CS198004B1 - Method of preparing yellow pigments derived from cyclobutene - Google Patents
Method of preparing yellow pigments derived from cyclobutene Download PDFInfo
- Publication number
- CS198004B1 CS198004B1 CS553878A CS553878A CS198004B1 CS 198004 B1 CS198004 B1 CS 198004B1 CS 553878 A CS553878 A CS 553878A CS 553878 A CS553878 A CS 553878A CS 198004 B1 CS198004 B1 CS 198004B1
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- CS
- Czechoslovakia
- Prior art keywords
- formula
- cyclobutene
- yellow pigments
- pigments derived
- preparing yellow
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 4
- 239000001052 yellow pigment Substances 0.000 title description 2
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 title 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 150000004982 aromatic amines Chemical class 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000049 pigment Substances 0.000 claims description 4
- SGIJJRKRLSRUIW-UHFFFAOYSA-N C1C[C+]=[C+]1 Chemical compound C1C[C+]=[C+]1 SGIJJRKRLSRUIW-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000975 dye Substances 0.000 description 4
- 230000000269 nucleophilic effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- PWEBUXCTKOWPCW-UHFFFAOYSA-N squaric acid Chemical compound OC1=C(O)C(=O)C1=O PWEBUXCTKOWPCW-UHFFFAOYSA-N 0.000 description 3
- CUYKNJBYIJFRCU-UHFFFAOYSA-N 3-aminopyridine Chemical compound NC1=CC=CN=C1 CUYKNJBYIJFRCU-UHFFFAOYSA-N 0.000 description 2
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- CUFNKYGDVFVPHO-UHFFFAOYSA-N azulene Chemical compound C1=CC=CC2=CC=CC2=C1 CUFNKYGDVFVPHO-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000001043 yellow dye Substances 0.000 description 2
- AIGNCQCMONAWOL-UHFFFAOYSA-N 1,3-benzoselenazole Chemical compound C1=CC=C2[se]C=NC2=C1 AIGNCQCMONAWOL-UHFFFAOYSA-N 0.000 description 1
- GPRYKVSEZCQIHD-UHFFFAOYSA-N 1-(4-aminophenyl)ethanone Chemical compound CC(=O)C1=CC=C(N)C=C1 GPRYKVSEZCQIHD-UHFFFAOYSA-N 0.000 description 1
- XHQBIYCRFVVHFD-UHFFFAOYSA-N 1-benzothiophen-3-ol Chemical compound C1=CC=C2C(O)=CSC2=C1 XHQBIYCRFVVHFD-UHFFFAOYSA-N 0.000 description 1
- CGPPWNTVTNCHDO-UHFFFAOYSA-N 2-bromo-4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1Br CGPPWNTVTNCHDO-UHFFFAOYSA-N 0.000 description 1
- QPQKUYVSJWQSDY-CCEZHUSRSA-N 4-(phenylazo)aniline Chemical compound C1=CC(N)=CC=C1\N=N\C1=CC=CC=C1 QPQKUYVSJWQSDY-CCEZHUSRSA-N 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical class C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 1
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical compound O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- -1 cyclobutenediyl Chemical group 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
(54) Způsob přípravy žlutých cyklobutendiyliových pigmentů(54) A process for preparing yellow cyclobutenediylium pigments
Předmětem vynálezu je způsob přípravy žlutých cyklobutendiyliových pigmentů vzorce I jednostupňovou syntézou, reakcí 1,2-dihydroxycyklobutendionu s různě substituovanými aromatickými primárními nebo sekundárními aminySUMMARY OF THE INVENTION The present invention provides a process for the preparation of yellow cyclobutenediylium pigments of formula I by a one-step synthesis, by reacting 1,2-dihydroxycyclobutenedione with variously substituted aromatic primary or secondary amines
kde X je -N02, -COCH-j, -COPh, -NRg, -N = N - Ph, Y je Cl, -Br, -OH, -OCHj, -OC2H5, -H, -alkyl /C^-C^/, Z je H, CH-j, -CgH^, CgH^CN, -COCH-j a Ph znamená fenylovou skupinu. Barviva vzorce I jsou nová a mohou být aplikována jako pigmenty pro barvení polymemíeh iwhere X is -NO 2 , -COCH 3, -COPh, -NR 8, -N = N - Ph, Y is Cl, -Br, -OH, -OCH 3, -OC 2 H 5 , -H, -alkyl) C 1 -C 4, Z is H, CH 3, -C 8 H 4, C 8 H 4 CN, -COCH 3, and Ph represents a phenyl group. The dyes of the formula I are novel and can be applied as pigments for polymer dyeing
materiálů ve hmotě.of materials in matter.
Doposud*byla připravena řada barevných málo rozpustných sloučenin kondenzací 1,2-dihydroxycyklobutendionu nebo jeho funkčních derivátů (estery, bisacetát) e nukleofilními činidly. Jako nukleofilní sloučeniny jsou pro tento účel uváděny již sekundární cykloalifatické a aromatické aminy. Na rozdíl od těchto bia-aminoderivátů cyklobutendiyliumdiolátu vznikají z N,Ν-dialkyleubstituovaných aromatických aminů nebo z nukleofilních terciér198 004To date, a series of colored, poorly soluble compounds have been prepared by condensing 1,2-dihydroxycyclobutenedione or its functional derivatives (esters, bisacetate) with nucleophilic agents. As the nucleophilic compounds, secondary cycloaliphatic and aromatic amines are already mentioned for this purpose. In contrast to these bia-amino derivatives of cyclobutenediylium dilate, they are formed from N, Ν-dialkyl-substituted aromatic amines or from nucleophilic tertiary compounds.
198 004 nich aminů «neminového charakteru deriváty odlišné struktury, jako je tomu například reak cí s aktivními pyroly, kdy vznikají různě substituovaná 1,3-bie-pyrolycyklobutendiyliumdioláty, Ν,Ν-dialkyleubstituované aniliny kondenzují naproti tomu v polohách para, kdežto N-alkylderivéty oO -metyl homologú pyridinu, chinolinu, benzthiazolu nebo benzselenazolu reagují na oO-metylové skupině. Obdobně jako pyrolová deriváty reagují některá fenoly jako rezorcin nebo fluoroglucin. Dále byly studovány nukleofilní složky jako 3-metyl, reep198,004 of these non-non-amine derivatives of different structure, such as by reaction with active pyrrols to form differently substituted 1,3-bie-pyrrolycyclobutenediylium dilates, Ν, dial-dialkyleubstituted anilines, on the other hand, condense at para positions, whereas N-alkyl derivatives The oO-methyl homologues of pyridine, quinoline, benzthiazole or benzselenazole react at the oO-methyl group. Like the pyrrole derivatives, some phenols such as resorcinol or fluoroglucin react. Further, nucleophilic components such as 3-methyl, reep were studied
2,3-dimetyl-l-fenylpyrazolon, azulen, kyselina barbiturová, 3-hydroxybenzothiofen, 3-aminopyridin, etyleater kyseliny 2,4-dimetyl-pyrolkarbonové.2,3-dimethyl-1-phenylpyrazolone, azulene, barbituric acid, 3-hydroxybenzothiophene, 3-aminopyridine, 2,4-dimethylpyrrolocarboxylic acid ethyl ester.
příprava těchto cyklobutendiyliových barviv je založena na reakci ee substituovanými arylaminy vzorce IIthe preparation of these cyclobutenediyli dyes is based on the reaction with ee substituted arylamines of formula II
NH (II) kde X a Y mají výěe uvedený význam. Jako arylaminů možno e výhodou použít 4-nitroarylaminů vzorce III (III)NH (II) wherein X and Y are as defined above. As arylamines, 4-nitroarylamines of formula III (III) may be advantageously used.
NO.NO.
nebo substituovaného 4-aminoecetofenonu vzorce IVor a substituted 4-aminoecetophenone of formula IV
ZOF
Y (IV) jY (IV) j
nebo N,N-diaikyl-p-fenylendiaminu vzorce Vor N, N-diaalkyl-p-phenylenediamine of formula V
HNZ (V) nebo azobenzenu vzorce VIHNZ (V) or azobenzene of formula VI
Y (VI)Y (VI)
198 004 kde X a Z mají shora uvedený význam.198 004 wherein X and Z are as defined above.
MéftŽŮSé 9é ěiibáÚtafinjml Drkámíiit nebo sekundárními iryliminy DPobíhd diéib schématuMeanwhile, the dramatic or secondary irylimines are running on the scheme.
v prostředí bezvodých organických rozpouštědel, jako benzen, xylen, toluen, butylalkohol a podobně, za katalytického působení H+ a za teploty odpovídající teplotě varu aměsi použitých rozpustidei. S výhodou lze použít směsi aromatických nepolárních rozpustidel a n-butanolem v poměru 1 : 10 až 1 : 1.in anhydrous organic solvents such as benzene, xylene, toluene, butyl alcohol and the like under the catalytic action of H + and at a temperature corresponding to the boiling point and mixture of the solvents used. Preferably, mixtures of aromatic apolar solvents and n-butanol in a ratio of 1:10 to 1: 1 can be used.
Postup přípravy cyklobutendiyliových barviv podle vynálezu je ilustrován v následujících příkladech, které však nejsou jeho omezením.The process for preparing the cyclobutenediyl dyes of the invention is illustrated by the following examples, but is not limited thereto.
Příklad 1Example 1
Do uzavřené aparatury, opatřené míchadlem a nástavcem pro azeotropické oddestilování reakcí vznikající vody, se předloží 500 ml směsi benzenu a n-butanolu 1:1a přidá se 1,05 mol 4-nitroanilinu. Suspenze se za stálého míchání zahřeje na teplotu 60 až 70 °C a po rozpuštění 4-nitroanilinu se přidá 0,5 mol 1,2-dihydroxycyklobutendionu a 0,005 mol HCIO^ jako katalyzátoru. Potom se nechá teplota vystoupit na teplotu varu reakční směsi a je udržována po dobu 8 hodin. Reakcí vznikající voda je během reakce oddělována v azeotropickém nástavci. Vyloučené žluté barvivo se po ochlazení odfiltruje a promyje horkou směeí použitých rozpustidel. Získané barvivo vzorce VII má teplotu tání 360 °C a získá se ve výtěžku 88 ».500 ml of a 1: 1 mixture of benzene and n-butanol are added to a closed apparatus equipped with a stirrer and azeotropic distillation head for the reaction of the resulting water, and 1.05 mol of 4-nitroaniline is added. The suspension is heated to 60-70 ° C with stirring, and after dissolution of 4-nitroaniline, 0.5 mol of 1,2-dihydroxycyclobutenedione and 0.005 mol of HClO 2 are added as catalyst. The temperature is then allowed to rise to the boiling point of the reaction mixture and is maintained for 8 hours. The water produced by the reaction is separated in the azeotropic cap during the reaction. The yellow precipitate formed is filtered off after cooling and washed with a hot mixture of the solvents used. The dye of formula VII obtained has a melting point of 360 DEG C. and is obtained in a yield of 88 DEG.
Příklad 2Example 2
Syntéza je prováděna za stejných podmínek jako v příkladu 1 s tím rozdílem, že jako výchozí aiylamin je použit 2-brom-4-nitroanilin. Po ochlazení, filtraci a promytí se zís4 (VIII)The synthesis is carried out under the same conditions as in Example 1, except that 2-bromo-4-nitroaniline is used as the starting amine. After cooling, filtration and washing, 4 (VIII) is obtained.
Příklad 3Example 3
Postup je obdobný jako v příkladu 1, jako arylamin je použit 4-aminoazobenzen. Reakce probíhá za stejných podmínek jako v předchozím příkladu 10 hodin. Získá se tmavě žlutá barvivo vzorce IX ve výtěžku 83 %, která do teploty 360 °C netaje.The procedure is analogous to Example 1 except that 4-aminoazobenzene is used as the arylamine. The reaction proceeds under the same conditions as in the previous example for 10 hours. A dark yellow dye of formula IX is obtained in a yield of 83%, which does not melt up to 360 ° C.
Příklad 4Example 4
Kondenzace probíhá za stejných podmínek jako v předchozích příkladech po dobu 6 hodin. Jako výchozí arylamin je použit 4-aminoacetofenon, který poskytuje žluté barvivo vzorce X ve výtěžku βΐ %. Tato látka do teploty 360 °C netaje.Condensation is carried out under the same conditions as in the previous examples for 6 hours. 4-Aminoacetophenone is used as the starting arylamine to give a yellow dye of formula X in a yield of βΐ%. This substance does not melt up to 360 ° C.
οΘοΘ
Příklad 5Example 5
Reakce probíhá za stejných podmínek jako v předchozích příkladech po dobu 8 hodin. Jako výchozí axylaain je použit N-acetyl-3-nitro-6-hydrozyanilin, který poskytuje světle žlutý pigment vzorce XI, ve výtěžku 90 % do teploty 360 °C netající.The reaction proceeds under the same conditions as in the previous examples for 8 hours. N-Acetyl-3-nitro-6-hydrozyaniline, which gives a pale yellow pigment of formula XI, in a yield of 90% up to a temperature of 360 ° C melting, is used as the starting axylaine.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS553878A CS198004B1 (en) | 1978-08-25 | 1978-08-25 | Method of preparing yellow pigments derived from cyclobutene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS553878A CS198004B1 (en) | 1978-08-25 | 1978-08-25 | Method of preparing yellow pigments derived from cyclobutene |
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| Publication Number | Publication Date |
|---|---|
| CS198004B1 true CS198004B1 (en) | 1980-05-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS553878A CS198004B1 (en) | 1978-08-25 | 1978-08-25 | Method of preparing yellow pigments derived from cyclobutene |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS198004B1 (en) |
-
1978
- 1978-08-25 CS CS553878A patent/CS198004B1/en unknown
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