CN110499042A - A kind of dione pyrrolo-pyrrole pigment derivative and application thereof and synthetic method - Google Patents
A kind of dione pyrrolo-pyrrole pigment derivative and application thereof and synthetic method Download PDFInfo
- Publication number
- CN110499042A CN110499042A CN201810464899.0A CN201810464899A CN110499042A CN 110499042 A CN110499042 A CN 110499042A CN 201810464899 A CN201810464899 A CN 201810464899A CN 110499042 A CN110499042 A CN 110499042A
- Authority
- CN
- China
- Prior art keywords
- product
- pigment
- pigment derivative
- sodium
- derivative
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- C09B57/00—Other synthetic dyes of known constitution
-
- 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
- C09B67/006—Preparation of organic pigments
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The present invention provides a kind of dione pyrrolo-pyrrole pigment derivative and application thereof and synthetic method, the pigment derivative includes one or more of compounds with chemical structure shown in Formulas I, aldehyde radical in Formulas I be independently located at phenyl ring it is adjacent, to one in, meta position, the pigment derivative has active aldehyde radical, can with many kinds of substance occur it is a variety of react, synthesize a variety of DPP class pigment, pigment modifier or DPP analog derivative；The pigment derivative uses the aldehyde by ethylene glycol protection aldehyde radical for cyanophenyl and the different ester condensation of succinic acid two; obtained condensation product releases protection of the ethylene glycol to aldehyde radical through hydrolysis; finally obtain the dione pyrrolo-pyrrole pigment derivative with reactivity; this synthetic method is easy to operate, yield is high; the pigment derivative purity is high of synthesis, has excellent performance.The present invention not only enriches the type and synthetic route of DPP class pigment, pigment modifier or DPP analog derivative, has also widened range of choice when synthesizing these products to raw material.
Description
Technical field
The present invention relates to technical field of fine, and in particular to a kind of dione pyrrolo-pyrrole pigment derivative and its
Synthetic method.
Background technique
Adding organic pigment derivative is one of most common pigment modification processing method, mainly there is following modified work
It uses: (1) as crystal inhibiting agent, reducing the partial size of pigment particles, and reduce the poly- of in subsequent drying and process of lapping particle
Collection effect；(2) height for changing pigment particles surface polarity improves pigment dispersibility in the medium and dispersion stabilization, drop
Low viscosity；(3) form and aspect of pigment are adjusted.The either high performance such as the classical organic pigment of azo or heterocycle, condensed ring is organic
Pigment finds suitable pigment derivative to improve the target that pigment performance is always researcher.
Pyrrolo-pyrrole-dione (abbreviation DPP) class pigment is a kind of high-performance developed by Ciba company in nineteen eighty-three
Organic pigment (U.S. patent Nos US4415685).DPP class pigment has chromatic colour, high color saturation and coloring
Power, excellent weatherability, covering power, good mobility, dispersibility and acid-fast alkali-proof performance are widely used in ink, apply
The fields such as material, plastics and colour filter.To meet the market needs growing to pigment performance, research institution and enterprise carry out
Research of many about DPP class pigment derivative.
Ciba company (Chinese patent CN1481425A) discloses a kind of pigment derivative as rheological property and changes agent, energy
For in DPP class organic pigment.The pigment derivative derives one or more sulfonate groups on pigment molecule skeleton, sun
Ion is quaternary ammonium salt and calcium salt.
Clariant company (Chinese patent CN1675315A) discloses a kind of DPP for colouring in partially crystalline plastics
Class pigment preparation is based on sulfonation diketopyrrolopyrrolecocrystals derivative comprising at least one in the pigment preparation, to have anti-
The characteristics of warpage.
BASF AG (Chinese patent CN102046731) discloses one kind for DPP class color compositions, mainly includes bromine
Substituted DPP pigment, and the DPP derivative and sulfonated derivative of part pair-or the substitution of three-azepine cyclopentyl-methyls are added,
And the DPP derivative replaced by least one chain containing multiple nitrogen-atoms.This color compositions are used for colour filter, have essence
Every advantages such as true tone, high saturating color rate, high contrast, high brightness.The DPP derivative tool that amide group replaces in embodiment
There is preferable effect.
In the prior art, DPP derivative there are two main classes synthesis path: first is that being closed using cyanophenyl derivative through multistep reaction
At second is that derivatization on the basis of DPP skeleton；The former will affect yield since steric hindrance is larger, and the latter's yield is higher, but need
Active group performs the derivatization.
It is well known that aldehyde radical has very high reactivity, relatively common has reduction reaction, oxidation reaction, nucleophilic to add
At reaction etc., a variety of important compounds such as alcohol, carboxylic acid, schiff bases, carbon-carbon bond or functional group, and usual reaction condition can be generated
Compare mildly, industrial production can be used for.In pigment industry, Sun Microsystems (United States Patent (USP) US5024698) proposition will have polyoxy second
The primary amine compound of alkene ether is reacted with acetoacetanilide generates schiff base compounds, is added in coupling reaction, makes pigment
With brilliant idea intensity of colour, glossiness and excellent mobile performance.Hangzhou Baihe Clariant Pigments Co., Ltd.'s (Chinese patent
CN102504573A a kind of azoic coupling component AS class azo organic pigment) is disclosed, synthetic method is derived by the pigment that aldehyde radical replaces
Object and the condensation reaction of electron deficient methylene generate carbon-carbon double bond.It follows that aldehyde radical has one in the synthesis and modification of pigment
Fixed application.
To sum up, DPP derivative can improve the application performance of organic pigment.Currently used DPP derivative mainly contains carboxylic
Acid, sulfonic acid and its salt, amide or sulfonamide, the substituent groups such as ether or thioether, synthetic route and type are subject to certain restrictions, Wu Faman
Sufficient market is to the increasing requirement of organic pigment performance.So the present invention provides a kind of DPP derivative conduct that aldehyde radical replaces
The intermediate of pigment modification agent can enrich the type and synthetic route of DPP derivative.
Summary of the invention
In order to overcome the shortcomings of the prior art, the present invention provides a kind of dione pyrrolo-pyrrole pigment derivative, and openly
A kind of synthetic method and multiple use of the pigment derivative.It is derivative not only to enrich a kind of dione pyrrolo-pyrrole pigment
The type of object has widened the synthesis material of DPP class pigment, pigment modifier or DPP analog derivative and the range of choice of route, also
Improve some do not synthesize so far or the compound prbability of the substance of difficult synthesis.
Dione pyrrolo-pyrrole pigment derivative (hereinafter referred to as DPP class pigment derivative) provided by the invention, including
One or more have the compound of structure shown in formula I.
I
Wherein, aldehyde radical independently positioned at the ortho position of phenyl ring, contraposition or meta position.
Preferably, two aldehyde radicals in formula I are located in the same position of corresponding phenyl ring simultaneously.
Further preferably, DPP class pigment derivative of the present invention is single compound, or includes multiple compounds
Mixture.
As shown in formula I, this DPP class pigment derivative band provided by the invention respectively has on each phenyl ring there are two phenyl ring
One aldehyde radical, this structure can not only sufficiently show the reactivity of aldehyde radical and phenyl ring, and make it have synthetic method it is simple,
Yield height, the wider array of advantage of application range.So DPP class pigment derivative shown in formula I can be used as in pigment modification agent
Mesosome is used to prepare pigment modification agent, is alternatively arranged as the intermediate of DPP class pigment synthesis, the centre of DPP analog derivative synthesis
Body, etc..Such as: DPP class pigment derivative of the present invention obtains a kind of color power with improvement paratonere 254 after aoxidizing
With the pigment modification agent of transparency effect.
Meanwhile the present invention also provides a kind of synthetic methods of the DPP class pigment derivative, comprising the following steps:
Step 1, the protection of aldehyde radical: aldehyde reacts under the catalytic action of p-methyl benzenesulfonic acid for cyanophenyl with ethylene glycol, is produced
Object 1, wherein aldehyde is 1:1.0-4.0 for cyanophenyl and the molar ratio of ethylene glycol, and aldehyde is for the molar ratio of cyanophenyl and p-methyl benzenesulfonic acid
100-500:1；
Step 2, the synthesis of product 2: product 1 reacts in alcohol sodium solution with the different ester of succinic acid two, obtains product 2, wherein
The molar ratio of diisopropyl ester amber acid and product 1 is 1:1.5-2.0；
Step 3, aldehyde radical is deprotected: 2 acid hydrolysis of product obtains dione pyrrolo-pyrrole pigment derivative, wherein produces
The molar ratio of object 2 and hydrochloric acid is 1:2-10, and reaction temperature is 40-70 DEG C.
Preferably, reaction described in step 1 carries out under the protection of inert gas, aldehyde is adjacent cyano benzene first for cyanophenyl
Aldehyde, cyanobenzaldehyde, to one of cyanobenzaldehyde or a variety of.
Further preferably, reaction described in step 1 carries out under nitrogen protection, and aldehyde is dissolved in toluene for cyanophenyl and ethylene glycol,
P-methyl benzenesulfonic acid is added, back flow reaction simultaneously divides water, obtains feed liquid 1, and feed liquid 1 adds weak base liquid separation after being cooled to room temperature, and what is obtained has
Machine layer is washed, it is dry, remove solvent, obtain product 1.Wherein, weak base is sodium carbonate liquor, and sodium carbonate and p-methyl benzenesulfonic acid rub
You are than being 10-100:1, and organic layer is washed using aqueous solution uses desiccant dryness afterwards at least twice, and desiccant is sodium sulphate, sulfuric acid
One or more of magnesium, calcium chloride or calcium sulfate.
Further preferably, the mass concentration of sodium carbonate liquor described in step 1 is 2-8%；Sodium carbonate with to toluene sulphur
The molar ratio of acid is 10-50:1；Aldehyde is 100-350:1 for cyanophenyl and the molar ratio of p-methyl benzenesulfonic acid；Desiccant be sodium sulphate or
Magnesium sulfate.
Preferably, product 1 and diisopropyl ester amber acid are dissolved in tert-pentyl alcohol in step 2, it is molten to be slowly dropped to sodium alkoxide
In liquid, react 3-6 hour, sequentially add methanol in obtained feed liquid 2 and glacial acetic acid flow back protonate, be filtered, washed, drying,
Crushing obtains product 2.Wherein, methanol usage is 0.8-1.2 times of tert-pentyl alcohol gross mass, and the molar ratio of glacial acetic acid and metallic sodium is
1:0.95-1.0.Tert-pentyl alcohol quality+sodium alkoxide of tert-pentyl alcohol gross mass described herein=refer to lysate 1 and the different ester of succinic acid two
The quality of tert-pentyl alcohol in solution.
Preferably, product 2 is dispersed in the aqueous hydrochloric acid solution that mass concentration is 4-15% in step 3, it is stirred to react 2-
It after 10h, filters, washes, it is dry, obtain dione pyrrolo-pyrrole pigment derivative.
Sodium alkoxide solution manufacturing method in DPP class pigment derivative synthesis process of the present invention are as follows: in nitrogen protection
Under, metallic sodium is dissolved in tert-pentyl alcohol, alcohol sodium solution is prepared, wherein the mass ratio of metallic sodium and tert-pentyl alcohol is 1:6-12.
Preferably, catalyst is added in sodium alkoxide solution preparation process, the catalyst is anhydrous ferric chloride, four chlorinations
One of titanium, aluminium chloride, bleeding agent OT, lauryl sodium sulfate are a variety of, and catalyst amount is the 0.1-5% of sodium quality.
The present invention is using the cyanophenyl that aldehyde radical replaces as starting material, and in order to retain aldehyde radical, contracting is made in raw material by step 1
Aldehyde product gets up aldehyde radical temporary protection, and this product has no effect on its condensation reaction with diisopropyl ester amber acid, step 3
Acetal hydro in product 2 that step 2 obtains can be obtained of the present invention having the active DPP class pigment of aldehyde radical derivative
Object.
Preferably, DPP class pigment derivative of the present invention, can now-making-now-using in process of production, can also be with
The form of product 2 saves, and uses after acid hydrolysis in use process.
Preferably, through the invention the DPP class pigment derivative of the method synthesis can by oxidation, reduction, add
At, replace etc. reactions be made pigment modifier, DPP class pigment, DPP analog derivative, etc..It is further preferred that being made by oxidation reaction
Pigment modifier.Such as: the hydrogen peroxide oxidation DPP class pigment derivative is used, the DPP class pigment that carboxyl obtained replaces is derivative
Object can significantly improve the coloured light of paratonere 254, Se Li and its in the dispersion stabilization of aqueous ink system, be a kind of good pigment
Modifier.
Compared with the prior art, the advantages of the present invention are as follows:
(1) a kind of DPP class pigment derivative is disclosed, the type of DPP analog derivative is enriched；
(2) a kind of synthetic method of the pigment derivative is provided, this method is easy to operate, yield is high, product purity height,
Performance is good；
(3) a kind of pigment modification agent intermediate is provided, the range of choice of pigment modifier synthesis material has been widened, is expanded
Pigment modifier synthetic route；
(4) a kind of DPP class pigment derivative and its synthetic method are provided, mentioned for organic pigment synthesis and technical field of modification
For new thinking and developing direction.
Specific embodiment
Embodiment 1
A kind of dione pyrrolo-pyrrole pigment derivative is the compound II with structure shown in Formula II
The synthetic method of the DPP class pigment derivative is as follows:
Step 1: under nitrogen protection, toluene being dissolved in cyanobenzaldehyde, 141 parts of ethylene glycol by 75 parts, 0.8 part of addition is right
Toluenesulfonic acid, back flow reaction simultaneously divide water, until the water in water segregator is not further added by, is cooled to room temperature, adds 120 parts of mass fractions
8% aqueous sodium carbonate stirs liquid separation, casts out water layer, washing is twice；20 parts of anhydrous magnesium sulfates, mistake are added in organic layer
Filter, revolving remove solvent, obtain acetal product 1, yield 95%；
Ethylene glycol: to cyanobenzaldehyde (molar ratio)=4.0:1；
Step 2: under nitrogen protection, 120 parts of tert-pentyl alcohols, 12.6 parts of metallic sodiums and 0.05 part of anhydrous chlorination being added in reaction kettle
Iron, back flow reaction to whole dissolutions；48 parts of acetal product 1 and 33.6 part diisopropyl ester amber acids are dissolved in tert-pentyl alcohol, are slowly dripped
Reaction kettle is added, reacts 5h；Sequentially add methanol and glacial acetic acid and the protonation that flows back；Filtering, it is colourless that methanol is washed till filtrate, go from
Son washing, is dried, and is crushed, is obtained totally 41.8 parts of product 2, yield 71%；
Product 1: diisopropyl ester amber acid (molar ratio)=1.6:1；
Step 3: 43 parts of products 2 are dispersed in the (molar ratio of product 2 and hydrochloric acid in 180 parts of 10% aqueous hydrochloric acid solutions of concentration
For 1:4.9), 4h is stirred at 60 DEG C, is filtered after the reaction was completed, wash, dry 34 parts of DPP class pigment derivative, yield
99%.
Infrared spectroscopy detection and Mass Spectrometer Method are done to obtained DPP class pigment derivative, as a result as follows:
FTIR (KBr): 3443,3134,2975,2857,1702,1640,1600,1565,1513,1442,1319,
1291,1221,1200,1142,1093,1032,939,830,800,745,661,630,518,472.Ir data is tested
The presence of functional group in product is demonstrate,proved.
MALDI-TOF (DHBA ,+H): 344.9, theoretical value 345.Mass spectrometric data proves that the molecular weight of product meets theory
Value.
Infrared spectroscopy detection and Mass Spectrometer Method the result shows that, be Formula II institute according to the product that the present embodiment step is prepared
The DPP class pigment derivative shown.
One of purposes of DPP class pigment derivative shown in Formula II is as follows:
Acetone and 30% hydrogen peroxide solution are added in sodium dihydrogen phosphate, phosphate buffer solution, by DPP class shown in Formula II
Pigment derivative disperses in the reaction system, sodium chlorite aqueous solution to be slowly added dropwise under ice bath, reacts 4 after dripping at room temperature
Hour, it filters, washing.Filter cake is dissolved in sodium hydroxide solution, 70 DEG C is heated to, is filtered to remove solid impurity while hot, in filtrate
Middle dropwise addition hydrochloric acid solution washes out product, until pH=3, filtering, are washed to neutrality, dry to obtain Formula V compound represented.Wherein,
DPP class pigment derivative shown in Formula II and the molar ratio of hydrogen peroxide, sodium chlorite are 1:2:1.8, yield 90%.
V
In the kneading process of paratonere 254, the Formula V compound represented of 254 weight 5% of paratonere is added.It is resulting
For pigment compared with the pigment that Formula V compound represented is not added, coloured light is slightly blue, and color power improves 15%, improves paratonere 254 in water
The dispersion stabilization of property ink system.
Embodiment 2
A kind of DPP class pigment derivative, is the compound with structure shown in formula III:
III
The synthetic method of the DPP class pigment derivative is as follows:
Step 1: under nitrogen protection, cyanobenzaldehyde, 75 parts of ethylene glycol between 75 parts being dissolved in toluene, 0.3 part of addition is right
Toluenesulfonic acid, back flow reaction simultaneously divide water, until the water in water segregator is not further added by, is cooled to room temperature, adds 100 parts of mass fractions
4.9% aqueous sodium carbonate stirs liquid separation, casts out water layer, washing is twice；10 parts of anhydrous sodium sulfates, mistake are added in organic layer
Filter, revolving remove solvent, obtain totally 96.4 parts of acetal product 1, yield 96%；
Ethylene glycol: to cyanobenzaldehyde (molar ratio)=2.1:1；
Step 2: under nitrogen protection, 108 parts of tert-pentyl alcohols, 13.6 parts of metallic sodiums and 0.03 part of anhydrous chlorination being added in reaction kettle
Iron, back flow reaction to whole dissolutions；48 parts of acetal product 1 and 36.6 part diisopropyl ester amber acids are dissolved in tert-pentyl alcohol, are slowly dripped
Reaction kettle is added, reacts 4h；Sequentially add methanol and glacial acetic acid and the protonation that flows back；Filtering, it is colourless that methanol is washed till filtrate, go from
Son washing, is dried, and is crushed, is obtained totally 43.6 parts of product 2, yield 74%；
Product 1: diisopropyl ester amber acid (molar ratio)=1.5:1；
Step 3: 43 parts of products 2 being dispersed in 400 parts of 5% aqueous hydrochloric acid solutions of concentration, 6h is stirred at 50 DEG C, has reacted
At rear filtering, washing, dry pigment modifier intermediate, yield 99%.
Product 2: hydrochloric acid (molar ratio)=1:5.5；
Ir data demonstrates the presence of functional group in product.FTIR (KBr): 3457,3160,2920,2851,
1705,1649,1616,1490,1445,1418,1300,1208,1191,1138,1045,886,796,735,680,664,
637,462.
Mass spectrometric data proves that the molecular weight of product meets theoretical value.MALDI-TOF (DHBA ,+H): 345.0, theoretical value is
345。
Infrared spectroscopy detection and Mass Spectrometer Method the result shows that, the product prepared according to the present embodiment step is formula III
Shown in DPP class pigment derivative.
One of purposes of DPP class pigment derivative shown in formula III is as follows:
Acetone and 30% hydrogen peroxide solution are added in sodium dihydrogen phosphate, phosphate buffer solution, by DPP shown in formula III
Class pigment derivative disperses in the reaction system, sodium chlorite aqueous solution to be slowly added dropwise under ice bath, anti-at room temperature after dripping
It answers 4 hours, filters, washing.Filter cake is dissolved in sodium hydroxide solution, 70 DEG C is heated to, is filtered to remove solid impurity while hot, is being filtered
Hydrochloric acid solution is added dropwise in liquid washes out product, until pH=3, filtering, are washed to neutrality, dry to obtain Formula IV compound represented.Its
In, the molar ratio of DPP class pigment derivative shown in formula III and hydrogen peroxide, sodium chlorite is 1:2.1:1.9, yield 92%.
VI
In the kneading process of paratonere 254, the Formula IV compound represented that 6% parts by weight are added is mediated together, gained
Pigment compared with the pigment that derivative is not added, coloured light is slightly yellow, color power improve 18%, improve paratonere 254 in aqueous ink body
The dispersion stabilization of system.
Embodiment 3
A kind of dione pyrrolo-pyrrole pigment derivative is the mixture with structure shown in formula IV.
IV
DPP class pigment derivative is synthesized according to the following steps:
Step 1: under nitrogen protection, by 37.5 parts to cyanobenzaldehyde, 140 parts of second two between cyanobenzaldehyde, 37.5 parts
Alcohol is dissolved in toluene, and 0.3 part of p-methyl benzenesulfonic acid is added, and back flow reaction simultaneously divides water, cooling until the water in water segregator is not further added by
To room temperature, the aqueous sodium carbonate of 100 parts of mass fractions 2% is added to stir liquid separation, casts out water layer, washing is twice；In organic layer
10 parts of anhydrous sodium sulfates are added, filter, revolving removes solvent, obtains acetal product 1, yield 96%；
Ethylene glycol: to cyanobenzaldehyde (molar ratio)=3.9:1；
Step 2: under nitrogen protection, 108 parts of tert-pentyl alcohols, 13.6 parts of metallic sodiums and 0.03 part of anhydrous chlorination being added in reaction kettle
Iron, back flow reaction to whole dissolutions；48 parts of acetal product 1 and 36.6 part diisopropyl ester amber acids are dissolved in tert-pentyl alcohol, are slowly dripped
Reaction kettle is added, reacts 6h；Sequentially add methanol and glacial acetic acid and the protonation that flows back；Filtering, it is colourless that methanol is washed till filtrate, go from
Son washing, is dried, and is crushed, is obtained product 2, yield 76%；
Product 1: diisopropyl ester amber acid (molar ratio)=1.5:1；
Step 3: 43 parts of products 2 being dispersed in 400 parts of 4% aqueous hydrochloric acid solutions of concentration, 7h is stirred at 42 DEG C, has reacted
At rear filtering, washing, dry Pigment Intermediates, yield 96%.
Product 2: hydrochloric acid (molar ratio)=1:4.4；
Ir data demonstrates the presence of functional group in product.FTIR (KBr): 3447,3138,2981,2851,
1704,1648,1614,1600,1559,1440,1411,1321,1293,1183,1140,1032,843,797,737,669,
626,519,467.
Mass spectrometric data proves that the molecular weight of product meets theoretical value.MALDI-TOF (DHBA ,+H): 344.9, theoretical value is
345。
Infrared spectroscopy detection and Mass Spectrometer Method the result shows that, be formula IV institute according to the product that the present embodiment step is prepared
The DPP class pigment derivative shown.
Embodiment 4
DPP class pigment derivative described in synthetic example 1 according to the following steps:
Step 1: under nitrogen protection, toluene being dissolved in cyanobenzaldehyde, 65 parts of ethylene glycol by 75 parts, 0.8 part of addition is right
Toluenesulfonic acid, back flow reaction simultaneously divide water, until the water in water segregator is not further added by, is cooled to room temperature, adds 120 parts of mass fractions
8% aqueous sodium carbonate stirs liquid separation, casts out water layer, washing is twice；20 parts of anhydrous magnesium sulfates, mistake are added in organic layer
Filter, revolving remove solvent, obtain acetal product 1, yield 93%；
Ethylene glycol: to cyanobenzaldehyde (molar ratio)=1.8:1；
Step 2: under nitrogen protection, 120 parts of tert-pentyl alcohols, 12.6 parts of metallic sodiums and 0.05 part of anhydrous chlorination being added in reaction kettle
Iron, back flow reaction to whole dissolutions；48 parts of acetal product 1 and 29.2 part diisopropyl ester amber acids are dissolved in tert-pentyl alcohol, are slowly dripped
Reaction kettle is added, reacts 5h；Sequentially add 80 parts of methanol and 18 parts of glacial acetic acids and the protonation that flows back；Filtering, is washed with 50 parts of methanol
Colourless to filtrate, deionization washing dries, crushes, obtain totally 41.2 parts of product 2, yield 70%；
Methanol usage is 0.8-1.2 times of tert-pentyl alcohol gross mass；
Product 1: diisopropyl ester amber acid (molar ratio)=1.9:1；
Step 3: 43 parts of products 2 being dispersed in 220 parts of 10% aqueous hydrochloric acid solutions of concentration, 4h is stirred at 60 DEG C, are reacted
It filters, washes after the completion, dry 34 parts of Pigment Intermediates, yield 99%.
Product 2: hydrochloric acid (molar ratio)=1:6.0；
Ir data demonstrates the presence of functional group in product.FTIR (KBr): 3443,3134,2975,2857,
1702,1640,1600,1565,1513,1442,1319,1291,1221,1200,1142,1093,1032,939,830,800,
745,661,630,518,472.
Mass spectrometric data proves that the molecular weight of product meets theoretical value.MALDI-TOF (DHBA ,+H): 344.9, theoretical value is
345。
Infrared spectroscopy detection and Mass Spectrometer Method the result shows that, be Formula II institute according to the product that the present embodiment step is prepared
The DPP class pigment derivative shown.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With.It can be applied to various suitable the field of the invention completely.It for those skilled in the art, can be easily
Realize other modification.Therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details.
Claims (10)
1. a kind of dione pyrrolo-pyrrole pigment derivative, which is characterized in that there is structure shown in Formulas I including one or more
Compound:
I
Wherein, aldehyde radical is independently located at the ortho position of phenyl ring, meta position, one in contraposition.
2. pigment derivative described in claim 1, which is characterized in that aldehyde radical is located on the same position of corresponding phenyl ring simultaneously.
3. a kind of pigment modification agent, which is characterized in that be with dione pyrrolo-pyrrole pigment derivative described in claim 1
Raw material is made by oxidation reaction.
4. a kind of synthetic method of dione pyrrolo-pyrrole pigment derivative, which comprises the following steps:
Step 1, the protection of aldehyde radical: aldehyde returns under the catalytic action of p-methyl benzenesulfonic acid, in organic solvent for cyanophenyl and ethylene glycol
Stream reaction, obtains product 1, wherein aldehyde is 1:1.0-4.0 for cyanophenyl and the molar ratio of ethylene glycol, and aldehyde is for cyanophenyl and to toluene sulphur
The molar ratio of acid is 100-500:1；
Step 2, the synthesis of product 2: product 1 reacts in alcohol sodium solution with the different ester of succinic acid two, obtains product 2, wherein fourth two
The molar ratio of sour diisopropyl ester and product 1 is 1:1.5-2.0；
Step 3, aldehyde radical is deprotected: 2 acid hydrolysis of product obtains dione pyrrolo-pyrrole pigment derivative, wherein product 2
Molar ratio with hydrochloric acid is 1:2-10, and reaction temperature is 40-70 DEG C.
5. synthetic method according to claim 4, which is characterized in that guarantor of the reaction described in step 1 in inert gas
Shield is lower to be carried out, and aldehyde for cyanophenyl is o-cyanobenzaldehyde, cyanobenzaldehyde, to one of cyanobenzaldehyde or a variety of.
6. synthetic method according to claim 4 or 5, which is characterized in that step 1 carries out under nitrogen protection, and aldehyde is for benzene
Nitrile carries out a point water with ethylene glycol after reflux in toluene is reacted, and obtained feed liquid 1 adds weak base liquid separation after being cooled to room temperature, and obtains
Organic layer is washed, it is dry, remove solvent, obtain product 1；The weak base is sodium carbonate liquor, sodium carbonate and p-methyl benzenesulfonic acid
Molar ratio be 100-10:1, organic layer using aqueous solution wash at least twice afterwards use desiccant dryness, desiccant be sodium sulphate,
One or more of magnesium sulfate, calcium chloride or calcium sulfate.
7. synthetic method according to claim 4, which is characterized in that in step 2, product 1 and diisopropyl ester amber acid are molten
It in tert-pentyl alcohol, is slowly dropped in alcohol sodium solution, is reacted 3-6 hours, sequentially add methanol and ice second in obtained feed liquid 2
Acid reflux protonate, is filtered, washed, drying, crushing and obtain product 2, wherein methanol usage for tert-pentyl alcohol gross mass 0.8-
1.2 times, the molar ratio of glacial acetic acid and metallic sodium is 1:0.95-1.0.
8. synthetic method according to claim 4, which is characterized in that in step 3, product 2, which is dispersed in mass concentration, is
In the aqueous hydrochloric acid solution of 4-15%, after being stirred to react 2-10h, filters, wash, it is dry, obtain dione pyrrolo-pyrrole pigment
Derivative.
9. synthetic method as claimed in claim 4, which is characterized in that sodium alkoxide solution manufacturing method described in step 2 are as follows: in nitrogen
Under gas shielded, metallic sodium is dissolved in tert-pentyl alcohol, the mass ratio of metallic sodium and tert-pentyl alcohol is 1:6-12.
10. method as claimed in claim 9, which is characterized in that catalyst, the catalyst are added in sodium alkoxide solution preparation process
For one of anhydrous ferric chloride, titanium tetrachloride, aluminium chloride, bleeding agent OT, lauryl sodium sulfate or a variety of, catalyst amount
For the 0.1-5% of sodium quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810464899.0A CN110499042A (en) | 2018-05-16 | 2018-05-16 | A kind of dione pyrrolo-pyrrole pigment derivative and application thereof and synthetic method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810464899.0A CN110499042A (en) | 2018-05-16 | 2018-05-16 | A kind of dione pyrrolo-pyrrole pigment derivative and application thereof and synthetic method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110499042A true CN110499042A (en) | 2019-11-26 |
Family
ID=68583871
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810464899.0A Pending CN110499042A (en) | 2018-05-16 | 2018-05-16 | A kind of dione pyrrolo-pyrrole pigment derivative and application thereof and synthetic method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110499042A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4791204A (en) * | 1985-11-26 | 1988-12-13 | Ciba-Geigy Corporation | 1,4-diketopyrrolo[3,4-c]pyrrole pigments |
| CN1165824A (en) * | 1996-01-30 | 1997-11-26 | 西巴特殊化学品控股有限公司 | Polymerizable diketopyrrolopyrroles and polymers prepared therewith |
| CN1867313A (en) * | 2003-10-17 | 2006-11-22 | 西巴特殊化学制品控股公司 | Cosmetic formulations comprising diketo diphenyl pyrrolo-pyrrole pigments |
-
2018
- 2018-05-16 CN CN201810464899.0A patent/CN110499042A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4791204A (en) * | 1985-11-26 | 1988-12-13 | Ciba-Geigy Corporation | 1,4-diketopyrrolo[3,4-c]pyrrole pigments |
| CN1165824A (en) * | 1996-01-30 | 1997-11-26 | 西巴特殊化学品控股有限公司 | Polymerizable diketopyrrolopyrroles and polymers prepared therewith |
| CN1867313A (en) * | 2003-10-17 | 2006-11-22 | 西巴特殊化学制品控股公司 | Cosmetic formulations comprising diketo diphenyl pyrrolo-pyrrole pigments |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112441942B (en) | Debromination method of sartan intermediate polybrominated substituent | |
| CN110499042A (en) | A kind of dione pyrrolo-pyrrole pigment derivative and application thereof and synthetic method | |
| EP0023645B1 (en) | Process for the preparation of 1,4-diamino-2,3-dicyanoanthraquinones | |
| CN110698352B (en) | Synthetic method of 3-bromo-5-aminocatechol dimethyl ether | |
| CN115626936B (en) | Synthesis method of complex luminescent material capable of finely regulating and controlling luminescence wavelength | |
| KR20150084165A (en) | Method for preparing of nafamostat mesilate | |
| CN110372547B (en) | Method for preparing 1-amino-4-sodium naphthalene sulfonate | |
| EP0043575B1 (en) | Water-soluble azo compounds, process for their preparation and their use as dyestuffs | |
| CH643824A5 (en) | METHOD FOR PRODUCING SULFUR SEMICONDESTERS. | |
| JP4637621B2 (en) | Phthalocyanine compounds | |
| US2318783A (en) | Preparation of copper phthalocyanines | |
| JP2003128669A (en) | Quinophtalone sulfonic acid derivative and production method thereof | |
| US2658899A (en) | Sulfonated anthraquinone naphthocarbazole dyestuffs and process for preparing them | |
| CN111217842A (en) | Spiro-dipyrromethene boron complex/dipyrromethene boron complex and preparation method and application thereof | |
| Sanislav et al. | Investigation of two textile anthraquinone dyes purity | |
| US4321390A (en) | Preparation of insoluble metal complex colorants | |
| JP4232073B2 (en) | Additive for quinacridone pigment, pigment composition and aqueous pigment dispersion | |
| US1702022A (en) | Alpha-di (methylamino)-alpha-dihydroxy-anthraquinone disulphonic acids and process of making the same | |
| CN105753873A (en) | Preparation method of octahydroxy Schiff base metal phthalocyanine | |
| Christie et al. | Metal salt azo pigments derived from 3-hydroxy-2-naphthohydroxamic acid | |
| JP2003096324A (en) | Method for preparing quinacridone sulfonic acid derivative | |
| SU759515A1 (en) | 6-oxy-7-nitrobenzthiazole ferrocomplex as dye for wool and molyamide fiber | |
| CN106256818B (en) | A kind of indone with trifluoromethylthio and its derivative and preparation method thereof | |
| CN114163371A (en) | Meropenem side chain optical isomer, preparation method and application thereof, and detection method of impurities in Meropenem side chain | |
| JPH07145327A (en) | Production of dioxazine compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20191126 |
|
| WD01 | Invention patent application deemed withdrawn after publication |