CA1071208A - Preparation of quinacridone using fecl3 - Google Patents
Preparation of quinacridone using fecl3Info
- Publication number
- CA1071208A CA1071208A CA261,796A CA261796A CA1071208A CA 1071208 A CA1071208 A CA 1071208A CA 261796 A CA261796 A CA 261796A CA 1071208 A CA1071208 A CA 1071208A
- Authority
- CA
- Canada
- Prior art keywords
- quinacridone
- dihydroquinacridone
- preparation
- liquid
- fecl3
- 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.)
- Expired
Links
Classifications
-
- 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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0025—Crystal modifications; Special X-ray patterns
- C09B67/0027—Crystal modifications; Special X-ray patterns of quinacridones
-
- 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
- C09B48/00—Quinacridones
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
ABSTRACT
Improved process for preparing quinacridone pigment by oxidizing the corresponding dihydroquinacridone wherein the dihydroquinacridone is oxidized in the liquid organic medium in which it is prepared using FeCl3 and, optionally, in the presence of N-methyl-2-pyrrolidone.
The process eliminates the need to isolate the dihydroquin-acridone prior to oxidation and enables recovery of the organic liquid employed.
Improved process for preparing quinacridone pigment by oxidizing the corresponding dihydroquinacridone wherein the dihydroquinacridone is oxidized in the liquid organic medium in which it is prepared using FeCl3 and, optionally, in the presence of N-methyl-2-pyrrolidone.
The process eliminates the need to isolate the dihydroquin-acridone prior to oxidation and enables recovery of the organic liquid employed.
Description
1~71Z08 This invention relates to an lmproved process for the preparation of quinacridone pigment and particularly to an improved process for oxidizing dihydroquinacridone to the corresponding quinacridone in a liquid organic medium with or without simultaneous control of the crystal phase in the quinacridone so produced.
A wide variety Or processes for preparing quin-acridone pigment by oxidation of the corresponding dihydro-qulnacridone are known in the art. The first such process involves cyclizing a dialkyl 2,5-diarylamino-3,6-dihydro-terephthalate in an organic liquid at elevated temperatures to rorm the corresponding dihydroquinacridone, separating the dihydroquinacridone from the organic liquid, and then oxldiæing. The oxidation is done in aqueous alcoholic alkali solutions with certain mild oxidlzing agents, such as the sodlum salt of nitrobenzene-m-sulfonic acid, air or oxygen. The phase Or the resulting quinacridone can be controlled by adJusting the concentration Or water, alkali, and alcohol in which the oxidation is carried out.
Since the reaction medium for the preparation of dihydroqulnacridone is different from that in which oxida-tlon and, ln some cases, phase control take place, the above-discussed processes require the isolation of dihydro-quinacridone prior to oxidation.
One attempt to provide a continuous process for producing quinacridone plgment, i.e., without the need to isolate the dihydroquinacridone, and to provide some means o~ phase control in the quinacridone so produced involves oxldatlon of dihydroquinacridone to the corresponding quin-acridone in a medium consisting essentially Or a mixture of E~y' ~07~Z08 an alkali~ water, and tetramethylene sulfone at an elevated temperature using less than the stoichiometric quantlty of a polycyclic aromatic quinone compound, e.g., anthraqulnone, naphthoquinone, phenanthraquinone, as the oxidant and con-- currently regenerating the quinone compound by blowing a gas containing elemental oxygen through the reaction mixture.
The resulting pigment ls then recovered ln the ~-phase by rapldly adding the oxldation mixture to a large volume of cold water or recovered in the y-phase by slowly adding hot .0 water to the oxidation mixture malntalned near the boiling point.
Although ln accordance wlth the process descrlbed above the dihydroqulnacrldone which can be syntheslzed in tetramethylene sulfone need not be isolated prior to oxida-tion, the presence of caustic and water for the oxidation renders recovery Or the organlc llquld, i.e., tetramethylene sulfone, extremely dlfflcult. Furthermore, ln order to obtaln qulnacrldone ln a predetermlned crystal phase addi-tlonal process steps are requlred.
'0 This lnvention provides ror an improved process ror the preparation of quinacridone utillzing FeC13 to rapidly oxldize dih~droquinacridone in the llquld organic medlum ln which it is prepared; this eliminated the need to isolate the dihydroqulnacrldone prlor to oxldatlon, permits eas~ recover~ Or the or~anlc liquid for reuse, and provides ror phase control ~lthout additional Drocessing.
In accordance wlth this invention there is pro-vided an lmproved process for the nreparation Or auin-acrldone pi~ment o~ the ~eneral formula - . - . .
107~Z()~
o H "
Xk~C~II '~ Ym O H
where X and Y are radicals sele~ted ~rom the group consist-ing of F, Cl, Br, alkyl having 1 to 3 carbon atoms, and alkoxy having 1 to 3 carbon atoms, or comblnations thereof, and k and m are integers from O to 2, by heating the cor-responding dialkyl 2, 5-diarylamino-3,6-dihydroterephthalate in a liquld organlc medium to form the corresponding dihydro-quinacrldone and oxidizlng said dihydroquinacridone at elevated temperatures to form said quinacridone. The lmprovement resldes ln conducting the oxidation in the presence of FeC13 a~ oxidizing agent and in the liquid organic medlum in which the dihydroquinacridone is prepared.
When the quinacridone produced in accordance with the lnvention is unsubstituted, phase control can be affected during oxidatlon by proper cholce of the llquld organlc medium ln whlch the oxldatlon 18 conducted. For example, qulnacrldone ln the ~-phase is produced using as the llquid organic medium tetramethylene sulrone alone or a mlxture of dlmethyl formamlde or an aliphatlc amide such AB N-methyl-2-pyrrolldone wlth a varlety of lnert aromatic llquids such as blphenyl, diphenyl oxide, terphenyl, 1-chloronaphthalene, or mlxtures thereof. Other aliphatic amldes whlch may be useful include 2-pyrrolldone, 2-piperldone, N-methyl-2-plperidone, dimethyl acetamide, and N,N-dlethylpropanamide. Unsubstltuted qulnacridone ln the ~-phase can be produced during the oxidation by utillzlng 1~712(~
a mixture of dlmethylformamide wlth the inert aromatic li~uids specified above. Mixtures of tetramethylene sulfone with the ~ne.t aromatic liquids specified above produce the quinacridone hydrochloride salt which must be hydrolyzed with phase control to produce quinacridone in the or ~-phase~
The FeC13 utilized as the oxidizing agent can be anhydrous or hydrated. Hydrated FeC13, particularly FeC13 hexahydratQ, is preferred to obtain a quinacridone of -. :
especially high purity. The FeC13 can be added to the llquld organic med~um as a substantially dry solid or in the form of an aqueous solution. In practice, good quality quinacrldone can be produced when the weight ratio of FeC13 to the dlhydroquinacridone is from 1.0:1 to 1.8:1. To insure the hlghest conversion of the dihydroqulnacridone and avoid unnecessary excess of FeC13, it is preferred that the welght ratlo of FeC13 to the dlhydroqulnacrldone to be oxi-dlzed be from 1.0:1 to 1.5:1.
For ease of handllng and high converslon, lt is preferred that the welght ratlo of the llquid organlc medium to the dlhydroqulnacrldone to be oxldized be from 5:1 to 35:1, although more dllute reaction mixtures can be success-fully oxldlzed. When mlxtures of N-methyl-2-pyrrolldone with lnert aromatlc liqulds are utlllzed for the oxldation, lt ls preferred that the welght ratlo of the N-methyl-2-pyrrolldone to dlhydroquinacrldone be from 1:1 to 6:1, and more preferably from 1.5:1 to 2.5:1 to insure optlmum phase control. For dimethyl formamide, it ls preferred that the weight ratio of dimethyl formamide to dlhydroquinacridone be from 1.5:1 ` 30 to 2.5:1 to lnsure optimum phsse control and good conversion ~71Z08 during the oxidation. ~arger amounts of dimethyl formamide or N-methyl 2-pyrrolidone are not recommended because these organic liquids complex with the FeC13 and prevent hlgh conversion.
As stated above, a mixture of tetramethylene sulfone and inert aromatic liquid can be ukilized as the A llquid organic medlum for the oxidation. In this case the quinacridone produced is in the form of a hydrochloride salt and must be sub~ected to hydrolysis under specific 10 conditions to produce quinacridone in a particular phase.
Adequate conversion to the quinacridone hydroch-loride salt is assured utilizing a weight ratio of tetramethylene sulfone to inert aromatic liquid from 1:4 to 1:20. For the best combination of high conversion and economy, a welght ratlo from 1:9 to 1:20 is preferred. The quin-acridone hydrochloride salt must first be isolated from the llquid organic medium and washed free of any impurities which may be present from cyclization. After isolat~on the qulnacridone hydrochloride salt is contacted with water 20 to produce ~-phase quinacridone or wlth alcohol, e.g., methanol, ethanol, to produce ~-phase quinacridone. To produce ~-phase quinacridone the quinacridone hydrochlorlde salt can be contacted with tetramethylene sulfone, N-methyl-
A wide variety Or processes for preparing quin-acridone pigment by oxidation of the corresponding dihydro-qulnacridone are known in the art. The first such process involves cyclizing a dialkyl 2,5-diarylamino-3,6-dihydro-terephthalate in an organic liquid at elevated temperatures to rorm the corresponding dihydroquinacridone, separating the dihydroquinacridone from the organic liquid, and then oxldiæing. The oxidation is done in aqueous alcoholic alkali solutions with certain mild oxidlzing agents, such as the sodlum salt of nitrobenzene-m-sulfonic acid, air or oxygen. The phase Or the resulting quinacridone can be controlled by adJusting the concentration Or water, alkali, and alcohol in which the oxidation is carried out.
Since the reaction medium for the preparation of dihydroqulnacridone is different from that in which oxida-tlon and, ln some cases, phase control take place, the above-discussed processes require the isolation of dihydro-quinacridone prior to oxidation.
One attempt to provide a continuous process for producing quinacridone plgment, i.e., without the need to isolate the dihydroquinacridone, and to provide some means o~ phase control in the quinacridone so produced involves oxldatlon of dihydroquinacridone to the corresponding quin-acridone in a medium consisting essentially Or a mixture of E~y' ~07~Z08 an alkali~ water, and tetramethylene sulfone at an elevated temperature using less than the stoichiometric quantlty of a polycyclic aromatic quinone compound, e.g., anthraqulnone, naphthoquinone, phenanthraquinone, as the oxidant and con-- currently regenerating the quinone compound by blowing a gas containing elemental oxygen through the reaction mixture.
The resulting pigment ls then recovered ln the ~-phase by rapldly adding the oxldation mixture to a large volume of cold water or recovered in the y-phase by slowly adding hot .0 water to the oxidation mixture malntalned near the boiling point.
Although ln accordance wlth the process descrlbed above the dihydroqulnacrldone which can be syntheslzed in tetramethylene sulfone need not be isolated prior to oxida-tion, the presence of caustic and water for the oxidation renders recovery Or the organlc llquld, i.e., tetramethylene sulfone, extremely dlfflcult. Furthermore, ln order to obtaln qulnacrldone ln a predetermlned crystal phase addi-tlonal process steps are requlred.
'0 This lnvention provides ror an improved process ror the preparation of quinacridone utillzing FeC13 to rapidly oxldize dih~droquinacridone in the llquld organic medlum ln which it is prepared; this eliminated the need to isolate the dihydroqulnacrldone prlor to oxldatlon, permits eas~ recover~ Or the or~anlc liquid for reuse, and provides ror phase control ~lthout additional Drocessing.
In accordance wlth this invention there is pro-vided an lmproved process for the nreparation Or auin-acrldone pi~ment o~ the ~eneral formula - . - . .
107~Z()~
o H "
Xk~C~II '~ Ym O H
where X and Y are radicals sele~ted ~rom the group consist-ing of F, Cl, Br, alkyl having 1 to 3 carbon atoms, and alkoxy having 1 to 3 carbon atoms, or comblnations thereof, and k and m are integers from O to 2, by heating the cor-responding dialkyl 2, 5-diarylamino-3,6-dihydroterephthalate in a liquld organlc medium to form the corresponding dihydro-quinacrldone and oxidizlng said dihydroquinacridone at elevated temperatures to form said quinacridone. The lmprovement resldes ln conducting the oxidation in the presence of FeC13 a~ oxidizing agent and in the liquid organic medlum in which the dihydroquinacridone is prepared.
When the quinacridone produced in accordance with the lnvention is unsubstituted, phase control can be affected during oxidatlon by proper cholce of the llquld organlc medium ln whlch the oxldatlon 18 conducted. For example, qulnacrldone ln the ~-phase is produced using as the llquid organic medium tetramethylene sulrone alone or a mlxture of dlmethyl formamlde or an aliphatlc amide such AB N-methyl-2-pyrrolldone wlth a varlety of lnert aromatic llquids such as blphenyl, diphenyl oxide, terphenyl, 1-chloronaphthalene, or mlxtures thereof. Other aliphatic amldes whlch may be useful include 2-pyrrolldone, 2-piperldone, N-methyl-2-plperidone, dimethyl acetamide, and N,N-dlethylpropanamide. Unsubstltuted qulnacridone ln the ~-phase can be produced during the oxidation by utillzlng 1~712(~
a mixture of dlmethylformamide wlth the inert aromatic li~uids specified above. Mixtures of tetramethylene sulfone with the ~ne.t aromatic liquids specified above produce the quinacridone hydrochloride salt which must be hydrolyzed with phase control to produce quinacridone in the or ~-phase~
The FeC13 utilized as the oxidizing agent can be anhydrous or hydrated. Hydrated FeC13, particularly FeC13 hexahydratQ, is preferred to obtain a quinacridone of -. :
especially high purity. The FeC13 can be added to the llquld organic med~um as a substantially dry solid or in the form of an aqueous solution. In practice, good quality quinacrldone can be produced when the weight ratio of FeC13 to the dlhydroquinacridone is from 1.0:1 to 1.8:1. To insure the hlghest conversion of the dihydroqulnacridone and avoid unnecessary excess of FeC13, it is preferred that the welght ratlo of FeC13 to the dlhydroqulnacrldone to be oxi-dlzed be from 1.0:1 to 1.5:1.
For ease of handllng and high converslon, lt is preferred that the welght ratlo of the llquid organlc medium to the dlhydroqulnacrldone to be oxldized be from 5:1 to 35:1, although more dllute reaction mixtures can be success-fully oxldlzed. When mlxtures of N-methyl-2-pyrrolldone with lnert aromatlc liqulds are utlllzed for the oxldation, lt ls preferred that the welght ratlo of the N-methyl-2-pyrrolldone to dlhydroquinacrldone be from 1:1 to 6:1, and more preferably from 1.5:1 to 2.5:1 to insure optlmum phase control. For dimethyl formamide, it ls preferred that the weight ratio of dimethyl formamide to dlhydroquinacridone be from 1.5:1 ` 30 to 2.5:1 to lnsure optimum phsse control and good conversion ~71Z08 during the oxidation. ~arger amounts of dimethyl formamide or N-methyl 2-pyrrolidone are not recommended because these organic liquids complex with the FeC13 and prevent hlgh conversion.
As stated above, a mixture of tetramethylene sulfone and inert aromatic liquid can be ukilized as the A llquid organic medlum for the oxidation. In this case the quinacridone produced is in the form of a hydrochloride salt and must be sub~ected to hydrolysis under specific 10 conditions to produce quinacridone in a particular phase.
Adequate conversion to the quinacridone hydroch-loride salt is assured utilizing a weight ratio of tetramethylene sulfone to inert aromatic liquid from 1:4 to 1:20. For the best combination of high conversion and economy, a welght ratlo from 1:9 to 1:20 is preferred. The quin-acridone hydrochloride salt must first be isolated from the llquid organic medium and washed free of any impurities which may be present from cyclization. After isolat~on the qulnacridone hydrochloride salt is contacted with water 20 to produce ~-phase quinacridone or wlth alcohol, e.g., methanol, ethanol, to produce ~-phase quinacridone. To produce ~-phase quinacridone the quinacridone hydrochlorlde salt can be contacted with tetramethylene sulfone, N-methyl-
2-pyrrolidone, or dimethylformamide, or mixtures thereof.
Slnce among the advantages afforded by the practice of the lnventlon are the eliminatlon of the need to lsolate the dlhydroqulnacrldone prior to oxldatlon and enablement of recovery of the llquid organic medlum, the liquid organlc medium employed in the oxidatlon must naturally be sub-30 stantlally the same as that utlllzed ln the synthesls of the dihydroquinacridone. Ilowever, in theevent that the weight ratio of the liquid organic med-~um used in the dihydroquinacrldone s~nthesis to the dihydroquinacridone so produced ls less than that preferred for the practice of the oxidation in accordance with this invention, it is recommended that sufficient additional liquid organic medium be added to the synthesis prior to oxidation or simultaneously with the addition Or FeC13 to bring the amount Or liquid or~anic medium up to the preferred ratio, Where N-methyl-2-pyrrolidone, dimethyl formamide, or tetra-methylene sulrone are employed in con,~unction with an inert aromatic liquid, the inert aromatic liquid must be the same as the liquid organic medium utilized in the synthesis of the dihydroquinacridone. Furthermore, the N-methyl-2-pyrrolidone, dlmethyl formamide, or tetramethylene sulfone are preferably added in the amounts specified above to the llquld organic medium prior to oxidation or simultaneously with the addltion of FeC13 to prevent these substances ~rom possibl,y interrering with the synthesis of the dihydro-quinacridone, The oxidation of the dlhydroquinacridone in accor-dance wlth the invention can be conducted at a temperature from 150C, to the bolllng point of the llquld organic medlum employed. In the case of the preparation of un-substltuted qulnacrldone in a predetermined crystal phase, it ls prererred that the oxidation be conducted at a temperature from 195C, to 205C~ to insure the prepara-tlon of a slngle phase product. For example at oxldation temperatures in excess of 225C., mixtures of e- and y-phase qulnacridone can be produced from the oxldation of .
. - ~ . .
1~7~Z08 dihydroquinacridone in an N-methyl-2-pyrrolidone, biphenyl, diphenyl oxide solvent system. In substantially the same solvent system oxidatlon at 150C. gives predominantly ~-phase quinacridone.
After oxidation the resulting quinacridone can be isolated rrom the liquid organic medium by filtra-tion and is preferably washed with methanol to remove iron salts and impurities which may be present from the prepara-tion of the dihydroquinacridone. The quinacridone can be used directly as a pigment for a variety of applications or sub~ected to further rinishing procedures well known to those skilled in the art. The liquid organic medium can be recycled without the need ror further processing ~or use in the synthesis Or dihydroquinacridone. In the ca~e where the liquid o~ganic medium in ~hich the oxidation is conducted consists essentially of a mixture Or N-methyl-2-pyrrolidone,dimethyl formamide, or tetramethylene sulrone with inert aromatlc li~uid, the solvent mixtures can be separated, for example, by fractional distillation prlor to recycling to the dihydro~uinacridone synthesis, if desired.
The dialkyl 2,5-diarylamino-3,6-dihydroterephtha-lates userul as startlng materials in the preparation Or the correspondlng dlhydroquinacridone are well known in the art and can be prepared, ror example, by known processes.
A typlcal process lnvolves condenslng two moles of dlalkyl succlnate ln a high boillng inert llquld in the presence Or an alkaline catalyst to rorm dlalkyl succinyl succinate, neutrallzlng the excess alkali, condensing the dlalkyl succinyl succinate with anillne or other aromatic amine in the presence of an excess of the amine and a catalytic amount of a salt of the amine soluble in the reactiorl mlx-ture, neutralizing the acld and removing the excess amine under nonoxidi%ing conditions.
The preparation of a dihydroquinacridone from the corresponding dialkyl 2,5-diarylamino-3,6-dlhydroterephthalate is commonly practiced in the art by heating the dialkyl 2,5-diarylamino-3,6-dihydroterephthalate to elevated temperatures, preferably from 225~C. to 300C., in an inert high boiling liquid to effect cyclization and thereby produce the corresponding dihydroquinacridone. The principal consideration, aside from inertness, governing the choice Or inert high boilin~ liguid in which to erfect cycli-zation ls the boiling point. The liquid should have a boiling point above the temperature at which the reaction ls to be carried out, yet it should not be so high as to preclude its removal from the reaction mixture by distillation.
For the practice of this invention it is desirable that, ln additlon to the crlteria known in the art, the lnert hlgh boiling llquid also be an appropriate reactlon medlum ln which to conduct the oxidation with FeC13. '~-That ls, the lnert high boiling liquld must not undergo reaction under the conditlons Or the cyclization and under the condltions Or the oxidation, Therefore it ls prererred that the lnert hlgh boiling liquid be an lnert aromatic liquld, A particularly sultable lnert aro-matic liquid for the cyclization of the dihydro esters to the corresponding dlhydroquinacridone is a eutectic mixture o~ biphenyl and dlphenyl oxide. Other liquid organic media such as tetramethylene sulfone, biphenyl, diphenyl oxlde, ~7~z08 terphenyl, and l-chloronaphthalene are also useful.
The quinacridone pigmentsprepared in accordance with the invention are well known and widely used to impart color to a variety of coating compositions such as emulsion paints, automotive enamels, etc. They can be mixed with conventional fillers, extenders, and vehicles by techniques well known in the art to produce useful paints exhibiting colors from bluish red to violet.
The examples detailed below are intended to illus-trate the practice of the invention.
Examples 1-7 Thirty-one grams of unsubstituted 6,13-dihydro-quinacridone, prepared ln accordance with the procedure descrlbed ln U. S. Patent 2,821,529 by heating diethyl 2,5-dlanilino-~,6-dlhydroterephthalate in a eutectic mixture Or 23.5% by weight oP biphenyl and 76.5% by weight Or diphenyl oxide to 250C.-257C. for one hour in a nitrogen atmosphere, is mixed with FeC13 6H20, r~-methyl-2-pyrrolidone, and the eutectic mixture described above in the amounts shown in Table I. The mlxture ls heated to 190C.-210C.
Por about two hours. Arter cooling the resulting quin- ~-acridone is lsolated from the mlxture by filtration, ~ashed wlth meth~nol, and drled. The respectlve products are analyzed by X-ray and Pound to conslst essentially Or y-phase quinacridone. The percent conversions to y-phase qulnacrldone are shown ln Table I.
Example 8 Four hundred grams Or a 19~ by weight slurry of qulnacrldone in a eutectic mixture of 23.5% by weight Or biphenyl and 76.5% by weight Or diphenyl oxlde at 200C., prepared in accordance with the procedure described~ln U. S.
Patent 2,821,529 by heating diethyl-2,5-dianilino-3,6-dihydroterephthalate in the eutectic mixture to 250C.-257C. for one hour in a nitrogen atmosphere, is mixed with a hot (200C.) solution Or 166.8 g ferric c~lloride hexa-hydrate in 126.8 g N-methyl-2-pyrrolidone. The mixture is held at 195C.-205C. for about 0.5 hour. The resultlng quinacridone is isolated from the mixture by filtration, washed with methanol, washed with water, and dried. Analysis Or the product by X-ray diffraction shows it to consist essentially of y-phase quinacridone (97% conversion).
Exam~le 9 Thirty-one grams of 6,13-dihydroquinacridone is combined with 450 g biphenyl, 50 g of tetramethylene sulfone, and 56.o g ferrlc chloride hexahydrate. The mixture ls heated to 180C. and held between 180C.-200C. for one hour. Filtration gives a purple quinacridone hydrochloride salt that is then reslurried in 200 milliliters of di-methylformami.de for 0.5 hour. The pigment is obtained by ~lltration, washing with methanol, washing with water, and dryin~. Analysis by X-ray diffraction shows the product to '~
conslst essentially of y-phase quinacridone (97% conversion).
ExamDle 10 Fl~teen and one-half ~rams of 6,13-dihydroquinacri-done is combined with 28.0 g ferric chloride, 509 g Or the biphenyl-diphenyl oxide eutectic, and 23.6 g dimethylformamide.
The mixture is heated to 180C. and held at 180C.-190C.
ror about 0.5 hour. The reaction mixture is allowed to cool, ~iltered, and the ~roduct washed with methanol followed by water. Drying gives a product which consists essentially of ~".
.
B-phase quinacridone, as determined by X-ray diffraction analysis, in 97% ,yield with 95% conversion.
Example 11 Three and one-tenth grams of 6,13-dihydroquinacridone is suspended in 50 milliliters of tetramethylene sulfone and 5.4 g of ferric chloride hexahydrate is added to the reaction mixture. The mixture is heated to 200C. and held at 195C.-205C. for about one hour. The reaction mixture is allowed to cool and is then filtered. The pigment is then washed wlth methanol, washed ~Jith water, and dried.
The product consists essentially of y-~has,e quinacridone as determined by X-ra,y diPfraction analysis. The conversion of 6,13-dihydroquinacridone to quinacridone in this reaction is 100%.
~1 ~ `
71208 ~ : -a~
o o .,, U~
h h c o a:) ~1 ~ In ~o r- O
O
C) I b~ ~ :
~' '~ ~1 J~ h L~ o O :~ ~i ~O a t_ ~ ~, ,~ .
J~ X IJ~
. ~ 3 3 3 J ~ 3 3 . ,' U~
~ I a) a~ ~u ~
~ I O
H ~1 r-l ~
a) ~r~ ~ G~ C~ ~ ~O ~) O
~1 ,I:~ol C~
m ~ ~ cc t~ 3 z r.
C
K O
::~
. oo ~t> 3 ~Y O
.
~ c~ J t-- O It~
C~ ~
~ ~ J ~ 3 X
~ .
Slnce among the advantages afforded by the practice of the lnventlon are the eliminatlon of the need to lsolate the dlhydroqulnacrldone prior to oxldatlon and enablement of recovery of the llquid organic medlum, the liquid organlc medium employed in the oxidatlon must naturally be sub-30 stantlally the same as that utlllzed ln the synthesls of the dihydroquinacridone. Ilowever, in theevent that the weight ratio of the liquid organic med-~um used in the dihydroquinacrldone s~nthesis to the dihydroquinacridone so produced ls less than that preferred for the practice of the oxidation in accordance with this invention, it is recommended that sufficient additional liquid organic medium be added to the synthesis prior to oxidation or simultaneously with the addition Or FeC13 to bring the amount Or liquid or~anic medium up to the preferred ratio, Where N-methyl-2-pyrrolidone, dimethyl formamide, or tetra-methylene sulrone are employed in con,~unction with an inert aromatic liquid, the inert aromatic liquid must be the same as the liquid organic medium utilized in the synthesis of the dihydroquinacridone. Furthermore, the N-methyl-2-pyrrolidone, dlmethyl formamide, or tetramethylene sulfone are preferably added in the amounts specified above to the llquld organic medium prior to oxidation or simultaneously with the addltion of FeC13 to prevent these substances ~rom possibl,y interrering with the synthesis of the dihydro-quinacridone, The oxidation of the dlhydroquinacridone in accor-dance wlth the invention can be conducted at a temperature from 150C, to the bolllng point of the llquld organic medlum employed. In the case of the preparation of un-substltuted qulnacrldone in a predetermined crystal phase, it ls prererred that the oxidation be conducted at a temperature from 195C, to 205C~ to insure the prepara-tlon of a slngle phase product. For example at oxldation temperatures in excess of 225C., mixtures of e- and y-phase qulnacridone can be produced from the oxldation of .
. - ~ . .
1~7~Z08 dihydroquinacridone in an N-methyl-2-pyrrolidone, biphenyl, diphenyl oxide solvent system. In substantially the same solvent system oxidatlon at 150C. gives predominantly ~-phase quinacridone.
After oxidation the resulting quinacridone can be isolated rrom the liquid organic medium by filtra-tion and is preferably washed with methanol to remove iron salts and impurities which may be present from the prepara-tion of the dihydroquinacridone. The quinacridone can be used directly as a pigment for a variety of applications or sub~ected to further rinishing procedures well known to those skilled in the art. The liquid organic medium can be recycled without the need ror further processing ~or use in the synthesis Or dihydroquinacridone. In the ca~e where the liquid o~ganic medium in ~hich the oxidation is conducted consists essentially of a mixture Or N-methyl-2-pyrrolidone,dimethyl formamide, or tetramethylene sulrone with inert aromatlc li~uid, the solvent mixtures can be separated, for example, by fractional distillation prlor to recycling to the dihydro~uinacridone synthesis, if desired.
The dialkyl 2,5-diarylamino-3,6-dihydroterephtha-lates userul as startlng materials in the preparation Or the correspondlng dlhydroquinacridone are well known in the art and can be prepared, ror example, by known processes.
A typlcal process lnvolves condenslng two moles of dlalkyl succlnate ln a high boillng inert llquld in the presence Or an alkaline catalyst to rorm dlalkyl succinyl succinate, neutrallzlng the excess alkali, condensing the dlalkyl succinyl succinate with anillne or other aromatic amine in the presence of an excess of the amine and a catalytic amount of a salt of the amine soluble in the reactiorl mlx-ture, neutralizing the acld and removing the excess amine under nonoxidi%ing conditions.
The preparation of a dihydroquinacridone from the corresponding dialkyl 2,5-diarylamino-3,6-dlhydroterephthalate is commonly practiced in the art by heating the dialkyl 2,5-diarylamino-3,6-dihydroterephthalate to elevated temperatures, preferably from 225~C. to 300C., in an inert high boiling liquid to effect cyclization and thereby produce the corresponding dihydroquinacridone. The principal consideration, aside from inertness, governing the choice Or inert high boilin~ liguid in which to erfect cycli-zation ls the boiling point. The liquid should have a boiling point above the temperature at which the reaction ls to be carried out, yet it should not be so high as to preclude its removal from the reaction mixture by distillation.
For the practice of this invention it is desirable that, ln additlon to the crlteria known in the art, the lnert hlgh boiling llquid also be an appropriate reactlon medlum ln which to conduct the oxidation with FeC13. '~-That ls, the lnert high boiling liquld must not undergo reaction under the conditlons Or the cyclization and under the condltions Or the oxidation, Therefore it ls prererred that the lnert hlgh boiling liquid be an lnert aromatic liquld, A particularly sultable lnert aro-matic liquid for the cyclization of the dihydro esters to the corresponding dlhydroquinacridone is a eutectic mixture o~ biphenyl and dlphenyl oxide. Other liquid organic media such as tetramethylene sulfone, biphenyl, diphenyl oxlde, ~7~z08 terphenyl, and l-chloronaphthalene are also useful.
The quinacridone pigmentsprepared in accordance with the invention are well known and widely used to impart color to a variety of coating compositions such as emulsion paints, automotive enamels, etc. They can be mixed with conventional fillers, extenders, and vehicles by techniques well known in the art to produce useful paints exhibiting colors from bluish red to violet.
The examples detailed below are intended to illus-trate the practice of the invention.
Examples 1-7 Thirty-one grams of unsubstituted 6,13-dihydro-quinacridone, prepared ln accordance with the procedure descrlbed ln U. S. Patent 2,821,529 by heating diethyl 2,5-dlanilino-~,6-dlhydroterephthalate in a eutectic mixture Or 23.5% by weight oP biphenyl and 76.5% by weight Or diphenyl oxide to 250C.-257C. for one hour in a nitrogen atmosphere, is mixed with FeC13 6H20, r~-methyl-2-pyrrolidone, and the eutectic mixture described above in the amounts shown in Table I. The mlxture ls heated to 190C.-210C.
Por about two hours. Arter cooling the resulting quin- ~-acridone is lsolated from the mlxture by filtration, ~ashed wlth meth~nol, and drled. The respectlve products are analyzed by X-ray and Pound to conslst essentially Or y-phase quinacridone. The percent conversions to y-phase qulnacrldone are shown ln Table I.
Example 8 Four hundred grams Or a 19~ by weight slurry of qulnacrldone in a eutectic mixture of 23.5% by weight Or biphenyl and 76.5% by weight Or diphenyl oxlde at 200C., prepared in accordance with the procedure described~ln U. S.
Patent 2,821,529 by heating diethyl-2,5-dianilino-3,6-dihydroterephthalate in the eutectic mixture to 250C.-257C. for one hour in a nitrogen atmosphere, is mixed with a hot (200C.) solution Or 166.8 g ferric c~lloride hexa-hydrate in 126.8 g N-methyl-2-pyrrolidone. The mixture is held at 195C.-205C. for about 0.5 hour. The resultlng quinacridone is isolated from the mixture by filtration, washed with methanol, washed with water, and dried. Analysis Or the product by X-ray diffraction shows it to consist essentially of y-phase quinacridone (97% conversion).
Exam~le 9 Thirty-one grams of 6,13-dihydroquinacridone is combined with 450 g biphenyl, 50 g of tetramethylene sulfone, and 56.o g ferrlc chloride hexahydrate. The mixture ls heated to 180C. and held between 180C.-200C. for one hour. Filtration gives a purple quinacridone hydrochloride salt that is then reslurried in 200 milliliters of di-methylformami.de for 0.5 hour. The pigment is obtained by ~lltration, washing with methanol, washing with water, and dryin~. Analysis by X-ray diffraction shows the product to '~
conslst essentially of y-phase quinacridone (97% conversion).
ExamDle 10 Fl~teen and one-half ~rams of 6,13-dihydroquinacri-done is combined with 28.0 g ferric chloride, 509 g Or the biphenyl-diphenyl oxide eutectic, and 23.6 g dimethylformamide.
The mixture is heated to 180C. and held at 180C.-190C.
ror about 0.5 hour. The reaction mixture is allowed to cool, ~iltered, and the ~roduct washed with methanol followed by water. Drying gives a product which consists essentially of ~".
.
B-phase quinacridone, as determined by X-ray diffraction analysis, in 97% ,yield with 95% conversion.
Example 11 Three and one-tenth grams of 6,13-dihydroquinacridone is suspended in 50 milliliters of tetramethylene sulfone and 5.4 g of ferric chloride hexahydrate is added to the reaction mixture. The mixture is heated to 200C. and held at 195C.-205C. for about one hour. The reaction mixture is allowed to cool and is then filtered. The pigment is then washed wlth methanol, washed ~Jith water, and dried.
The product consists essentially of y-~has,e quinacridone as determined by X-ra,y diPfraction analysis. The conversion of 6,13-dihydroquinacridone to quinacridone in this reaction is 100%.
~1 ~ `
71208 ~ : -a~
o o .,, U~
h h c o a:) ~1 ~ In ~o r- O
O
C) I b~ ~ :
~' '~ ~1 J~ h L~ o O :~ ~i ~O a t_ ~ ~, ,~ .
J~ X IJ~
. ~ 3 3 3 J ~ 3 3 . ,' U~
~ I a) a~ ~u ~
~ I O
H ~1 r-l ~
a) ~r~ ~ G~ C~ ~ ~O ~) O
~1 ,I:~ol C~
m ~ ~ cc t~ 3 z r.
C
K O
::~
. oo ~t> 3 ~Y O
.
~ c~ J t-- O It~
C~ ~
~ ~ J ~ 3 X
~ .
Claims (5)
1. In a process for the preparation of quinacri-done pigment of the general formula where X and Y are radicals selected from the group con-sisting of F, Cl, Br, alkyl having 1 to 3 carbon atoms and alkoxy having 1 to 3 carbon atoms, or combinations thereof, and k and m are integers from 0 to 2, by heating the corresponding dialkyl 2,5-diarylamino-3,6-dihydro-terephthalate in a liquid organic medium to form the corre-sponding dihydroquinacridone and oxidizing said dihydro-quinacridone at an elevated temperature to form said quinacridone, the improvement comprising conducting the oxida-tion in said liquid organic medium in the presence of FeCl3.
2. Process for the preparation of quinacridone pigment according to Claim 1 wherein the weight ratio of said FeCl3 to said dihydroquinacridone is from 1.0:1 to 1.8:,1.
3. Process for the preparation of quinacridone pigment according to Claim 2 wherein the weight ratio of said FeCl3 to said dihydroquinacridone is from 1.0:1 to 1.5:1.
4. Process for the preparation of quinacridone pigment according to Claim 2 wherein the weight ratio of said liquid organic medium to said dihydroquinacridone is from 5:1 to 35:1.
5. Process for the preparation of quinacridone pigment according to Claim 4 wherein said liquid organic medium is selected from the group consisting of tetra-methylene sulfone and mixtures of at least one of tetra-methylene sulfone, dimethyl formamide and an aliphatic amide with an inert aromatic liquid.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US61683875A | 1975-09-25 | 1975-09-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1071208A true CA1071208A (en) | 1980-02-05 |
Family
ID=24471145
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA261,796A Expired CA1071208A (en) | 1975-09-25 | 1976-09-22 | Preparation of quinacridone using fecl3 |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS5240528A (en) |
| CA (1) | CA1071208A (en) |
| DE (1) | DE2642638A1 (en) |
| FR (1) | FR2325696A1 (en) |
| GB (1) | GB1559407A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015010160A1 (en) | 2013-07-26 | 2015-01-29 | Flinders Ports Pty Ltd | A misting apparatus and dust suppression system employing the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1346126A (en) * | 1963-01-31 | 1963-12-13 | Cassella Farbwerke Mainkur Ag | Process for the preparation of quinacridones |
| US3738988A (en) * | 1970-10-08 | 1973-06-12 | Du Pont | Process for oxidation of dihydroquinacridones to quinacridones |
-
1976
- 1976-09-22 CA CA261,796A patent/CA1071208A/en not_active Expired
- 1976-09-22 DE DE19762642638 patent/DE2642638A1/en active Pending
- 1976-09-24 FR FR7628789A patent/FR2325696A1/en not_active Withdrawn
- 1976-09-24 GB GB3976176A patent/GB1559407A/en not_active Expired
- 1976-09-24 JP JP11376276A patent/JPS5240528A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE2642638A1 (en) | 1977-04-07 |
| GB1559407A (en) | 1980-01-16 |
| FR2325696A1 (en) | 1977-04-22 |
| JPS5240528A (en) | 1977-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100282074B1 (en) | Manufacturing method of 2,6-naphthalenedicarboxylic acid | |
| US2821530A (en) | Tetrahalogen substituted quinacridones | |
| KR100230612B1 (en) | Pigment composition of copper phthalocyanine | |
| EP0860475B1 (en) | Synthesis of bis(Phthalocyanylalumino)tetraphenyldisiloxanes | |
| CA1071208A (en) | Preparation of quinacridone using fecl3 | |
| JP3055365B2 (en) | Process for producing dialkyl 2,5-di (arylamino) -3,6-dihydroterephthalate and process for producing quinacridone using the same as an intermediate | |
| EP0266219B1 (en) | Process for producing copper phthalocyanine pigment | |
| EP0682089A1 (en) | Preparation of phthalocyanine pigments | |
| US4286998A (en) | Light stable quinacridonequinone yellow pigment | |
| EP0837107B1 (en) | Process for the manufacture of dioxazine compounds | |
| CN113292407A (en) | Production method for synthesizing anthracene-associated anthrone by solid superacid catalysis | |
| EP0012432B1 (en) | Light-stable quinacridonequinone yellow pigment and post treatment to improve its dispersibility | |
| CA1049527A (en) | Process for the preparation of 7-oxo-7h-dibenzo(d e, h) -quinolin-2-ol | |
| EP0504182A1 (en) | Method of preparation of quinophthalone derivatives. | |
| CN117024986B (en) | Environment-friendly solvent violet 13 and one-pot production process thereof | |
| US3892751A (en) | Zeta form of quinacridone | |
| DE3009602A1 (en) | METHOD FOR SHAPING ORGANIC PIGMENTS | |
| JPS6342944B2 (en) | ||
| JP3496276B2 (en) | Method for producing copper phthalocyanine | |
| CN115960473A (en) | Method for preparing metal phthalocyanine pigment by solvent method | |
| US4077973A (en) | Synthesis of metal phthalocyanines | |
| US3530136A (en) | Quinacridone synthesis from dianilinoterephthalic acid with silicon tetrachloride | |
| JPS5911620B2 (en) | Method for producing vivid copper phthalocyanine pigments | |
| JPS597736B2 (en) | Method for producing quinophthalone compounds | |
| US4011227A (en) | O-(3-hydroxy-1-isoquinolinyl)-benzoic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |