DE1052017B - Process for the production of substituted naphthyrones - Google Patents
Process for the production of substituted naphthyronesInfo
- Publication number
- DE1052017B DE1052017B DEB41484A DEB0041484A DE1052017B DE 1052017 B DE1052017 B DE 1052017B DE B41484 A DEB41484 A DE B41484A DE B0041484 A DEB0041484 A DE B0041484A DE 1052017 B DE1052017 B DE 1052017B
- Authority
- DE
- Germany
- Prior art keywords
- parts
- naphthyrones
- substituted
- yellow
- membered
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 6
- 239000007858 starting material Substances 0.000 claims description 4
- -1 aliphatic alcohols Chemical class 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- 238000004040 coloring Methods 0.000 claims 1
- 150000002238 fumaric acids Chemical class 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000001052 yellow pigment Substances 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000049 pigment Substances 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- OQHAOYHGURHBDD-UHFFFAOYSA-N butane-1,1-diol propane Chemical compound CCC.CCCC(O)O OQHAOYHGURHBDD-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 125000005059 halophenyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
-
- 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
- C09B57/00—Other synthetic dyes of known constitution
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von substituierten Naphthyronen Es ist bekannt, daß der von Pechmann (Ber. deutsch. Chem. Ges., Bd. 15, S. 881 bis 892) beschriebene rote Farbstoff ein Fünfring-D.ilaktön der Diphenacylfumarsäure darstellt. Weiterhin ist bekannt (s. Bogert und Ritter, J. Amer. Chem. Soc., Bd. 46 [1924], S. 2871 bis 2878, und Chovin, Bull. Soc. Chi!m. France, Bd. 11 [1944], S. 91 bis 96), daß man das rote Fünfring-Dilakton in ein gelbes Sechsring-Dilakton, das sogenannte Diphenylnaphühyron, umlagern kann. Diese Umlagerung erfolgte bisher über die Aufspaltung des Fünfring-Dilaktons mittels alkoholischer Kalilauge und anschließendem Ringschluß in saurem Medium, wobei nicht Fünfringschluß, sondern Sechsringschluß eintritt: E. K 1 i n g s b e r g beschreibt in den Chem. Reviews, Bd.54 (1954), S.59 bis 77, den Mechanismus der Umlagerung eingehend.Process for the production of substituted naphthyrones It is known that the red dye described by Pechmann (Ber. Deutsch. Chem. Ges., Vol. 15, pp. 881 to 892) is a five-membered ring of diphenacylfumaric acid. It is also known (see Bogert and Ritter, J. Amer. Chem. Soc., Vol. 46 [1924], pp. 2871 to 2878, and Chovin, Bull. Soc. Chi! M. France, Vol. 11 [1944 ], Pp. 91 to 96) that the red five-membered dilactone can be rearranged into a yellow six-membered dilactone, the so-called diphenylnaphyron. This rearrangement has so far taken place via the splitting of the five-membered dilactone by means of alcoholic potassium hydroxide and subsequent ring closure in an acidic medium, whereby not five-membered ring but six-membered ring occurs: E. K 1 ingsberg describes the mechanism of the rearrangement in detail in Chem. Reviews, Vol. 54 (1954), pp. 59 to 77.
Eine Herstellung der gelben Verbindung (= Diphenylnaphthyron) auf diesem Wege ist jedoch nicht vorteilhaft, da die Ausbeuten sehr schlecht sind.A production of the yellow compound (= Diphenylnaphthyrone) on however, this route is not advantageous because the yields are very poor.
Es wurde nun gefunden, daß man in einfacher Weise rote »Fünfring-Dilaktone« in gelbe »Sechsring-D,ilaktone (= Diphenylnaphthyrone) umlagern kann, indem man erstere mit einem Lösungsmittel auf 100 bis 250° C, vorzugsweise auf 200° C, erwärmt.It has now been found that red "five-membered dilactones" can rearrange into yellow »six-membered D, ilaktone (= Diphenylnaphthyrone) by the former heated to 100 to 250 ° C, preferably to 200 ° C, with a solvent.
Als Lösungsmittel besonders geeignet sind zwei-und mehrwertige aliphatische Alkohole, wie Äthylenglykol, Propan-butandiol, Butantriol sowie Diäthylenglykol und Polyäther des Äthylenglykols. Es ist jedoch wegen der Schwerlöslichkeit der Ausgangsstoffe in .den angeführten Lösungsmitteln vorteilhaft, Gemische mit anderen, die Löslichkeit verbessernden Lösungsmitteln, wie Nitrobenzol, Trichlorbenzol oder Benzylalkohol, zu verwenden.Divalent and polyvalent aliphatic solvents are particularly suitable Alcohols such as ethylene glycol, propan-butanediol, butanetriol and diethylene glycol and polyethylene glycol polyethers. However, it is because of the poor solubility of the Starting materials in the listed solvents are advantageous, mixtures with others, Solubility-improving solvents such as nitrobenzene, trichlorobenzene or Benzyl alcohol, to use.
Als Ausgangsstoffe eignen sich alle Verbindungen der allgemeinen Formel wobei R und R' nichtannelierte Arylgruppen, wie Phenyl, Tolyl, Xylyl, Halogenphenyl, Anisyl, Phenetyl, Styryl oder Diphenylyl, bedeuten.All compounds of the general formula are suitable as starting materials where R and R 'are non-fused aryl groups such as phenyl, tolyl, xylyl, halophenyl, anisyl, phenetyl, styryl or diphenylyl.
Eine Übersicht über die verschiedenen Darstellungsmethoden solcher Ausgangsstoffe bietet die bereits erwähnte Arbeit von E. K 1 i n g s b e r g : »Die Chemie der Pechmann-Farbstoffe«, in den Chem. Reviews, Bd. 54 (1954), S. 59 bis 77.An overview of the various display methods for such The already mentioned work by E. K 1 in g s b e r g offers starting materials: »Die Chemistry of Pechmann Dyes ", in the Chem. Reviews, Vol. 54 (1954), pp. 59 bis 77.
Die auf diese Weise leicht zugänglichen Diarylnaphthyrone lassen sich auf Grund ihrer Leuchtkraft und hervorragenden Lichtechtheit als Fluoreszenzfarbstoffe und Tageslichtleuchtstoffe verwenden.The diarylnaphthyrones, which are easily accessible in this way, can be due to their luminosity and excellent lightfastness as fluorescent dyes and use daylight phosphors.
Die in den Beispielen genannten Teile sind Gewichtsteile.The parts mentioned in the examples are parts by weight.
Beispiel 1 30 Teile des Fünfring-Dilaktons der Diphenacylfumarsäure vom F. 317° C werden in einem Gemisch von 250 Teilen Nitrobenzol und 250 Teilen Äthylenglykol unter Rühren und Erwärmen auf 200° C gelöst. Die Lösungsfarbe schlägt bei Temperaturen von 180° C an aufwärts bereits nach Gelb um. Wenn nie Substanz vollkommen gelöst ist, läßt man abkühlen; dabei kristallisiert zum großen Teil das Naphthyron in orangegelben Kristallen aus. Nach Zugabe von 500 Teilen Äthanol zu dem noch warmen Gemisch kristallisiert der Rest des Produktes aus. Es wird kalt abgesaugt und zuerst mit 150 Teilen Salzsäure (1 :1) und dann mit wenig Äthanol nachgewaschen und getrocknet. Man erhält 27 Teile eines leuchtendorangegel.ben Pigmentes vom F. 332° C mit intensiv gelborangefarbener Fluoreszenz. Beispiel 2 30 Teile des Fünfring-Dilaktons der p,p =Dimethyldiphenacylfumarsäure (F. 337° C) werden in einem Gemisch von 250 Teilen Nitrobenzol und 250 Teilen Diäthylenglykol wie im Beispiel 1 umgesetzt und aufgearbeitet.Example 1 30 parts of the five-membered dilactone of diphenacylfumaric acid with a temperature of 317 ° C are in a mixture of 250 parts of nitrobenzene and 250 parts Ethylene glycol dissolved with stirring and heating to 200 ° C. the Solution color changes to yellow at temperatures from 180 ° C upwards. If the substance is never completely dissolved, it is allowed to cool; crystallized in the process for the most part the naphthyrone in orange-yellow crystals. After adding 500 When adding ethanol to the still warm mixture, the remainder of the product crystallizes the end. It is suctioned off cold and first with 150 parts of hydrochloric acid (1: 1) and then washed with a little ethanol and dried. You get 27 parts of a luminous orange yellow Pigment with a melting point of 332 ° C with intense yellow-orange fluorescence. Example 2 30 parts of the five-membered dilactone of p, p = dimethyldiphenacylfumaric acid (mp 337 ° C) are in a mixture of 250 parts of nitrobenzene and 250 parts of diethylene glycol implemented as in Example 1 and worked up.
Die Ausbeute an orangegelbem Pigment beträgt 26 Teile. Es zeigt eine intensive gelborange Fluoreszenz. Beispiel 3 30 Teile .des Fünfring-Dilaktons der 2,4-, 2',4'-Tetramethyldiphenacylfumarsäure (F. 252° C) werden in einem Gemisch von 250 Teilen Benzylalkohol und 250 Teilen Butandiol wie im Beispiel 1 gelöst, umgesetzt und aufgearbeitet.The yield of the orange-yellow pigment is 26 parts. It shows a intense yellow-orange fluorescence. Example 3 30 parts of the five-membered dilactone from 2,4-, 2 ', 4'-Tetramethyldiphenacylfumaric acid (mp 252 ° C) are in a mixture of 250 parts of benzyl alcohol and 250 parts of butanediol dissolved as in Example 1, implemented and processed.
Man erhält 26 Teile eines leuehtendorangegelben Pigmentes vom F. 228° C mit intensiv gelborangefarbener Fluoreszenz. Beispiel 4 30 Teile des Fünfring-Dilaktons der 2,4,6-, 2',4',6'-Hexamethyl-diphenylacylfumarsäure (F. 295° C) werden in einem Gemisch von 72 Teilen Nitrobenzol und 48 Teilen Diäthylenglykol unter Rühren und Erwärmen auf 200° C gelöst. Die Aufarbeitung erfolgt wie im Beispiel 1, nur daß man an Stelle von 500 Teilen nur 120 Teile Äthanol und statt 150 Teilen Salzsäure (1 :1) nur 36 Teile davon verwendet.26 parts of a Leuehtendorang-yellow pigment with a melting point of 228 ° are obtained C with intense yellow-orange fluorescence. Example 4 30 parts of the five-membered dilactone the 2,4,6-, 2 ', 4', 6'-hexamethyl-diphenylacylfumaric acid (mp 295 ° C) are in a Mixture of 72 parts of nitrobenzene and 48 parts of diethylene glycol with stirring and Warming to 200 ° C dissolved. The work-up is carried out as in Example 1, only that instead of 500 parts only 120 parts of ethanol and instead of 150 parts of hydrochloric acid (1: 1) only used 36 parts of it.
Man erhält 27 Teile eines leuchtendgelben Pigmentes vom F. 300° C. Seine Fluoreszenz ist intensiv orangegelb.27 parts of a bright yellow pigment with a melting point of 300 ° C. are obtained. Its fluorescence is intense orange-yellow.
Beispiel 5 30 Teile des Fünfring-Dilaktons der p,p =Dichlordiphenacylfum,arsäure werden in einem Gemisch von 500T.eilen Nitrobenzol und 500Teilen Butantriol-1,2,4 wie im Beispiel 1 umgesetzt und aufgearbeitet. Man erhält 26 Teile eines leuchtendorangefarbenen Pigmentes mit starker orangefarbener Fluoreszenz. Beispiel 6 30 Teile des Fünf ring-Dilaktons der p,p =Dimethoxydiphenacylfumarsäure (F. 310° C) werden in einem Gemisch von 250 Teilen Nitrobenzol und 250 Teilen Propandiol-(1,2) [oder-(1,3) ] wie im Beispiel 1 umgesetzt und aufgearbeitet. Man erhält 25 Teile eines leuchtendorangefarbenen Pigmentes vom F.325 bis 327° C. Seine Fluoreszenz ist intensiv orangerot.Example 5 30 parts of the five-membered dilactone of p, p = dichlorodiphenacylfum, aric acid are in a mixture of 500 parts nitrobenzene and 500 parts butanetriol-1,2,4 implemented as in Example 1 and worked up. 26 parts of a bright orange color are obtained Pigment with strong orange fluorescence. Example 6 30 parts of the five ring dilactone the p, p = dimethoxydiphenacylfumaric acid (m.p. 310 ° C) are in a mixture of 250 Parts of nitrobenzene and 250 parts of propanediol- (1,2) [or- (1,3)] as in the example 1 implemented and processed. 25 parts of a bright orange color are obtained Pigment from F.325 to 327 ° C. Its fluorescence is intense orange-red.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB41484A DE1052017B (en) | 1956-08-22 | 1956-08-22 | Process for the production of substituted naphthyrones |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB41484A DE1052017B (en) | 1956-08-22 | 1956-08-22 | Process for the production of substituted naphthyrones |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1052017B true DE1052017B (en) | 1959-03-05 |
Family
ID=6966407
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEB41484A Pending DE1052017B (en) | 1956-08-22 | 1956-08-22 | Process for the production of substituted naphthyrones |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1052017B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999052909A3 (en) * | 1998-04-08 | 2000-01-13 | Ciba Sc Holding Ag | Dibenzonaphthyrones and their use for colouring/pigmenting high-molecular-weight organic material |
-
1956
- 1956-08-22 DE DEB41484A patent/DE1052017B/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999052909A3 (en) * | 1998-04-08 | 2000-01-13 | Ciba Sc Holding Ag | Dibenzonaphthyrones and their use for colouring/pigmenting high-molecular-weight organic material |
| US6281361B1 (en) | 1998-04-08 | 2001-08-28 | Ciba Specialty Chemicals Corp. | Dibenzonaphthyrones |
| US6533825B2 (en) | 1998-04-08 | 2003-03-18 | Ciba Specialty Chemicals Corporation | Dibenzonaphthyrones |
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