylic acids, whose carboxylic acid groups are connected to each other by means of a group of two carbon atoms of which at least one is bound to an oxy group, at both carboxylic acid groups with primary arylamines , which in the adjacent position to the amino group contains an oxy group. As dicarboxylic acids of the mentioned composition, e.g. tartaric acid, but especially malic acid, into consideration, and from these acids one thus obtains acylamino compounds of the above-mentioned composition, whose residue - R4 - corresponds to the formula
De primære arylaminer som skal kondenseres med de alifatiske dikarbonsyrer inneholder i nabostilling til den til et aryl-kullstoffatom bundne aminogruppe en oksygruppe. Det kan f. eks. anvendes nafta-liner, som inneholder aminogruppen og oksygruppen i 1,2-stilling eller 2,1-stilling. Med fordel anvender man arylaminer fra benzolrekken, f. eks. slike, som oppviser en eneste benzolkjerne som dog ved siden av o-oksyaminogrupperingen kan inneholde videre substituenter, f. eks. laveremole-kylære alkyl- eller alkoksygrupper, slik som etyl-, metyl-, etoksy- eller metoksy-grupper, halogenatomer, slike som klor, nitrogrupper. Som eksempler skal nevnes følgende o-oksyaminoarylforbindelser: The primary arylamines to be condensed with the aliphatic dicarboxylic acids contain an oxy group adjacent to the amino group bound to an aryl carbon atom. It can e.g. naphthalenes are used, which contain the amino group and the oxy group in the 1,2-position or 2,1-position. Arylamines from the benzene series are advantageously used, e.g. such, which exhibit a single benzene nucleus which, however, next to the o-oxyamino grouping may contain further substituents, e.g. lower molecular alkyl or alkoxy groups, such as ethyl, methyl, ethoxy or methoxy groups, halogen atoms, such as chlorine, nitro groups. The following o-oxyaminoaryl compounds should be mentioned as examples:
1 - amino-2-oksy naftalin, l-amino-2-oksybenzol, l-amino-2-oksy-5-metylbenzol, l-amino-2-oksy-4-metylbenzol, l-amino-2-oksy-3,5-dimetylbenzol, l-amino-2-oksy-5-tertiærbutylbenzol, l-amino-2-oksy-5-metoksybenzol, l-amino-2-oksy-4- eller -5-nitrobenzol, l-amino-2-oksyr5-klorbenzol, 1 - amino-2-oxy naphthalene, l-amino-2-oxybenzene, l-amino-2-oxy-5-methylbenzene, l-amino-2-oxy-4-methylbenzene, l-amino-2-oxy-3 ,5-dimethylbenzene, l-amino-2-oxy-5-tertiarybutylbenzene, l-amino-2-oxy-5-methoxybenzene, l-amino-2-oxy-4- or -5-nitrobenzene, l-amino-2 -oxyr5-chlorobenzene,
l-amino-2-oksy-3,5-diklorbenzol. 1-amino-2-oxy-3,5-dichlorobenzene.
For framstilling av asymmetriske acylaminoforbindelser kan de alifatiske dikarbonsyrer kondenseres med to forskjel-lige aminoarylforbindelser av den angitte sammensetning og i de således erholdte forbindelser av formel (2) er R3 og R2 ikke de samme rester. Foreliggende framgangsmåte egner seg imidlertid framfor alt til framstilling av symmetriske forbindelser, dvs. slike med to like aminoarylrester, som man får når man kondenserer den alifatiske dikarbonsyre i molekylarforholdet 1 : 2 med et eneste arylamin, og som således tilsvarer formelen For the production of asymmetric acylamino compounds, the aliphatic dicarboxylic acids can be condensed with two different aminoaryl compounds of the specified composition and in the thus obtained compounds of formula (2) R3 and R2 are not the same residues. However, the present procedure is above all suitable for the production of symmetrical compounds, i.e. those with two identical aminoaryl residues, which are obtained when the aliphatic dicarboxylic acid is condensed in the molecular ratio 1:2 with a single arylamine, and which thus correspond to the formula
hvori Rx og R4 har den til å begynne med angitte betydning. wherein Rx and R4 have the meaning initially indicated.
For kondensasjonen kan det anvendes dikarbonsyrene som sådanne, således at det som regel ikke er nødvendig å omsette dem i form av egnede funksjonelle derivater, f. eks. i form av syreesteren, med arylaminer. Kondensasjonen utføres fordelaktig i nærvær av et inert organisk oppløsnings - middel. For dette kan det anvendes for-skjellige oppløsningsmidler, hvori begge utgangsstoffer er bestandige. Med fordel anvender man oppløsningsmidler med for-holdsvis høyt kokepunkt, f. eks. et slikt som ligger høyere enn 100°. Gode resultater fåes f. eks. med over 100° kokende oppløsnings-midler fra benzolrekken, slik som totuol, xyloler, kumol, klorbenzol, di- eller triklor-benzoler eller nitrobenzoler. For ikke å strekke ut omsetningstiden, unødvendig, anbefales det å arbeide ved temperaturer over 100°, men imidlertid skal man i al-minnelighet ikke gå over 200°. For the condensation, the dicarboxylic acids can be used as such, so that it is usually not necessary to convert them in the form of suitable functional derivatives, e.g. in the form of the acid ester, with arylamines. The condensation is advantageously carried out in the presence of an inert organic solvent. For this, different solvents can be used, in which both starting substances are stable. It is advantageous to use solvents with a relatively high boiling point, e.g. one that is higher than 100°. Good results are obtained e.g. with solvents boiling above 100° from the benzene range, such as totuol, xylenes, cumene, chlorobenzene, di- or trichlorobenzenes or nitrobenzenes. In order not to extend the turnover time unnecessarily, it is recommended to work at temperatures above 100°, but however you should not go above 200° as a general rule.
Etter foretatt omsetning kan acylaminoforbindelsene isoleres på vanlig i og for seg kjent måte fra reaksjonsblandingen. I mange tilfelle er de så tungt oppløselige i det anvendte oppløsningsmiddel at de eventuelt etter avkjølingen av blandingen faller ut i meget godt utbytte og renhet. After the reaction has taken place, the acylamino compounds can be isolated from the reaction mixture in a manner known per se. In many cases, they are so poorly soluble in the solvent used that they possibly precipitate out after cooling the mixture in very good yield and purity.
De således framstillbare acylamino-forbiridelser med formel (2) behandles med vannavspaltende midler, hvorved det på den ene siden finner sted en dobbelt ring-slutning under dannelse av oksazolringen og på den annen side en vannavspaltning i broleddet R3 under dannelse av en etylen-gruppe. Som vannavspaltende middel kommer f. eks. borsyre, propionsyre eller eddik-syre i betraktning. Som særlig hensiktsmessig vannavspaltende middel har sinkklorid vist seg å være. Ved behandling av acylaminoforbindelsene i en sinkklorid-smelte, som før opphetningen med fordel ennå tilsettes noe vann, lar den ønskede omsetning seg på enkel måte og med godt resultat utføre. Egnede temperaturer for vannavspaltningen ved hjelp av sinkklorid er f. eks. slike på 140—180°, fortrinnsvis ca. 160°. Etter avsluttet omsetning kan produktene på enkel måte ved tilsetning av vann til smeiten og ansyring av blandingen utskilles og skilles fra ved filtre-ring. For videre rensning kan man om-krystallisere dem fra egnede organiske oppløsningsmidler. Som videre vannavspaltende middel kan nevnes svovel-trioksyd, hensiktsmessig i form av oleum. Ved vannavspaltningen og ringslutningen ved hjelp av oleum finner det som regel sted ennå en sulfonering. The acylamino derivatives of formula (2) that can be prepared in this way are treated with water-splitting agents, whereby on the one hand a double ring closure takes place to form the oxazole ring and on the other hand a water splitting occurs in the bridge link R3 with the formation of an ethylene group . As a water-releasing agent, e.g. boric acid, propionic acid or acetic acid into consideration. Zinc chloride has proven to be a particularly suitable water-splitting agent. When treating the acylamino compounds in a zinc chloride melt, to which some water is advantageously added before heating, the desired reaction can be carried out in a simple way and with good results. Suitable temperatures for the water separation using zinc chloride are e.g. such at 140-180°, preferably approx. 160°. After completion of the reaction, the products can be easily separated by adding water to the mixture and acidifying the mixture and separated by filtration. For further purification, they can be recrystallized from suitable organic solvents. Sulfur trioxide, suitably in the form of oleum, can be mentioned as a further water-releasing agent. During the water splitting and ring closure with the help of oleum, a further sulphonation usually takes place.
Av de heterocykliske forbindelser som kan framstilles ifølge foreliggende framgangsmåte, er slike som broledd - R3 - inneholder en - CH = CH-gruppe delvis kjent. Nye er forbindelser med formelen Of the heterocyclic compounds that can be produced according to the present method, those whose bridge link - R3 - contains a - CH = CH group are partially known. New are compounds with the formula
hvori R1 og R2 hver betyr en på den angitte måte med heteroringen kondensert arylrest. Disse nye forbindelser fluorescerer i ultraviolett lys og kan anvendes for å oppnå optiske virkninger. Nye og som optiske blekemidler meget verdifulle forbindelser med formelen wherein R1 and R2 each mean an aryl residue fused to the heteroring in the manner indicated. These new compounds fluoresce in ultraviolet light and can be used to achieve optical effects. New and as optical brighteners very valuable compounds with the formula
hvori Rj og R2 hver betyr en på den angitte måte med heteroringen kondensert wherein R 1 and R 2 each mean one in the indicated manner with the heteroring fused
benzolrest, idet i det minste en av disse benzolringer som substituenter inneholder en laveremolekylar alkylgruppe, f .eks. en etylgruppe eller særlig en metylgruppe. Alkylgruppene befinner seg f. eks. i 5-stilling av benzoksazolrestene. benzene residue, with at least one of these benzene rings as substituents containing a lower molecular weight alkyl group, e.g. an ethyl group or especially a methyl group. The alkyl groups are found, e.g. in the 5-position of the benzoxazole residues.
Generelt skal fremheves at forbindel-sene med formel (1) lar seg framstille vesentlig lettere og renere ifølge foreliggende forbindelse enn ifølge de kjente framgangsmåter ved opphetning av oksy-forbindelser med dikarbonsyrer av typen ravsyre og etterfølgende dehydrogenering eller ved sammensmeltning av oksyaminoarylforbindelser med umettede dikarbonsyrer. In general, it should be emphasized that the compounds with formula (1) can be produced significantly easier and cleaner according to the present compound than according to the known methods by heating oxy compounds with dicarboxylic acids of the succinic acid type and subsequent dehydrogenation or by fusing oxyaminoaryl compounds with unsaturated dicarboxylic acids.
I de følgende eksempler betyr delene, In the following examples, the parts mean,
såfremt intet annet bemerkes, vektsdeler, prosentene vektsprosent, og temperaturene er, slik som i den foregående beskrivelse, angitt i Celsiusgrader. unless otherwise noted, parts by weight, percentages by weight, and temperatures are, as in the preceding description, given in degrees Celsius.
Eksempel 1: Example 1:
En smelte av 10 deler vann og 150 deler sinkklorid tilsettes ved 160 til 170° 30 deler av acylforbindelsen med formelen og deretter holdes blandingen 10 til 18 timer ved den angitte temperatur. Deretter tildryppes idet man lar temperaturen synke 600 deler kaldt vann. Etter tilsetning av saltsyre inntil sur reaksjon rører man en time ved 80 til 100°, filtrerer fra det erholdte produkt, vasker det med vann, tørker det og krystalliserer det fra dioksan. Man får det kjente a, /?-di-[benzoksazolyl-(2)]-etylen med formelen som et krystallinsk pulver, som, omkrystal-lisert fra dioksan, smelter ved 242 til 245°. Erstatter man de 30 deler av acylforbindelsen med slike med formelen To a melt of 10 parts of water and 150 parts of zinc chloride is added at 160 to 170° 30 parts of the acyl compound of the formula and then the mixture is kept for 10 to 18 hours at the specified temperature. 600 parts of cold water are then added drop by drop while allowing the temperature to drop. After adding hydrochloric acid until an acidic reaction, the mixture is stirred for one hour at 80 to 100°, the product obtained is filtered, washed with water, dried and crystallized from dioxane. The known α, /?-di-[benzoxazolyl-(2)]-ethylene is obtained with the formula as a crystalline powder, which, recrystallized from dioxane, melts at 242 to 245°. If you replace the 30 parts of the acyl compound with those with the formula
får man a, ^-di-[(5)-klorbenzoksazolyl-(2)]-etylen, som har liknende egenskaper og etter omkrystallisasjon fra dioksan smelter ved 262 til 263°. a, ^-di-[(5)-chlorobenzoxazolyl-(2)]-ethylene is obtained, which has similar properties and after recrystallization from dioxane melts at 262 to 263°.
De acylforbindelser som her tjener som utgangsstoffer lar seg framstille som følger: The acyl compounds that serve as starting materials here can be prepared as follows:
109 deler l-amino-2-oksybenzol og 109 parts l-amino-2-oxybenzene and
67 deler eplesyre utrøres lett kokende med 67 parts of malic acid are stirred in while boiling
550 deler klorbenzol, under utelukkelse 550 parts chlorobenzene, under exclusion
av luft i 8 timer, hvorved det dannede vann avdestilleres sammen med noe klorbenzol. Deretter lar man avkjøle, og det erholdte kondensasjonsprodukt f raf Utreres og vaskes med klorbenzol, alkohol og vann. For å fjerne ikke omsatte utgangsstoffer behandles filtrermaterialet med fortynnet saltsyre, filtreres, vaskes med vann inntil fil- of air for 8 hours, whereby the water formed is distilled off together with some chlorobenzene. It is then allowed to cool, and the condensation product obtained from raf is extracted and washed with chlorobenzene, alcohol and water. To remove unreacted starting materials, the filter material is treated with dilute hydrochloric acid, filtered, washed with water until
tratet reagerer nøytralt og tørkes. Det erholdte produkt fra den første formel i dette eksempel og som kan fåes rent ved gjentatt oppløsning i fortynnet natrium-hydroksydoppløsning danner et lyst pulver, som er oppløselig i alkohol eller dioksan. Sm.p. 165°. the funnel reacts neutrally and is dried. The product obtained from the first formula in this example and which can be obtained pure by repeated dissolution in dilute sodium hydroxide solution forms a bright powder, which is soluble in alcohol or dioxane. Sm.p. 165°.
Erstatter man de 109 deler l-amino-2-oksybenzol med den ekvimolekylare mengde l-amino-2-oksy-5-klorbenzol, får man acylforbindelsen med den tredje formel i foreliggende eksempel, og som har liknende egenskaper. If you replace the 109 parts of 1-amino-2-oxybenzene with the equimolecular amount of 1-amino-2-oxy-5-chlorobenzene, you get the acyl compound with the third formula in the present example, which has similar properties.
Eksempel 2: Example 2:
Fra forbindelsen med formelen From the connection with the formula
framstilles ved hjelp av sinkklorid ifølge metylbenzoksazolyl-(2)]-etylen med forme-det som er angitt i eksempel 1 a, /?-di-[5- len som etter omkrystallisasjon fra metylen-kloridalkohol smelter ved 183—184°. Den acylaminoforbindelse som herved tjener som utgangsstoff kan fåes som føl-ger: 369 deler l-amino-2-oksy-5-metyl-benzol, 208 deler eplesyre og 2000 deler klorbenzol utrøres lett kokende under utelukkelse av luft i 8 timer, hvorved man lar reaksjonsvannet avdestillere. Deretter lar man avkjøle, frafiltrerer det erholdte kondensasjonsprodukt, vasker med etanol og benzol og tørker. Man får acylforbindelsen som lyst, krystallinsk pulver med sm.p. 230°. Anvender man i ovenstående eksempel i stedet for l-amino-2-oksy-5-metylbenzol l-amino-2-oksy-4-metylbenzol, så får man etter ringslutningen ved hjelp av sinkklorid a, /3-di-[6-metylbenzoksazolyl-(2)]-etylen med formelen is prepared using zinc chloride according to methylbenzoxazolyl-(2)]-ethylene of the form indicated in example 1 a, ?-di-[5-lene which, after recrystallization from methylene chloride alcohol, melts at 183-184°. The acylamino compound that serves as a starting material can be obtained as follows: 369 parts of 1-amino-2-oxy-5-methyl-benzene, 208 parts of malic acid and 2000 parts of chlorobenzene are stirred at a gentle boil under exclusion of air for 8 hours, whereby allow the water of reaction to distill off. It is then allowed to cool, the condensation product obtained is filtered off, washed with ethanol and benzene and dried. The acyl compound is obtained as a light, crystalline powder with m.p. 230°. In the above example, instead of l-amino-2-oxy-5-methylbenzene, l-amino-2-oxy-4-methylbenzene is used, then after the ring closure with zinc chloride a, /3-di-[6- methylbenzoxazolyl-(2)]-ethylene with the formula
som ved omkrystallisasjon fra metylen-klorid-etanol smelter ved 190 til 191°. which on recrystallization from methylene chloride ethanol melts at 190 to 191°.
Eksempel 3: Example 3:
En smelte av 10 deler vann og 150 deler sinkklorid tilsettes ved 160 til 170° 20 deler av acylforbindelsen med formelen Heretter holdes blandingen 12 timer ved 160—170° Deretter tildryppes idet man lar temperaturen synke 600 deler kaldt vann. Etter tilsetning av saltsyre inntil sur reaksjon, rører man en time ved 80 til 100°, filtrerer fra det erholdte produkt, vasker det og tørker det. Man får et svakt grønn-liggult farget pulver, som er uoppløselig i vann og som har den antatte formel I henholdsvis A melt of 10 parts of water and 150 parts of zinc chloride is added at 160 to 170° 20 parts of the acyl compound with the formula The mixture is then kept for 12 hours at 160-170° Then 600 parts of cold water are added drop by drop while allowing the temperature to drop. After adding hydrochloric acid until an acidic reaction, the mixture is stirred for one hour at 80 to 100°, the product obtained is filtered, washed and dried. A weak greenish-yellow colored powder is obtained, which is insoluble in water and which has the assumed formula I respectively
Den acylforbindelse som tjener som utgangsstoff lar seg framstille som følger: 75 deler vinsyre og 109 deler 1-amino-2-oksybenzol utrører lett kokende i 1000 deler klorbenzol ved 130 til 135° under utelukkelse av luft i 8 timer, hvorved det dannede vann avdestilleres fortløpende. Man lar avkjøle, filtrerer fra kondensasjonsproduktet og vasker det med klorbenzol, alkohol og vann. For å fjerne ikke omsatte utgangsstoffer, behandles filter-materialet med fortynnet saltsyre, filtreres og vaskes nøytralt med vann og tørkes. Etter omkrystallisasjon fra alkohol-vann, smelter det erholdte kondensasjonsprodukt med den til å begynne med i dette eksempel angitte formel ved 242 til 243°. settes til en til 160—170° oppvarmet smelte av 2 deler vann og 35 deler sinkklorid og røres i 3 timer ved denne temperatur. Deretter tildrypper man ennå i det man lar temperaturen synke 60 deler vann og rører ved 90 til 100° inntil det oppstår en homo- gen oppløsning. I tilslutning til dette stilles kongosur med konsentrert saltsyre, videre-røres i en halv time ved 50°, filtreres ennå varmt, nøytralvaskes med vann ved 50° og tørkes. Reaksjonsproduktet med formelen The acyl compound which serves as starting material can be prepared as follows: 75 parts of tartaric acid and 109 parts of 1-amino-2-oxybenzene are stirred at a low boiling point in 1000 parts of chlorobenzene at 130 to 135° under exclusion of air for 8 hours, whereby the water formed is distilled off consecutively. Allow to cool, filter off the condensation product and wash it with chlorobenzene, alcohol and water. To remove unreacted starting substances, the filter material is treated with dilute hydrochloric acid, filtered and washed neutrally with water and dried. After recrystallization from alcohol-water, the obtained condensation product with the formula initially stated in this example melts at 242 to 243°. is added to a heated to 160-170° melt of 2 parts water and 35 parts zinc chloride and stirred for 3 hours at this temperature. Then, while allowing the temperature to drop, 60 parts of water are added drop by drop and stirred at 90 to 100° until a homogeneous gene resolution. In addition to this, Congo acid is added with concentrated hydrochloric acid, further stirred for half an hour at 50°, filtered while still hot, neutral washed with water at 50° and dried. The reaction product with the formula
får man etter omkrystallisasjon fra dioksan-vann i form av gule nåler med sm.p. 153 til 154°. is obtained after recrystallization from dioxane-water in the form of yellow needles with m.p. 153 to 154°.
Den acylforbindelse som tjener som utgangsstoff kan framstilles som følger: 16,5 deler l-amino-2-oksy-5-tertiærbutyl-benzol, 6,7 deler eplesyre, røres med 100 deler xylol under utelukkelse av luft i 6 timer med tilbakeløpskjøler, idet det dannede vann skilles fra med vannutskil-ler. Deretter avkjøles til romtemperatur, og The acyl compound which serves as starting material can be prepared as follows: 16.5 parts of 1-amino-2-oxy-5-tertiarybutyl-benzene, 6.7 parts of malic acid, stirred with 100 parts of xylol under exclusion of air for 6 hours with a reflux condenser, as the water formed is separated with a water separator. Then cool to room temperature, and
kondensasjonsproduktet f raf Utreres, etter-vaskes med xylol og tørkes. De erholdte the condensation product from raf is extracted, washed with xylol and dried. They obtained
fargeløse krystaller er oppløselige i dioksan og etanol og viser et smeltepunkt på 215 til 216°. colorless crystals are soluble in dioxane and ethanol and show a melting point of 215 to 216°.
Eksempel 5: Example 5:
10 deler av acylforbindelsen med formelen settes under avkjøling til 100 deler oleum med et svoveltrioksydinnhold på 24 %. Det hele opphetes innen to timer til 115° og holdes 3 timer ved 115 til i20°. Etter av-kjøling heller man på isvann, tilsetter natriumklorid, filtrerer fra den utskilte sulfonsyre og vasker den med natrium-kloridoppløsning. Nå utrøres filtermassen | med vann ved 60 til 80°, nøytraliseres med natriumhydroksydoppløsning, eventuelt frafiltreres fra små faste forurensninger, og filtratet inndampes til tørrhet. Det erholdte natriumsalt av «, /?-di-[5-metylbenzoksazolyl- (2) ] -etylen-disulf on-syre med formelen er oppløselig i vann med blålig fluorescens. På den angitte måte kan man også fra acylforbindelsen med formelen framstille a, /3-di-[benzoksazolyl-(2)-]-etylen-disulfonsyre med formelen 10 parts of the acyl compound with the formula is added under cooling to 100 parts of oleum with a sulfur trioxide content of 24%. The whole is heated within two hours to 115° and held for 3 hours at 115 to i20°. After cooling, ice water is poured, sodium chloride is added, the separated sulphonic acid is filtered off and it is washed with sodium chloride solution. Now the filter mass is stirred | with water at 60 to 80°, neutralized with sodium hydroxide solution, optionally filtered off from small solid impurities, and the filtrate evaporated to dryness. The obtained sodium salt of «, /?-di-[5-methylbenzoxazolyl-(2) ]-ethylene-disulfonic acid with the formula is soluble in water with bluish fluorescence. In the indicated manner, one can also from the acyl compound with the formula prepare a, /3-di-[benzoxazolyl-(2)-]-ethylene-disulfonic acid of the formula
hvis natriumsalt likeledes er oppløselig il vann med blålig fluorescens. whose sodium salt is likewise soluble in water with a bluish fluorescence.
I Eksempel 6: In Example 6:
17,2 deler av acylforbindelsen med formelen 17.2 parts of the acyl compound with the formula
kokes med 200 deler iseddik i 10 timer med tilbakeløpskjøler og deretter helles i en stor mengde vann. Det utskilte kondensasjonsprodukt frafiltreres, vaskes med vann, og om nødvendig krystalliseres fra etanol. Man får det i eksempel 2 beskrevne a, /?-di-[5-metyl-benzoksazolyl-(2)]-etylen. boiled with 200 parts glacial acetic acid for 10 hours with a reflux condenser and then poured into a large quantity of water. The separated condensation product is filtered off, washed with water and, if necessary, crystallized from ethanol. The a, ?-di-[5-methyl-benzoxazolyl-(2)]-ethylene described in Example 2 is obtained.
I stedet for iseddik kan man også an-vende propionsyre. Instead of glacial acetic acid, you can also use propionic acid.
Eksempel 7: Example 7:
19,25 deler av acylforbindelsen med formelen 19.25 parts of the acyl compound with the formula
utrøres lett kokende med 2 deler borsyre i 300 volumdeler xylol under utelukkelse av luft, idet det dannede vann avdestilleres fortløpende. Så snart vannavspaltningen er fullstendig, lar man avkjøle, tilsetter 200 volumdeler etanol, filtrerer fra kon- is stirred while boiling with 2 parts boric acid in 300 parts xylol by volume while excluding air, the water formed being continuously distilled off. As soon as the water separation is complete, it is allowed to cool, 200 parts by volume of ethanol are added, filtered from con-
densasjonsproduktet, vasker det med eta- densation product, wash it with eta-
nol og vann og tørker. Etter omkrystallisa- nol and water and dries. After recrystallization
sjon fra dioksan smelter det erholdte a, ( i-di- [5-klorbenzoksazolyl- (2) ] -etylen med formelen tion from dioxane melts the obtained a, ( i-di- [5-chlorobenzoxazolyl-(2) ] -ethylene with the formula
som etter omkrystallisasjon fra dioksan as after recrystallization from dioxane
smelter ved 183—184°. melts at 183-184°.
Claims (6)
Applications Claiming Priority (1)
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US580266A US3381432A (en) | 1966-09-19 | 1966-09-19 | Stressed-skin span structure |
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NO121015B true NO121015B (en) | 1971-01-04 |
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GB (1) | GB1142267A (en) |
IL (1) | IL28637A (en) |
NL (1) | NL6712765A (en) |
NO (1) | NO121015B (en) |
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US3783572A (en) * | 1970-07-07 | 1974-01-08 | F Sironi | A facing panel |
DE2047410A1 (en) * | 1970-09-26 | 1972-03-30 | Wagenknecht geb. Hißbach, Katharina, 7500 Karlsruhe | Composite construction element for creating load-bearing or non-load-bearing surfaces and bodies |
NL7203683A (en) * | 1971-05-21 | 1972-11-23 | ||
US3748796A (en) * | 1971-11-16 | 1973-07-31 | P Quellet | Building structure with composite arched units and method of construction thereof |
US3967430A (en) * | 1972-02-14 | 1976-07-06 | Knudson Gary Art | Building method |
CA985869A (en) * | 1972-02-14 | 1976-03-23 | Gary A. Knudson | Panel for self-supporting building, building method and panel forming apparatus |
US3902288A (en) * | 1972-02-14 | 1975-09-02 | Knudson Gary Art | Arched roof self-supporting building |
US3866376A (en) * | 1972-10-05 | 1975-02-18 | United States Gypsum Co | Metal clad gypsum walls |
DE2441226A1 (en) * | 1973-08-31 | 1975-03-20 | Romillo Francisco De La Concha | PROTECTIVE COVERS MADE OF INDIVIDUAL ELEMENTS |
US3922828A (en) * | 1973-11-15 | 1975-12-02 | Tri International Corp | Structural member |
US4076013A (en) * | 1976-03-11 | 1978-02-28 | Universal Construction Industries, Inc. | Solar heating system |
US4071984A (en) * | 1976-09-16 | 1978-02-07 | Kenneth Larrow | House assembly with prefabricated elements |
US4180771A (en) * | 1977-12-02 | 1979-12-25 | Airco, Inc. | Chemical-sensitive field-effect transistor |
US4197689A (en) * | 1978-01-13 | 1980-04-15 | Demuth Steel Products Company | Bulk storage vessels |
CH637724A5 (en) * | 1979-06-05 | 1983-08-15 | Idc Chemie Ag | INSULATED EXTERNAL CLOTHING FOR BUILDING WALLS. |
US4397608A (en) * | 1980-05-01 | 1983-08-09 | Automation Industries, Inc. | Energy-absorbing turbine missile shield |
DE8910744U1 (en) * | 1989-09-08 | 1991-01-17 | Schmidt, Rene P., Oberweningen, Ch | |
DE9315037U1 (en) * | 1993-10-05 | 1994-10-13 | Wittenauer Roman | Supporting structure for a flat or pent roof |
NL9400028A (en) * | 1994-01-07 | 1995-08-01 | Bennenk Hendrik W | Cantilevered roof construction. |
US20100101171A1 (en) * | 2007-05-25 | 2010-04-29 | George Charles Clifton | Panels |
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US2150217A (en) * | 1938-03-12 | 1939-03-14 | Gettelman Fredrick | Roof |
US3148230A (en) * | 1961-12-05 | 1964-09-08 | North American Refractories | Refractory structure |
US3315424A (en) * | 1963-09-20 | 1967-04-25 | Eugene S Smith | Building construction |
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1966
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1967
- 1967-09-14 GB GB41996/67A patent/GB1142267A/en not_active Expired
- 1967-09-15 IL IL28637A patent/IL28637A/en unknown
- 1967-09-16 DE DE19671658799 patent/DE1658799A1/en active Pending
- 1967-09-18 NO NO169775A patent/NO121015B/no unknown
- 1967-09-18 BR BR193022/67A patent/BR6793022D0/en unknown
- 1967-09-18 BE BE703976D patent/BE703976A/xx unknown
- 1967-09-18 SE SE12839/67A patent/SE306409B/xx unknown
- 1967-09-19 NL NL6712765A patent/NL6712765A/xx unknown
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SE306409B (en) | 1968-11-25 |
BR6793022D0 (en) | 1973-01-23 |
NL6712765A (en) | 1968-03-20 |
US3381432A (en) | 1968-05-07 |
GB1142267A (en) | 1969-02-05 |
IL28637A (en) | 1971-05-26 |
BE703976A (en) | 1968-02-01 |
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