Title of Invention

PROCESS FOR THE PREPARATION OF QUINOPHTHALONE PIGMENT

Abstract Process for preparation of Quinopthalone (I) pigment using a solvent mixture (I) 10 comprising of an aromatic carboxylic acid or substituted aromatic carboxylic acid having melting point between 110°C to 180°C with the aromatic hydrocarbon or chlorinated aromatic hydrocarbons on heating at predetermined temperature with simultaneous removal of water formed during the process of reaction for a certain duration of time to complete the reaction and obtain high yield of end product after filtration.
Full Text FORM 2
The Patent Act 1970,
(39 of 1970)
&
The Patent rule 2003
Complete Specification
(See Section 10 and Rule 13)
1. TITLE OF THE INVENTION
"PROCESS FOR THE PREPARATION OF QUINOPHTHALONE PIGMENT"
2. APPLICANT(S)
(a) NAME : GHARDA CHEMICALS LTD
(b) NATIONALITY : INDIAN
(c) ADDRESS: B-27/29, MIDC, PHASE 1, DOMBIVLI.
DIST. THANE, PIN 421 203 MAHARASHTRA INDIA
3. PREAMBLE OF THE DESCRIPTION
The following specification particularly describes the invention and the manner in which it is to be performed.

FIELD OF INVENTION

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(I) The invention relates to a process for preparation of Quinopthalone pigments (I) by condensation of 8-aminoquinaldine with 3,4,5,6-Tetrachloro phthalic anhydride using improved solvent mixture consisting of an aromatic carboxylic acid or substituted aromatic carboxylic acid with a melting point between 110°C to 180°C and aromatic hydrocarbon with alkyl or chloro substituents.
BACKGROUND OF INVENTION
Quinopthalone pigments are disclosed in US 1963374,US 3622583, US 4150025 and US 5106980. The process for the preparation of Quinopthalone pigment (I) involves condensation reaction of 8-Amino quinaldine with 3,4,5,6 Tetrachloro
phthalic anhydride using different solvents or mixture of solvents, e.g. US 1963374 discloses use of aromatic solvents like o- dichlorobenzene whereas US 3622583 discloses use of aromatic solvents like o- dichlorobenzene, 1,2,4, trichloro benzene, diphenyl ether or mixture of chloroaromatic solvents along with diphenyl ether.
US patent 4150025 teaches us the process for the preparation of Quinophthalone pigment using catalyst like ZnCI2 along with aromatic chloro
solvents to accelerate the kinetics. It is further noted in the above patent that this
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compound can be prepared by reacting a corresponding quinaldine derivative with a tetrahalo phthalic anhydride. A yellow organic pigment comprising this compound as a coloring ingredient is useful for coloring polymers. The reaction sufficiently proceeds by heating the two starting material under the above
reaction conditions. Advantageously, however, the reaction can be carried out in the presence of a catalytic amount of Friedel-Craft catalyst of zinc chloride, aluminium chloride, antimony pentoxide, iron trichloride, tin tetrachloride or titanium tetrachloride. The presence of the catalyst is especially necessary when the reaction temperature is relatively low, for example, not more than 250°C because at such temperatures, the rate of the reaction decreases. Water formed, as a by product in the above reaction should desirably be removed out of the reaction system during the reaction by a suitable means such as evaporation, use of dehydrating agent or azeotropic distillation.
US patent 5106980 discloses A process for the preparation of a quinophthalone by condensing 8-aminoquinaldine with phthalic anhydride, optionally monosubstituted or polysubstituted by chlorine or bromine, in the presence of
molten benzoic acid as diluent.
However, the above processes have drawbacks. For example, a reaction temperature of more than 200°C. is usually necessary. At such high temperature, partial decomposition of the amino components might cause undesirable dulling, necessitating perhaps, expensive post purification steps. Another method to obtain pigments showing a high degree of brilliance it is necessary to work with an excess of tetrachlorophthalic anhydride (approx.30 to 50% molar), This excess tetrachloro phthalic anhydride is usually lost when the diluent used is regenerated.
It is thus an object of the present invention to provide a novel process for the preparation of quinophthalones which no longer suffers from the above drawbacks and is simple to carry into effect industrially. A further object is to obtain the end product in good yield & to high degree of purity.
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OBJECT OF INVENTION
The object of this invention is to provide novel quinoline pigments having superior thermal stability, weatherability, migration resistance & resistance to solvents.
STATEMENT OF THE INVENTION
Process for the preparation of Quinophthalone (I) pigment using a mixture comprising of an aromatic carboxylic acid or substituted aromatic carboxylic acid having melting point between 110°C to 180°C with an aromatic hydrocarbon or chlorinated aromatic hydrocarbons on heating at predetermined temperature with simultaneous removal of water formed during the process of reaction for a certain duration of time to complete the reaction and obtain high yield of end product.
DESCRIPTION OF THE INVENTION
According to invention, it is found that preparation of Quinophthalone (I) by condensation of 3,4,5,6-Tetrachloro phthalic anhydride with 8-Aminoquinaldine using mix solvent system containing aromatic carboxylic acid or substituted aromatic carboxylic acid e.g.benzoic acid or o-chloro benzoic acid and aromatic hydrocarbon solvent like xylene or chlorinated benzene have many advantages. The mix solvent system achieves intimate mixing, helps remove water formed from the zone of reaction and improves overall kinetics, and allows the quantification of the rate of reaction.
The process of the invention is conveniently carried out at atmospheric pressure or in vacuum at temperature from 150-200°C without the need of any external
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catalyst. Usually aromatic carboxylic acid & any one solvent stated above is charged in the reactor & heated to 110-150°C to get a well stirrable mass.
8-Aminoquinaldine & 3,4,5,6-Tetrachloro phthalic anhydride are added into
mixture of solvent and total mixture is heated to a temperature from 150°C to 200°C to get a reflux of a solvent. As reaction proceeds, water generated due to reaction process in reactor is removed azeotropically from the reaction medium to prevent hydrolysis of the final product. The water so collected is measured to monitor the extent of condensation the reactants and the completion of the reaction.
The reaction mixture is initially heated to 150-155°C to get a good reflux and maintained at this temperature for about 3-4 hrs before further heating to 200°C Water generated during reaction is removed which allows quantitative conversion of reactants. Water generated and removed during the reaction, helps in estimating the rate of reaction and therefore the conversion of the reactants. After ceasation of water formation, temperature of reaction mass is raised to 200°C for removal of solvent from the reaction mass & to perform a good continuous reflux.
The compound 8-Aminoquinaldine and 3,4,5,6-Tetrachloro phthalic anhydride are generally used in a molar ratio of from 1:2.1 to 1:2.3 For one part of 8-Aminoquinaldine, generally 10 to 20 times by weight of aromatic carboxylic acid is used as a solvent medium and 5 to 15 times by weight of organic solvent is used as a co solvent
Thus with this novel process i.e. with the use of mixt solvent, Quinophthalone (I) pigment is produced in good yield & high state of purity
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The invention is illustrated below by the following examples.
Example:-1
500 gm of benzoic acid and 315 gm of monochloro benzene is charged into reaction vessel and heated to 120-130°C. To the molten mass, 158 gm of 3,4,5,6-Tetrachloro phthalic anhydride is added at same temperature followed by 39.5 gm of 8-Aminoquinaldine. The mixture is heated to 150-155°C to get reflux & stir at reflux temperature for 3 hrs with removal of water azeotropically. Gradually temperature of reaction mass raised to 200°C with removal of water along with some solvent from the reaction mass & stirred for 3-5 hrs to get complete evolution of water. The reaction mixture is cooled to 130°C and 500 gm. of monochlorobenzene is added and stirred at 100-120°C for 2-4 hrs. Pigment is filtered hot, washed with 500 ml. of hot monochloro benzene. The Quinophthalone pigment, isolated with vacuum drying obtained 165 gm. (95%) of the Formula (I)
Example:-2
750 gm of benzoic acid and 375 gm of monochloro benzene is charged into reaction vessel and heated to 120-130°C. To the molten mass, 158 gm of 3,4,5,6-Tetrachloro phthalic anhydride is added at same temperature followed by 39.5 gm of 8-Aminoquinaldine. The mixture is heated to 145-150°C to get reflux and stir at reflux temperature for 3 hrs with removal of water azeotropically. Gradually temperature of reaction mass raised to 190°C with removal of solvent from the reaction mass & stirred for 3-5 hrs to get complete evolution of water. The reaction mixture is cooled to 130°C & 500 gm. of monochlorobenzene is added & stirred at 100-120°C for 2-4 hrs. Pigment is filtered hot, washed with 500 ml. of hot monochlorobenzene. The
Quinophthalone pigment, isolated with vacuum drying obtained 170 gm. (98%) Filtrate +wash containing benzoic acid is evaporated completely & residual mass is vacuum distilled to get 720 gm (96%) of benzoic acid.
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Example: -3
500 gm of o-Chloro benzoic acid and 315 gm of monochloro benzene is charged into reaction vessel and heated to 140-145°C. To the molten mass, 158 gm of
3,4,5,6-Tetrachloro phthalic anhydride is added at same temperature followed by
39.5 gm of 8-Aminoquinaldine. The mixture is heated to 150-155°C to get reflux & stir at reflux temperature for 3 hrs with removal of water azeotropically. Gradually temperature of reaction mass raised to 200°C with removal of water
along with some solvent from the reaction mass & stirred for 3-5 hrs to get complete evolution of water. The reaction mixture is cooled to 130°C and 750 gm. of monochlorobenzene is added and stirred at 100-120°C for 2-4 hrs. Pigment is filtered hot, washed with 500 ml. of hot monochloro benzene. The Quinophthalone pigment, isolated with vacuum drying obtained 165 gm. (95%) of the Formula (I)
Example:-4
Example 1 is repeated with benzoic acid recovered from pigment batch. There were obtained 165 gm (95%) of pigment.
Example: 5
Example 2 is repeated using Xylene as a solvent instead of monochloro benzene. There were obtained 165 gm (95%) of pigment.
Different embodiments of the invention are possible to achieve the best method of performance and to obtain the product as stated above to meet the object of the invention. It will be understood that skilled person with many modifications, variations and adaptation may carry out the invention into practice without departing from its spirit or exceeding the scope of claims in describing the invention for the purpose of illustration.
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WE CLAIM
1. A novel process for preparation of Quinophthalone pigment (I) using a solvent
mixture comprising of an aromatic carboxylic acid or substituted aromatic
carboxylic acid having melting point between 110°C to 180°C with the aromatic hydrocarbon or chlorinated aromatic hydrocarbons on heating at predetermined temperature with simultaneous removal of water formed during the process of reaction for a certain duration of time to complete the reaction and obtain high yield of end product after filtration.
2. Process as claimed in claim 1 wherein the aromatic carboxylic acid is benzoic acid or o-Chloro benzoic acid.
3. Process as claimed in claim 1 wherein the aromatic hydrocarbon is xylene, or mono chlorobenzene.
4. Process as claimed in claim 1 wherein the reflux temperature is 150C to 200°C.
5. Process as claimed in claim 1, wherein water of reaction is removed azeotropically from the reaction mass, thus monitoring the reaction with water quantification.
6. A process as claimed in claim 1, wherein recovery of benzoic acid is done with additional excess of aromatic hydrocarbon, chlorinated hydrocarbon solvent into reaction mass after completion of reaction
7. Process as claimed 1 wherein the reaction product is cooled to 100°C to 120°C & kept for certain period preferably 2-4 hrs.
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8. Process as claimed in claim 1 wherein the product is filtered at 100°C to
120°C & washed with adequate volume of aromatic hydrocarbon solvent,
chlorinated hydrocarbon solvent & collected product dried under vacuum.
9. Process as claimed in preceding claims substantially as herein described.
Dated the 17th Aug 2005 Applicant

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ABSTRACT
Process for preparation of Quinopthalone (I) pigment using a solvent mixture
(I)
10
comprising of an aromatic carboxylic acid or substituted aromatic carboxylic acid having melting point between 110°C to 180°C with the aromatic hydrocarbon or chlorinated aromatic hydrocarbons on heating at predetermined temperature with simultaneous removal of water formed during the process of reaction for a certain duration of time to complete the reaction and obtain high yield of end product after filtration.


Documents:

958-MUM-2005-ABSTRACT(19-11-2010).pdf

958-MUM-2005-ABSTRACT(4-1-2010).pdf

958-MUM-2005-ABSTRACT(AMENDED)-(19-11-2010).pdf

958-MUM-2005-ABSTRACT(AMENDED)-(4-1-2010).pdf

958-MUM-2005-ABSTRACT(GRANTED)-(24-8-2011).pdf

958-mum-2005-abstract.doc

958-mum-2005-abstract.pdf

958-MUM-2005-CANCELLED PAGES(4-1-2010).pdf

958-MUM-2005-CLAIMS(AMANDED)-(4-1-2010).pdf

958-MUM-2005-CLAIMS(AMENDED)-(19-11-2010).pdf

958-MUM-2005-CLAIMS(GRANTED)-(24-8-2011).pdf

958-mum-2005-claims.doc

958-mum-2005-claims.pdf

958-MUM-2005-CORRESPONDENCE(19-11-2010).pdf

958-MUM-2005-CORRESPONDENCE(24-3-2011).pdf

958-MUM-2005-CORRESPONDENCE(24-8-2009).pdf

958-MUM-2005-CORRESPONDENCE(3-6-2009).pdf

958-MUM-2005-CORRESPONDENCE(7-1-2009).pdf

958-MUM-2005-CORRESPONDENCE(IPO)-(24-8-2011).pdf

958-mum-2005-description (complete).pdf

958-MUM-2005-DESCRIPTION(GRANTED)-(24-8-2011).pdf

958-mum-2005-form 18(9-10-2007).pdf

958-MUM-2005-FORM 2(GRANTED)-24-8-2011).pdf

958-MUM-2005-FORM 2(TITLE PAGE)-(19-11-2010).pdf

958-MUM-2005-FORM 2(TITLE PAGE)-(4-1-2010).pdf

958-MUM-2005-FORM 2(TITLE PAGE)-(GRANTED)-24-8-2011).pdf

958-MUM-2005-FORM 3(17-8-2005).pdf

958-MUM-2005-FORM 3(24-3-2011).pdf

958-MUM-2005-FORM 3(3-6-2009).pdf

958-MUM-2005-FORM 3(4-1-2010).pdf

958-MUM-2005-FORM 3(7-1-2009).pdf

958-MUM-2005-FORM 5(24-8-2009).pdf

958-MUM-2005-FORM 5(4-1-2010).pdf

958-mum-2005-form-1.pdf

958-mum-2005-form-2.doc

958-mum-2005-form-2.pdf

958-mum-2005-form-3.pdf

958-MUM-2005-REPLY TO EXAMINATION REPORT(4-1-2010).pdf

958-MUM-2005-SPECIFICATION(AMANDED)-(4-1-2010).pdf

958-MUM-2005-SPECIFICATION(AMENDED)-(19-11-2010).pdf

958-MUM-2005-SPECIFICATION(AMENDED)-(4-1-2010).pdf

abstract1.jpg


Patent Number 248775
Indian Patent Application Number 958/MUM/2005
PG Journal Number 34/2011
Publication Date 26-Aug-2011
Grant Date 24-Aug-2011
Date of Filing 17-Aug-2005
Name of Patentee GHARDA CHEMICALS LTD.
Applicant Address B-27/29,MIDC, PHASE 1, DOMBIVLI, DIST. THANE. PIN 421 203,
Inventors:
# Inventor's Name Inventor's Address
1 MATHUR SUCHET SARAN B-27/29,MIDC, PHASE 1, DOMBVILI, DIST. THANE. PIN 421 203, MAHARASHTRA INDIA
2 JOSEPH PULINATTU CHERIAN B-27/29,MIDC, PHASE 1, DOMBVILI, DIST. THANE. PIN 421 203, MAHARASHTRA INDIA
3 JAIN NANDKUMAR JANARDAN B-27/29,MIDC, PHASE 1, DOMBVILI, DIST. THANE. PIN 421 203, MAHARASHTRA INDIA
4 DESAI JIGNESH RANJITRAI B-27/29,MIDC, PHASE 1, DOMBVILI, DIST. THANE. PIN 421 203, MAHARASHTRA INDIA
PCT International Classification Number C07D3/00
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NA