CH450421A - Process for the preparation of azolyl thiophene compounds - Google Patents
Process for the preparation of azolyl thiophene compoundsInfo
- Publication number
- CH450421A CH450421A CH1505862A CH1505862A CH450421A CH 450421 A CH450421 A CH 450421A CH 1505862 A CH1505862 A CH 1505862A CH 1505862 A CH1505862 A CH 1505862A CH 450421 A CH450421 A CH 450421A
- Authority
- CH
- Switzerland
- Prior art keywords
- compounds
- formula
- radical
- preparation
- carboxyl group
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 7
- 238000002360 preparation method Methods 0.000 title claims description 5
- XCJMGRZQOXNTRE-UHFFFAOYSA-N 2-thiophen-2-yl-1h-pyrrole Chemical class C1=CNC(C=2SC=CC=2)=C1 XCJMGRZQOXNTRE-UHFFFAOYSA-N 0.000 title description 7
- 150000001875 compounds Chemical class 0.000 claims description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 5
- AVRAFQYKQWOZHV-UHFFFAOYSA-N 2-thiophen-2-yl-1,3-oxazole Chemical class C1=CSC(C=2OC=CN=2)=C1 AVRAFQYKQWOZHV-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 229930192474 thiophene Natural products 0.000 claims description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- 125000002883 imidazolyl group Chemical group 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 125000000335 thiazolyl group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 125000002843 carboxylic acid group Chemical group 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical group NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- UZLSJAUHCCPJMC-UHFFFAOYSA-N 2-thiophen-2-yl-1h-imidazole Chemical class C1=CSC(C=2NC=CN=2)=C1 UZLSJAUHCCPJMC-UHFFFAOYSA-N 0.000 description 1
- QGMFBCDNJUZQBZ-UHFFFAOYSA-N 5-phenylthiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=CC=C1 QGMFBCDNJUZQBZ-UHFFFAOYSA-N 0.000 description 1
- UFFRSDWQMJYQNE-UHFFFAOYSA-N 6-azaniumylhexylazanium;hexanedioate Chemical compound [NH3+]CCCCCC[NH3+].[O-]C(=O)CCCCC([O-])=O UFFRSDWQMJYQNE-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- VNQABZCSYCTZMS-UHFFFAOYSA-N Orthoform Chemical compound COC(=O)C1=CC=C(O)C(N)=C1 VNQABZCSYCTZMS-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000003943 azolyl group Chemical group 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- -1 ethylene glycol ester Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/06—Dyes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Polyamides (AREA)
- Artificial Filaments (AREA)
Description
Verfahren zur Herstellung von Azolyl-thiophenverbindungen In der schweizerischen Patentschrift Nr. 412 312 sind Azolyl-thiophenverbindungen der Formel
EMI0001.0003
beschrieben worden, worin R1 für einen Benzol- oder Naphthalinrest und R für einen in 2-Stellung an R1 und in 5-Stellung an den Azolylring gebundenen Thio- phenrest stehen,
X die Ergänzung zum Azolring und R2 einen in der durch die Valenzstriche angegebenen Weise mit dem Azolring kondensierten Benzol- oder Naphthalinrest bedeuten.
Es wurde nunmehr gefunden, dass eine besonders wertvolle Gruppe von Imidazolyl-, Thiazolyl- oder Oxa- zolyl-thiophenverbindungen gemäss vorstehender allge meiner Formel - nämlich solche, welche mindestens eine direkt an ein Ringkohlenstoffatom von R2 ge bundene, gegebenenfalls funktionell abgewandelte, sauer stoffhaltige Carbonsäuregruppe enthalten - in vorteil hafter Weise hergestellt werden können, indem man Monocarbonsäuren der Formel (2) R1-R-COOH ,
worin R1 für einen gegebenenfalls substituierten Phe- nyl- oder Naphthylrest und R für einen in 2-Stellung an R1 und in 5-Stellung an die Carboxylgruppe gebun denen, gegebenenfalls weitersubstituierten Thiophenrest stehen, mit Aminoverbindungen der Formel
EMI0001.0038
worin X für ein Sauerstoffatom,
ein Schwefelatom oder eine NH-Gruppe steht und R- einen gegebenenfalls weitersubstituierten Phenylen- oder Napthylenrest be deutet, der mindestens eine direkt an ein Ringkohlen stoffatom gebundene, veresterte Carboxylgruppe ent hält, umsetzt.
Gemäss einer Variante des vorstehend bezeichneten Verfahrens werden die korrespondierenden Verbindun gen mit freier Carboxylgruppe durch eine anschliessende Verseifung erhalten. Die verfahrensgemäss erhältlichen Verbindungen können ferner zur Herstellung der ent sprechenden Säureamide verwendet werden, indem die freien Säuren über die Säurechloride in die entspre chenden Säureamide überführt werden.
Sowohl die freie Carbonsäuregruppe als auch funk tionell abgewandelte Carbonsäuregruppen müssen je doch das Oxo-Sauerstoffatom enthalten. Unter den funk tionell abgewandelten Carbonsäuregruppen sind vor al lem die Carbonsäureestergruppen zu erwähnen und un ter diesen die Alkylestergruppen;
ferner Alkenyl-, Aryl- und Aralkylestergruppen. Weiterhin sind Carbonsäure- amid- und Carbonsäurehydrazidgruppen von Interesse, wobei in beiden Fällen die Stickstoffatome noch Sub- stituenten tragen können. Die gegebenenfalls funktionell abgewandelten Carbonsäuregruppen sind an den Rest R2 gebunden.
--- Wie die Azolyl-thiophenverbindungen der obenge nannten Patentschrift können auch die hier vorliegenden Imidazolylthiophenverbindungen, Thiazolyl-thiophenver- bindungen oder vorzugsweise Oxazolyl-thiophenverbin- dungen sein.
Vor allem sind Oxazolyl-thiophenverbin- dungen der Formel
EMI0001.0075
zu erwähnen, worin R und R2 die angegebene Bedeu tung haben und der Rest R2 eine direkt an den Ben- zolring gebundene Carbonsäure-, Carbonsäureester-,
Carbonsäureamid- oder Carbonsäurehydrazidgruppe
EMI0002.0008
worin Y ein Wasserstoffatom oder eine Alkylgruppe mit höchstens 4 Kohlenstoffatomen und Z eine Car- bonsäure- oder Carbonsäureestergruppe bedeuten.
EMI0002.0014
entsprechen, worin U, und U2 Wasserstoffatome, Ha logenatome, Alkyl- oder Alkoxygruppen mit 1 bis 4 Kohlenstoffatomen, U3 ein Wasserstoffatom oder eine Alkoxygruppe mit 1 bis 4 Kohlenstoffatomen,
Y ein Sauerstoffatom oder eine Alkylgruppe mit 1 bis 4 Koh- lenstoffatomen und Z eine Carbonsäure- oder Carbon- säurealkylestergruppe bedeuten.
Die für das Herstellungsverfahren als Ausgangs stoffe dienenden Monocarbonsäuren der Formel (2) und Aminocarbonsäureester der Formel (3) sind entweder bekannt oder können nach an sich bekannten Methoden gewonnen werden. Die Umsetzungen können analog den Angaben der obengenannten schweizerischen Patent schrift Nr. 412 312 ausgeführt werden. Dabei erhält man zunächst Ester, vorzugsweise Alkylester, mit nied- rigmolekularen Alkylgruppen, z. B. Methylester. Diese lassen sich z. B.
Umestern oder verseifen, und aus den so erhaltenen freien Carbonsäuren können in üblicher Weise die Säurehalogenide und aus den letzteren Säure- amide oder Säurehydrazide hergestellt werden.
Die Azolyl-thiophenverbindungen der vorliegenden Erfindung lassen sich für die gleichen Zwecke ver wenden wie diejenigen der obengenannten Patentschrift. Sie erweisen sich aber besonders vorteilhaft zum opti schen Aufhellen von synthetischen Fasern, insbesondere Polyesterfasern und Polyamidfasern. Die neuen Azolyl- thiophenverbindungen können auch vor oder während der Polykondensation bzw. Polymerisation zu Poly-
EMI0002.0048
vom Schmelzpunkt 178 bis 180 C.
33,5 Teile der Verbindung der Formel (7) werden mit 40 Teilen Natriumhydroxyd, 100 Teilen Wasser und 400 Volumteilen Äthanol während 24 Stunden am Rückfluss gekocht. Sodann verdünnt man mit 500 Tei- aufweist. Neben dieser letzteren Gruppe kann der Rest R2 noch weitere Substituenten enthalten. Es kommen in erster Linie Alkylgruppen in Betracht.
Somit ent spricht der Rest R2 vorzugsweise der Formel Auch der Rest R1 kann Substituenten enthalten, so dass die Azolyl-thiophenverbindungen beispielsweise der Formel estern und Polyamiden den Reaktionsgemischen zuge setzt werden.
In den nachfolgenden Beispielen bedeuten die Teile, sofern nichts anderes bemerkt wird, Gewichtsteile, die Prozente Gewichtsprozente, und die Temperaturen sind in Celsiusgraden angegeben.
<I>Beispiel 1</I> 51 Teile 5-Phenylthiophen-2-carbonsäure, 40 Teile 4-Hydroxy-3-aminobenzol-l-carbonsäuremethylester und 2 Teile Borsäure werden im Stickstoffstrom mit 150 Volumteilen Diäthylenglykoldiäthyläther verrührt. Innerhalb einer Stunde wird das Reaktionsgemisch auf 185 bis 190 C aufgeheizt, wobei eine trübe dunkle Lösung entsteht und Wasser entweicht. Man rührt 1 bis 2 Stunden bei dieser Temperatur und dampft sodann das Lösungsmittel langsam ab. Das Reaktionsgemisch geht in eine trübe dunkle Schmelze über, welche wäh rend etwa 2 Stunden bei 260 C gerührt wird.
Man lässt nun erkalten und löst die erstarrte Schmelze in 1000 Volumteilen heissem Dimethylformamid, filtriert vom ungelösten Rückstand ab, engt stark ein und fällt das Reaktionsprodukt mit Methanol aus. Nach dem Er kalten nutscht man den Niederschlag, presst gut ab und wäscht das Nutschgut mit Methylalkohol.
Man kristallisiert den Rückstand aus Dioxan um und erhält etwa 50 Teile eines hellbeigen Pulvers der Formel len Wasser und saugt das Äthanol am Vakuum ab. Nach dem Ansäuern filtriert man den Niederschlag und wäscht mit Wasser, bis das Filtrat neutral reagiert. Man erhält etwa 27 Teile eines braunen Pulvers. Die mehrmals aus Dichlorbenzol umkristallisierte Verbin dung der Formel
EMI0003.0001
erhält man als gelbliches Pulver vom Schmelzpunkt 281 bis 283,5 C.
<I>Beispiel 2</I> 100 Teile Polyester-Granulat aus Polytherephthal- säureäthylenglykolester werden innig mit 0,05 bis 0,1 Teil der Verbindung der Formel (8) vermischt und bei 285 C unter Rühren geschmolzen. Nach dem Ausspin nen der Spinnmasse durch übliche Spinndüsen werden stark aufgehellte Polyesterfasern erhalten.
Ähnliche Aufhelleffekte werden erzielt, wenn man anstelle der Verbindung der Formel (8) die Verbindung der Formel (7) verwendet.
<I>Beispiel 3</I> 10 000 Teile eines aus Hexamethylendiaminadipat in bekannter Weise hergestellten Polyamides in Schnit- zelform werden mit 30 Teilen Titandioxyd (Rutil-Modi- fikation) und 10 Teilen der Verbindung der Formel (8) in einem Rollgefäss während 12 Stunden gemischt. Die so behandelten Schnitzel werden nach Verdrängung des Luftsauerstoffs durch überhitzten Wasserdampf in einem mit Öl- oder Diphenyldampf auf 300 bis 3l0 C be heizten Kessel geschmolzen und während einer halben Stunde gerührt.
Die Schmelze wird hierauf unter Stick stoffdruck von 5 Atü durch eine Spinndüse ausge presst und das derart gesponnene abgekühlte Filament auf eine Spinnspule aufgewickelt. Die entstandenen Fä den zeigen einen ausgezeichneten thermofixierbeständi- gen Aufhelleffekt von guter Wasch- und Lichtechtheit.
Verwendet man anstelle der Verbindung der Formel (8) die Verbindung der Formel (7), so erhält man ähn liche Aufhelleffekte.
Process for the preparation of azolyl-thiophene compounds In Swiss Patent No. 412 312, azolyl-thiophene compounds are of the formula
EMI0001.0003
has been described in which R1 is a benzene or naphthalene radical and R is a thiophene radical bonded to R1 in the 2-position and to the azolyl ring in the 5-position,
X is the addition to the azole ring and R2 is a benzene or naphthalene residue condensed with the azole ring in the manner indicated by the valence lines.
It has now been found that a particularly valuable group of imidazolyl, thiazolyl or oxazolyl thiophene compounds according to the above general formula - namely those which have at least one, optionally functionally modified, oxygen-containing carboxylic acid group bonded directly to a ring carbon atom of R2 contain - can be prepared in an advantageous manner by monocarboxylic acids of the formula (2) R1-R-COOH,
where R1 is an optionally substituted phenyl or naphthyl radical and R is an optionally further substituted thiophene radical bonded to R1 in the 2-position and to the carboxyl group in the 5-position, with amino compounds of the formula
EMI0001.0038
where X is an oxygen atom,
a sulfur atom or an NH group and R- denotes an optionally further substituted phenylene or naphthylene radical containing at least one esterified carboxyl group bonded directly to a ring carbon atom.
According to a variant of the method described above, the corresponding compounds with free carboxyl groups are obtained by a subsequent saponification. The compounds obtainable according to the process can also be used to prepare the corresponding acid amides by converting the free acids into the corresponding acid amides via the acid chlorides.
Both the free carboxylic acid group and functionally modified carboxylic acid groups must, however, contain the oxo-oxygen atom. Among the functionally modified carboxylic acid groups are to be mentioned above all the carboxylic acid ester groups and below these the alkyl ester groups;
also alkenyl, aryl and aralkyl ester groups. Furthermore, carboxylic acid amide and carboxylic acid hydrazide groups are of interest, and in both cases the nitrogen atoms can still carry substituents. The optionally functionally modified carboxylic acid groups are bound to the radical R2.
--- Like the azolyl-thiophene compounds of the above-mentioned patent, the imidazolyl-thiophene compounds present here can also be thiazolyl-thiophene compounds or, preferably, oxazolyl-thiophene compounds.
In particular, oxazolyl-thiophene compounds of the formula
EMI0001.0075
to be mentioned in which R and R2 have the meaning given and the radical R2 is a carboxylic acid, carboxylic acid ester,
Carboxylic acid amide or carboxylic acid hydrazide group
EMI0002.0008
where Y is a hydrogen atom or an alkyl group having at most 4 carbon atoms and Z is a carboxylic acid or carboxylic acid ester group.
EMI0002.0014
correspond, in which U, and U2 are hydrogen atoms, halogen atoms, alkyl or alkoxy groups with 1 to 4 carbon atoms, U3 is a hydrogen atom or an alkoxy group with 1 to 4 carbon atoms,
Y denotes an oxygen atom or an alkyl group with 1 to 4 carbon atoms and Z denotes a carboxylic acid or carboxylic acid alkyl ester group.
The monocarboxylic acids of the formula (2) and aminocarboxylic acid esters of the formula (3) used as starting materials for the preparation process are either known or can be obtained by methods known per se. The reactions can be carried out analogously to the information in the above-mentioned Swiss patent no. 412 312. Esters, preferably alkyl esters, with low molecular weight alkyl groups, eg. B. methyl ester. These can be z. B.
Transesterification or saponification, and the acid halides can be prepared in the customary manner from the free carboxylic acids obtained in this way, and acid amides or acid hydrazides can be prepared from the latter.
The azolyl thiophene compounds of the present invention can be used for the same purposes as those of the above-mentioned patent. However, they prove to be particularly advantageous for optical lightening of synthetic fibers, especially polyester fibers and polyamide fibers. The new azolyl thiophene compounds can also be used before or during the polycondensation or polymerization to poly
EMI0002.0048
from melting point 178 to 180 C.
33.5 parts of the compound of the formula (7) are refluxed with 40 parts of sodium hydroxide, 100 parts of water and 400 parts by volume of ethanol for 24 hours. Then it is diluted with 500 parts. In addition to this latter group, the radical R2 can also contain further substituents. Primarily alkyl groups come into consideration.
The radical R2 thus preferably corresponds to the formula The radical R1 can also contain substituents, so that the azolyl-thiophene compounds, for example of the formula esters and polyamides, are added to the reaction mixtures.
In the following examples, unless otherwise noted, the parts are parts by weight, the percentages are percentages by weight, and the temperatures are given in degrees Celsius.
<I> Example 1 </I> 51 parts of 5-phenylthiophene-2-carboxylic acid, 40 parts of 4-hydroxy-3-aminobenzene-1-carboxylic acid methyl ester and 2 parts of boric acid are stirred with 150 parts by volume of diethylene glycol diethyl ether in a stream of nitrogen. The reaction mixture is heated to 185 to 190 ° C. within one hour, a cloudy, dark solution forming and water escaping. The mixture is stirred for 1 to 2 hours at this temperature and then the solvent is slowly evaporated off. The reaction mixture turns into a cloudy, dark melt, which is stirred at 260 ° C. for about 2 hours.
The mixture is now allowed to cool and the solidified melt is dissolved in 1000 parts by volume of hot dimethylformamide, the undissolved residue is filtered off, concentrated and the reaction product is precipitated with methanol. After it has cooled down, the precipitate is sucked off, pressed off well and the material on the filter is washed with methyl alcohol.
The residue is recrystallized from dioxane and about 50 parts of a light beige powder of the formula len water are obtained and the ethanol is suctioned off in vacuo. After acidification, the precipitate is filtered off and washed with water until the filtrate has a neutral reaction. About 27 parts of a brown powder are obtained. The compound of the formula recrystallized several times from dichlorobenzene
EMI0003.0001
is obtained as a yellowish powder with a melting point of 281 to 283.5 C.
<I> Example 2 </I> 100 parts of polyester granules made from polytherephthalic acid ethylene glycol ester are intimately mixed with 0.05 to 0.1 part of the compound of the formula (8) and melted at 285 ° C. with stirring. After spinning out the spinning mass through conventional spinnerets, heavily lightened polyester fibers are obtained.
Similar lightening effects are achieved if the compound of the formula (7) is used instead of the compound of the formula (8).
<I> Example 3 </I> 10,000 parts of a cut-form polyamide produced in a known manner from hexamethylenediamine adipate are mixed with 30 parts of titanium dioxide (rutile modification) and 10 parts of the compound of the formula (8) in a roller vessel during Mixed for 12 hours. The chips treated in this way are melted after displacement of the atmospheric oxygen by superheated steam in a kettle heated to 300 to 30 ° C. with oil or diphenyl vapor and stirred for half an hour.
The melt is then pressed out through a spinneret under nitrogen pressure of 5 atmospheres, and the cooled filament spun in this way is wound onto a spinning bobbin. The resulting threads show an excellent heat-setting-resistant lightening effect of good washing and lightfastness.
If, instead of the compound of the formula (8), the compound of the formula (7) is used, similar whitening effects are obtained.
Claims (1)
Priority Applications (18)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL302367D NL302367A (en) | 1961-07-19 | ||
| BE620372D BE620372A (en) | 1961-07-19 | ||
| NL122317D NL122317C (en) | 1961-07-19 | ||
| NL281101D NL281101A (en) | 1961-07-19 | ||
| CH379364A CH443664A (en) | 1961-07-19 | 1962-06-19 | Use of new azolyl thiophene derivatives as optical brightening agents for non-textile organic materials |
| FR903875A FR1335174A (en) | 1961-07-19 | 1962-07-13 | New azolyl-thiofenes for use as optical brighteners and process for their preparation |
| GB27631/62A GB990397A (en) | 1961-07-19 | 1962-07-18 | New azolylthiophene compounds useful as optical brightening agents and process for their production |
| DE1962C0027492 DE1238873B (en) | 1961-07-19 | 1962-07-18 | Optical brighteners |
| CH1505862A CH450421A (en) | 1962-12-21 | 1962-12-21 | Process for the preparation of azolyl thiophene compounds |
| DE1444006A DE1444006C3 (en) | 1961-07-19 | 1963-11-25 | Use of azolyl thiophene compounds as optical brightening agents for organic materials |
| GB4693863A GB1016365A (en) | 1961-07-19 | 1963-11-27 | New azolyl-thiophene derivatives, process for their preparation and their use |
| US328058A US3328310A (en) | 1961-07-19 | 1963-12-04 | Optically brightened organic compositions |
| US328112A US3264315A (en) | 1961-07-19 | 1963-12-04 | Azolyl-thiophene compounds |
| FR957342A FR84935E (en) | 1961-07-19 | 1963-12-16 | Novel azolyl-thiophenes for use as optical brighteners and process for preparing them |
| SE14131/63A SE300603B (en) | 1961-07-19 | 1963-12-18 | |
| BE641607D BE641607A (en) | 1961-07-19 | 1963-12-20 | |
| ES294732A ES294732A2 (en) | 1962-12-21 | 1963-12-20 | Procedure for the optical clarification of organic materials (Machine-translation by Google Translate, not legally binding) |
| AT1028663A AT243739B (en) | 1962-12-21 | 1963-12-20 | Optical brighteners |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1505862A CH450421A (en) | 1962-12-21 | 1962-12-21 | Process for the preparation of azolyl thiophene compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH450421A true CH450421A (en) | 1968-01-31 |
Family
ID=4405989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH1505862A CH450421A (en) | 1961-07-19 | 1962-12-21 | Process for the preparation of azolyl thiophene compounds |
Country Status (3)
| Country | Link |
|---|---|
| AT (1) | AT243739B (en) |
| CH (1) | CH450421A (en) |
| ES (1) | ES294732A2 (en) |
-
1962
- 1962-12-21 CH CH1505862A patent/CH450421A/en unknown
-
1963
- 1963-12-20 AT AT1028663A patent/AT243739B/en active
- 1963-12-20 ES ES294732A patent/ES294732A2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| AT243739B (en) | 1965-11-25 |
| ES294732A2 (en) | 1964-05-16 |
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