CN109400460A - A kind of preparation method of 3,9- dioctyl phthalate - Google Patents
A kind of preparation method of 3,9- dioctyl phthalate Download PDFInfo
- Publication number
- CN109400460A CN109400460A CN201811201010.6A CN201811201010A CN109400460A CN 109400460 A CN109400460 A CN 109400460A CN 201811201010 A CN201811201010 A CN 201811201010A CN 109400460 A CN109400460 A CN 109400460A
- Authority
- CN
- China
- Prior art keywords
- added
- under
- room temperature
- filter cake
- reaction
- 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
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/04—Ortho- or peri-condensed ring systems
- C07D221/06—Ring systems of three rings
- C07D221/14—Aza-phenalenes, e.g. 1,8-naphthalimide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/083—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid anhydrides
- C07C51/087—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid anhydrides by hydrolysis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
- C07D311/82—Xanthenes
- C07D311/90—Xanthenes with hydrocarbon radicals, substituted by amino radicals, directly attached in position 9
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/06—Peri-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/10—Spiro-condensed systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses the preparation methods of one kind 3,9- dioctyl phthalate, and the specific steps are in glacial acetic acid solvent, acenaphthene aoxidizes under the action of sodium dichromate and obtains 1,8- naphthalic anhydride；The acylation under the action of ammonium hydroxide of saturation of 1,8- naphthalic anhydride obtains 1,8- naphthalene Asia amide；C-C is coupled to obtain 3,4,9,10- tetracarboxylic acid diimide 1,8- naphthalene Asia amide under the conditions of alkaline environment high temperature under the alkaline environment that potassium hydroxide and anhydrous sodium acetate manufacture；3,4,9,10- tetracarboxylic acid diimide is converted into 3,4,9,10- tetracid glycosides under strong acid effect；3,4,9,10- tetracid glycosides obtains 3,9- dioctyl phthalate in microwave reactor neutral and alkali hydrolysis decarboxylation.Synthesis technology of the invention is more economical, environmentally friendly, efficient and easy.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to the preparation method of one kind 3,9- dioctyl phthalate.
Background technique
Based compound is the condensed ring macromolecular class compound of a kind of plane, rigidity, conjugation, has good photochemistry steady
Qualitative and stronger fluorescence property, the dyeing as reducing dye for cotton fiber and fabric always, because it is with high
Using fastness, scientists are developed into a series of high-performance organic dyestuff；Current such dyestuff is stepped on by " Colour Index "
More than ten a kinds of record, mainly based on red, such as C.I. pigment red 123,149,178,179,190,224 and C.I. pigment
Purple 29 and the black system pigment C.I. pigment black 31 and 32 etc. newly developed come out, thus it is main in based compound getting up early research
It is used as pigments or dyes.In recent years, with the development of science and technology, research discovery based compound or one kind are good organic
Semiconductor material, photoelectricity, electro-optical properties and luminosity are significant, in organic photoconductor, have function conversion, organic photoelectric point
Showed Very Brisk is reported in the research of the functional aspect such as sub- device and cell fluorescence probe.Wherein formic acid based compound is as organic
The research of conductive photoreceptor body is an importance of its application and development, such as photosensitive is led using tetracarboxylic compound is good
Electrical property applies it to organic photoconductor Xeroxing；The solid solar electricity constituted using tetracarboxylic compound
Pond, photoelectric conversion rate can reach 2%；Furthermore with tetrabasic carboxylic acid body two-photon selective reduction characteristic, carry out reversible
Electron transfer reaction switchs to carry out the photosensitive molecular of light operation, has developed the microelectronic component of a variety of organic molecule grades.
Summary of the invention
Good photochemistry that is simple the technical problem to be solved by the present invention is to provide a kind of synthesis technology and facilitating operation
The preparation method of 3, the 9- dioctyl phthalate of stability and stronger fluorescence property, this method is easy to operate, and yield is higher, have compared with
Good industrial applications prospect.
The present invention adopts the following technical scheme that, the preparation method of one kind 3,9- dioctyl phthalate, it is characterised in that specific steps
Are as follows:
(1) in glacial acetic acid solvent, acenaphthene aoxidizes under the action of sodium dichromate and obtains 1,8- naphthalic anhydride；
(2) 1,8- naphthalic anhydride acylation under the action of the ammonium hydroxide of saturation obtains 1,8- naphthalene Asia amide；
(3) 1,8- naphthalene Asia amide alkaline environment high temperature item under the alkaline environment that potassium hydroxide and anhydrous sodium acetate manufacture
C-C is coupled to obtain 3,4,9,10- tetracarboxylic acid diimide under part；
(4) 3,4,9,10- tetracarboxylic acid diimide is converted into 3,4,9,10- tetracid glycosides under strong acid effect；
(5) 3,4,9,10- tetracid glycosides obtains 3,9- dioctyl phthalate in microwave reactor neutral and alkali hydrolysis decarboxylation.
Further preferably, the detailed process of step (1) are as follows: acenaphthene is added in glacial acetic acid, sodium dichromate is added,
It is to slowly warm up to 80 DEG C after mixing evenly under room temperature, keeps thermotonus to raw material fully reacting, reaction solution is fallen while hot
Enter in ice water, there is solid precipitation, filters reaction solution, 1,8- naphthalene dicarboxylic anhydride is obtained after filter cake is dried.
Further preferably, the detailed process of step (2) are as follows: 1,8- naphthalene diacid glycosides is added in the ammonium hydroxide of saturation, in room
The mixing liquid that yellow is stirred to get under the conditions of temperature is heated slowly to 70 DEG C, after keeping the thermotonus to raw material fully reacting
Stop heating, is slowly dropped to room temperature, there is solid precipitation, filtering reacting liquid, filter cake is washed with water to neutrality, then in 60 DEG C of conditions
Lower drying obtains 1,8- naphthalene diamides.
Further preferably, the detailed process of step (3) are as follows: in microwave reactor, potassium hydroxide and anhydrous sodium acetate
It is added in dimethyl sulfoxide, 1,8- benzene-naphthalene diimide is added under nitrogen protection, certain temperature reaction is continuously heating to after adding
For a period of time, water is added after reaction, reaction solution is poured into water after mixing evenly, stirs at room temperature a large amount of to having
Solid is precipitated, and filters reaction solution, and filter cake is added in the hydrochloric acid solution of saturation after being washed with water, is heated to 75 DEG C and is stirred to react one
The section time, filtering reacting liquid, filter cake dry under the conditions of 80 DEG C and obtain 3,4,9,10- tetracarboxylic acid diimide crude products again；
3,4,9,10- tetracarboxylic acid diimide hydrochloride, crudes are added in the concentrated sulfuric acid, are to slowly warm up to 80 DEG C, crude product is completely molten
Solution drips in the sulfuric acid that concentration is being slowly added dropwise is 50% and is warming up to 100 DEG C entirely, be cooled to room after the reaction was continued a period of time
Temperature has a large amount of solids to be precipitated, filtering reacting liquid, and filter cake is dried under the conditions of 80 DEG C again after being washed with the sulfuric acid solution that concentration is 78%
Obtain the 3,4,9,10- tetracarboxylic acid diimide sterling of aubergine；The certain temperature is 70~130 DEG C.
Further preferably, the detailed process of step (4) are as follows: in the reaction vessel, under room temperature, 3,4,9,10-
Tetracarboxylic acid diimide is slowly added into the concentrated sulfuric acid, and 220 DEG C are to slowly warm up to after adding, and keeps thermotonus for a period of time,
Then it is slowly dropped to room temperature, there are a large amount of solids to be precipitated in temperature-fall period, filter cake is washed with water to neutrality, 80 in filtering reacting liquid
Filter cake is dried under the conditions of DEG C obtains 3,4,9,10- glycosides crude product；Under the conditions of being protected from light, obtained crude product be all added to water and
In the mixed solution of potassium hydroxide, under nitrogen protection, 90 DEG C is slowly heated to, is dropped after keeping temperature to be stirred to react a period of time
To room temperature, there are a large amount of solids to be precipitated, reaction solution is filtered by vacuum, filter cake is washed with water；Under the conditions of nitrogen protection is with being protected from light, to filter
Potassium hydroxide and active carbon are added in liquid, ferric sulfate and water is added after stirring 30min at room temperature, room temperature condition is kept to stir
It mixes reaction a period of time, filtering reacting liquid, the hydrochloric acid solution of saturation is added in filtrate, is heated to 80~90 DEG C of stirring 1h, have big
It measures solid to occur, is cooled to room temperature filtering reacting liquid, drying filter cake obtains the 3 of grey, 4,9,10- tetracid glycosides.
Further preferably, the detailed process of step (5) are as follows: in microwave reactor, 3,4,9,10- tetra- acid anhydrides are added
In aqueous solution containing potassium hydroxide, it is warming up to certain temperature after mixing evenly, insulation reaction is cooled to room temperature afterwards for a period of time,
Adjusting reaction solution pH with 10% hydrochloric acid solution is 8~9, filtering reacting liquid, continues to adjust filtrate pH with 10% hydrochloric acid solution
It is 2~3, there are a large amount of solids to be precipitated at this time, filtering reacting liquid, filter cake is washed twice with saturated sodium chloride solution, and drying filter cake obtains
To 3,9- dioctyl phthalate；The certain temperature is 100~150 DEG C.
3,9- dioctyl phthalate chemical combination of the present invention with good photochemical stability and stronger fluorescence property
The preparation method of object, it is characterised in that the reaction equation in preparation process are as follows:
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this
The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair
Bright range.
Embodiment 1
In reaction flask, acenaphthene 15g is added in glacial acetic acid 500mL, sodium dichromate 55g is added, in room temperature condition
Under be to slowly warm up to 80 DEG C after mixing evenly, keep thermotonus 6h, TLC to monitor raw material fully reacting, reaction solution is fallen while hot
Enter in ice water 2000mL, there is solid precipitation, filters reaction solution, 1,8- naphthalene dicarboxylic anhydride 16g is obtained after filter cake is dried,1H NMR
(400MHz,DMSO-d6):δ8.55(dd,J1=8.0Hz, J1=4.0Hz, 4H), 7.93 (t, J1=4.0Hz, J1=8.0Hz,
2H)；13C NMR(100MHz,DMSO-d6):161.19,135.86,132.93,130.22,128.03,119.54ppm。
Embodiment 2
In reaction flask, 1,8- naphthalene diacid glycosides 50g (0.25mol) is added in the ammonium hydroxide 1000mL of saturation, in room temperature
Under the conditions of stirring 10min obtain the mixing liquid of yellow, be heated slowly to 70 DEG C, keep thermotonus 90min, TLC monitoring
Stop heating after raw material fully reacting, be slowly dropped to room temperature, there is a solid precipitation, filtering reacting liquid, filter cake with water 500mL wash to
Neutrality, then drying obtains 1,8- naphthalene diamides 44g under the conditions of 60 DEG C；1H NMR(400MHz,DMSO-d6):δ8.42(d,J
=4.0Hz, 4H), 7.83 (t, J1=8.0Hz, J2=4.0Hz, 2H)；13C NMR(100MHz,DMSO-d6):164.56,
134.78,132.03,130.42,127.53,122.93ppm。
Embodiment 3
In microwave reactor, diformazan is added in potassium hydroxide potassium hydroxide 100g (content 85%) and anhydrous sodium acetate 5g
In base sulfoxide, 1,8- benzene-naphthalene diimide 12g is added under nitrogen protection, adds rear microwave reaction and is warming up to 100 DEG C of reaction 6h, instead
Water is added after answering, water 100mL is added, reaction solution is poured into water 500mL after stirring 10min, is stirred at room temperature
1h has a large amount of solids to be precipitated, and filters reaction solution, and filter cake is added in the hydrochloric acid solution of saturation after being washed with water, and is heated to 75 DEG C
It is stirred to react 1h, again filtering reacting liquid, filter cake dries that obtain 3,4,9,10- tetracarboxylic acid diimides thick under the conditions of 80 DEG C
Product；3,4,9,10- tetracarboxylic acid diimide hydrochloride, crudes are added in concentrated sulfuric acid 200g, are to slowly warm up to 80 DEG C, slightly
Product are completely dissolved, and sulfuric acid 100g of the concentration for 50% is being slowly added dropwise, and about 1h is added dropwise completely, is warming up to 100 DEG C, the reaction was continued
It is cooled to room temperature after 30min, there are a large amount of solids to be precipitated, filtering reacting liquid, after filter cake is washed with the sulfuric acid solution that concentration is 78%
Drying obtains the 3,4,9,10- tetracarboxylic acid diimide sterling 11g of aubergine under the conditions of 80 DEG C again.
Embodiment 4
In microwave reactor, diformazan is added in potassium hydroxide potassium hydroxide 100g (content 85%) and anhydrous sodium acetate 5g
In base sulfoxide, 1,8- benzene-naphthalene diimide 12g is added under nitrogen protection, adds rear microwave reaction and is warming up to 70 DEG C of reaction 6h, instead
Water is added after answering, water 100mL is added, reaction solution is poured into water 500mL after stirring 10min, is stirred at room temperature
1h has a large amount of solids to be precipitated, and filters reaction solution, and filter cake is added in the hydrochloric acid solution of saturation after being washed with water, and is heated to 75 DEG C
It is stirred to react 1h, again filtering reacting liquid, filter cake dries that obtain 3,4,9,10- tetracarboxylic acid diimides thick under the conditions of 80 DEG C
Product；3,4,9,10- tetracarboxylic acid diimide hydrochloride, crudes are added in concentrated sulfuric acid 200g, are to slowly warm up to 80 DEG C, slightly
Product are completely dissolved, and sulfuric acid 100g of the concentration for 50% is being slowly added dropwise, and about 1h is added dropwise completely, is warming up to 100 DEG C, the reaction was continued
It is cooled to room temperature after 30min, there are a large amount of solids to be precipitated, filtering reacting liquid, after filter cake is washed with the sulfuric acid solution that concentration is 78%
Drying obtains the 3,4,9,10- tetracarboxylic acid diimide sterling 5g of aubergine under the conditions of 80 DEG C again.
Embodiment 5
In microwave reactor, diformazan is added in potassium hydroxide potassium hydroxide 100g (content 85%) and anhydrous sodium acetate 5g
In base sulfoxide, 1,8- benzene-naphthalene diimide 12g is added under nitrogen protection, adds rear microwave reaction and is warming up to 120 DEG C of reaction 6h, instead
Water is added after answering, water 100mL is added, reaction solution is poured into water 500mL after stirring 10min, is stirred at room temperature
1h has a large amount of solids to be precipitated, and filters reaction solution, and filter cake is added in the hydrochloric acid solution of saturation after being washed with water, and is heated to 75 DEG C
It is stirred to react 1h, again filtering reacting liquid, filter cake dries that obtain 3,4,9,10- tetracarboxylic acid diimides thick under the conditions of 80 DEG C
Product；3,4,9,10- tetracarboxylic acid diimide hydrochloride, crudes are added in concentrated sulfuric acid 200g, are to slowly warm up to 80 DEG C, slightly
Product are completely dissolved, and sulfuric acid 100g of the concentration for 50% is being slowly added dropwise, and about 1h is added dropwise completely, is warming up to 100 DEG C, the reaction was continued
It is cooled to room temperature after 30min, there are a large amount of solids to be precipitated, filtering reacting liquid, after filter cake is washed with the sulfuric acid solution that concentration is 78%
Drying obtains the 3,4,9,10- tetracarboxylic acid diimide sterling 8g of aubergine under the conditions of 80 DEG C again.
Embodiment 6
In reaction flask, under room temperature, 3,4,9,10- tetracarboxylic acid diimide 200g are slowly added into the concentrated sulfuric acid
In 800g (content 95%), it is to slowly warm up to 220 DEG C after adding, keeps thermotonus 2h, is then slowly dropped to room temperature, cooled down
The a large amount of solids of Cheng Zhongyou are precipitated, filtering reacting liquid, and filter cake is washed with water to neutrality, dries filter cake under the conditions of 80 DEG C and obtains 3,4,
9,10- glycosides crude product；Under the conditions of being protected from light, obtained crude product is all added to water 6000mL and potassium hydroxide 140g (content
85%) in mixed solution, under nitrogen protection, 90 DEG C are slowly heated to, are down to room temperature after keeping temperature to be stirred to react 1h, have
A large amount of solids are precipitated, and reaction solution is filtered by vacuum, and filter cake is washed with water 100mL；Under the conditions of nitrogen protection is with being protected from light, into filtrate
Potassium hydroxide 60g (content 85%) and active carbon 60g is added, ferric sulfate 60g and water is added after stirring 30min at room temperature
600mL keeps room temperature condition to be stirred to react 30min, filtering reacting liquid, and the hydrochloric acid solution 600g of saturation, heating are added in filtrate
To 80~90 DEG C of stirring 1h, there are a large amount of solids to occur, is cooled to room temperature filtering reacting liquid, drying filter cake obtains the 3 of grey, and 4,9,
10- tetracid glycosides 162g.
Embodiment 7
In microwave reactor, the aqueous solution containing potassium hydroxide 33.5g is added in 3,4,9,10- tetra- acid anhydrides 40g
In 200mL, microwave reaction is warming up to 120 DEG C after mixing evenly, is cooled to room temperature after insulation reaction 5h, with 10% hydrochloric acid solution
Adjusting reaction solution pH is 8~9, filtering reacting liquid, continues to adjust filtrate pH with 10% hydrochloric acid solution to be 2~3, have at this time a large amount of
Solid is precipitated, and filtering reacting liquid, filter cake is washed twice with saturated sodium chloride solution 200mL, and drying filter cake obtains 3,9- diformazan
Sour 31g；1H NMR(400MHz,DMSO-d6): δ 8.90-8.81 (m, 2H), 8.55-8.42 (m, 4H), 8.16 (d, J=4.0Hz,
2H), 7.72 (dd, J=8.0Hz, J=8.0Hz, 2H)；13C NMR(100MHz,DMSO-d6):δ168.90,133.79,
132.45,130.93,128.68,128.34,126.38,122.20,121.68,120.98,99.98ppm。
Embodiment 8
In microwave reactor, the aqueous solution containing potassium hydroxide 33.5g is added in 3,4,9,10- tetra- acid anhydrides 40g
In 200mL, microwave reaction is warming up to 100 DEG C after mixing evenly, is cooled to room temperature after insulation reaction 5h, with 10% hydrochloric acid solution
Adjusting reaction solution pH is 8~9, filtering reacting liquid, continues to adjust filtrate pH with 10% hydrochloric acid solution to be 2~3, have at this time a large amount of
Solid is precipitated, and filtering reacting liquid, filter cake is washed twice with saturated sodium chloride solution 200mL, and drying filter cake obtains 3,9- diformazan
Sour 25g；1H NMR(400MHz,DMSO-d6): δ 8.90-8.81 (m, 2H), 8.55-8.42 (m, 4H), 8.16 (d, J=4.0Hz,
2H), 7.72 (dd, J=8.0Hz, J=8.0Hz, 2H)；13C NMR(100MHz,DMSO-d6):δ168.90,133.79,
132.45,130.93,128.68,128.34,126.38,122.20,121.68,120.98,99.98ppm。
Embodiment 9
In microwave reactor, the aqueous solution containing potassium hydroxide 33.5g is added in 3,4,9,10- tetra- acid anhydrides 40g
In 200mL, microwave reaction is warming up to 150 DEG C after mixing evenly, is cooled to room temperature after insulation reaction 5h, with 10% hydrochloric acid solution
Adjusting reaction solution pH is 8~9, filtering reacting liquid, continues to adjust filtrate pH with 10% hydrochloric acid solution to be 2~3, have at this time a large amount of
Solid is precipitated, and filtering reacting liquid, filter cake is washed twice with saturated sodium chloride solution 200mL, and drying filter cake obtains 3,9- diformazan
Sour 29g；1H NMR(400MHz,DMSO-d6): δ 8.90-8.81 (m, 2H), 8.55-8.42 (m, 4H), 8.16 (d, J=4.0Hz,
2H), 7.72 (dd, J=8.0Hz, J=8.0Hz, 2H)；13C NMR(100MHz,DMSO-d6):δ168.90,133.79,
132.45,130.93,128.68,128.34,126.38,122.20,121.68,120.98,99.98ppm。
Embodiment above describes basic principles and main features of the invention and advantage, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention
Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (6)
1. one kind 3, the preparation method of 9- dioctyl phthalate, it is characterised in that specific steps are as follows:
Step (1), in glacial acetic acid solvent, acenaphthene aoxidizes under the action of sodium dichromate and obtains 1,8- naphthalic anhydride；
The acylation under the action of ammonium hydroxide of saturation of step (2), 1,8- naphthalic anhydride obtains 1,8- naphthalene Asia amide；
Step (3), 1,8- naphthalene Asia the amide microwave in alkaline environment under the alkaline environment that potassium hydroxide and anhydrous sodium acetate manufacture
C-C is coupled to obtain 3,4,9,10- tetracarboxylic acid diimide under reaction condition；
Step (4), 3,4,9,10- tetracarboxylic acid diimide are converted into 3,4,9,10- tetracid glycosides under strong acid effect；
Step (5), 3,4,9,10- tetracid glycosides obtain 3,9- dioctyl phthalate in microwave reactor neutral and alkali hydrolysis decarboxylation.
2. a kind of preparation method of 3,9- dioctyl phthalate according to claim 1, it is characterised in that: step (1) it is specific
Process are as follows: acenaphthene is added in glacial acetic acid, sodium dichromate is added, is to slowly warm up to 80 after mixing evenly at room temperature
DEG C, holding thermotonus to raw material fully reacting is while hot poured into reaction solution in ice water, there is solid precipitation, reaction solution is filtered,
1,8- naphthalene dicarboxylic anhydride is obtained after filter cake drying.
3. a kind of preparation method of 3,9- dioctyl phthalate according to claim 1, it is characterised in that: step (2) it is specific
Process are as follows: 1,8- naphthalene diacid glycosides is added in the ammonium hydroxide of saturation, stirs to get the mixing liquid of yellow at room temperature, is delayed
Slowly 70 DEG C are heated to, stop heating after keeping the thermotonus to raw material fully reacting, is slowly dropped to room temperature, there is solid precipitation,
Filtering reacting liquid, filter cake are washed with water to neutrality, and then drying obtains 1,8- naphthalene diamides under the conditions of 60 DEG C.
4. a kind of preparation method of 3,9- dioctyl phthalate according to claim 1, it is characterised in that: step (3) it is specific
Process are as follows: in microwave reactor, potassium hydroxide and anhydrous sodium acetate are added in dimethyl sulfoxide, are added under nitrogen protection
1,8- benzene-naphthalene diimide adds rear microwave reaction and is warming up to 100 DEG C of reaction 6h, and water is added after reaction, stirs handle after 10min
Reaction solution is poured into water, and stirs 3h at room temperature, has a large amount of solids to be precipitated, and filters reaction solution, and filter cake adds after being washed with water
Enter into the hydrochloric acid solution of saturation, be heated to 75 DEG C and be stirred to react 1h, again filtering reacting liquid, filter cake is dried under the conditions of 80 DEG C
Obtain 3,4,9,10- tetracarboxylic acid diimide crude product；3,4,9,10- tetracarboxylic acid diimide hydrochloride, crude is added to
In the concentrated sulfuric acid, 80 DEG C are to slowly warm up to, crude product is completely dissolved, and sulfuric acid of the concentration for 50% is being slowly added dropwise, and about 1h is added dropwise completely,
100 DEG C are warming up to, is cooled to room temperature after the reaction was continued 30min, there are a large amount of solids to be precipitated, filtering reacting liquid, filter cake is with concentration
After 78% sulfuric acid solution washing again under the conditions of 80 DEG C drying obtain aubergine 3,4,9,10- tetracarboxylic acid diimide it is pure
Product.
5. a kind of preparation method of 3,9- dioctyl phthalate according to claim 1, it is characterised in that: step (4) it is specific
Process are as follows: in the reaction vessel, under room temperature, 3,4,9,10- tetracarboxylic acid diimides are slowly added into the concentrated sulfuric acid,
It is to slowly warm up to 220 DEG C after adding, keeps thermotonus 2h, is then slowly dropped to room temperature, there are a large amount of solids to analyse in temperature-fall period
Out, filtering reacting liquid is washed with water filter cake to neutrality, dries filter cake under the conditions of 80 DEG C and obtain 3,4,9,10- glycosides crude products；?
Under the conditions of being protected from light, obtained crude product is all added in the mixed solution of water and potassium hydroxide, under nitrogen protection, is slowly added
Heat is down to room temperature after keeping temperature to be stirred to react 1h to 90 DEG C, has a large amount of solids to be precipitated, and reaction solution, filter cake water is filtered by vacuum
Washing；Under the conditions of nitrogen protection is with being protected from light, potassium hydroxide and active carbon are added into filtrate, stirs at room temperature
Ferric sulfate and water are added after 30min, room temperature condition is kept to be stirred to react 30min, the salt of saturation is added in filtrate for filtering reacting liquid
Acid solution is heated to 80~90 DEG C of stirring 1h, has a large amount of solids to occur, and is cooled to room temperature filtering reacting liquid, and drying filter cake obtains
The 3,4,9,10- tetracid glycosides of grey.
6. a kind of preparation method of 3,9- dioctyl phthalate according to claim 1, it is characterised in that: step (5) it is specific
Process are as follows: in microwave reactor, 3,4,9,10- tetra- acid anhydrides are added in the aqueous solution containing potassium hydroxide, are stirred evenly
After be warming up to 120 DEG C, insulation reaction is cooled to room temperature afterwards for a period of time, with 10% hydrochloric acid solution adjust reaction solution pH be 8~
9, filtering reacting liquid continues to adjust filtrate pH with 10% hydrochloric acid solution to be 2~3, has a large amount of solids to be precipitated at this time, filtering reaction
Liquid, filter cake are washed twice with saturated sodium chloride solution, and drying filter cake obtains 3,9- dioctyl phthalate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811201010.6A CN109400460A (en) | 2018-10-16 | 2018-10-16 | A kind of preparation method of 3,9- dioctyl phthalate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811201010.6A CN109400460A (en) | 2018-10-16 | 2018-10-16 | A kind of preparation method of 3,9- dioctyl phthalate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109400460A true CN109400460A (en) | 2019-03-01 |
Family
ID=65467211
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811201010.6A Pending CN109400460A (en) | 2018-10-16 | 2018-10-16 | A kind of preparation method of 3,9- dioctyl phthalate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109400460A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1135495A (en) * | 1997-07-25 | 1999-02-09 | Kawamura Inst Of Chem Res | Reagent for condensation reaction, and condensation of condensed polycyclic aromatic compound by using the reagent |
| CN103773080A (en) * | 2013-12-25 | 2014-05-07 | 连云港锐华化工有限公司 | Solvent green 5 isomer based solvent dye |
| CN106752059A (en) * | 2016-12-06 | 2017-05-31 | 浙江力禾集团有限公司 | The preparation method of Yi Zhong perylene red Lumogen Red F300 |
| CN108976237A (en) * | 2018-09-10 | 2018-12-11 | 河南湾流生物科技有限公司 | The preparation method and application of novel sour drug molecule with anti-tumor activity |
-
2018
- 2018-10-16 CN CN201811201010.6A patent/CN109400460A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1135495A (en) * | 1997-07-25 | 1999-02-09 | Kawamura Inst Of Chem Res | Reagent for condensation reaction, and condensation of condensed polycyclic aromatic compound by using the reagent |
| CN103773080A (en) * | 2013-12-25 | 2014-05-07 | 连云港锐华化工有限公司 | Solvent green 5 isomer based solvent dye |
| CN106752059A (en) * | 2016-12-06 | 2017-05-31 | 浙江力禾集团有限公司 | The preparation method of Yi Zhong perylene red Lumogen Red F300 |
| CN108976237A (en) * | 2018-09-10 | 2018-12-11 | 河南湾流生物科技有限公司 | The preparation method and application of novel sour drug molecule with anti-tumor activity |
Non-Patent Citations (3)
| Title |
|---|
| DASHEVSKII, M. M. 等: ""Oxidation of 4-nitroacenaphthene to nitrophthalic acid"", 《ZHURNAL OBSHCHEI KHIMII》 * |
| KARISHIN, A. P.等: ""Synthesis of naphthalimide and its derivatives"", 《 ZHURNAL OBSHCHEI KHIMII》 * |
| 刘明娣等: ""3,9-苝二甲酸的合成研究"", 《河南师范大学学报（自然科学版）》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1995012A (en) | Process for preparing 1,4-diamino-2,3-dicyan anthraquinone | |
| CN106752059A (en) | The preparation method of Yi Zhong perylene red Lumogen Red F300 | |
| CN104828780A (en) | Colorful environmentally friendly pearl powder bismuth oxychloride preparation method | |
| CN102093741B (en) | Preparation method of pigment yellow 138 | |
| WO2022166441A1 (en) | Preparation method for 2-acetyl-1,10-phenanthroline | |
| CN103709784A (en) | Blue reactive dye for printing, and preparation methods thereof | |
| KR100983298B1 (en) | Method for converting perylen-3,4:9,10-tetracarboxylic acid diimides into a form suitable for use as a fluorescent dye | |
| CN108976237B (en) | Preparation method and application of perylene acid drug molecule with anti-tumor activity | |
| CN109400460A (en) | A kind of preparation method of 3,9- dioctyl phthalate | |
| CN102212029A (en) | Synthesis method of disperse blue 60 intermediate | |
| CN102911526B (en) | turquoise blue reactive dye and preparation method thereof | |
| CN101880465B (en) | Production method for acid dye finished product | |
| CN101294005B (en) | Red naphtocyclinon solvent dye and preparation method thereof | |
| Jin et al. | Synthesis, application, and recovery of alkali-clearable disperse dyes containing azo pyridone structure | |
| Greene | Perylene pigments | |
| CN108929297B (en) | Dianhydride monomer containing asymmetric fluorophore structure and preparation method and application thereof | |
| CN103289431B (en) | Method for preparing reactive brilliant blue 3G for wool | |
| CN103242208B (en) | Process for preparing 1, 4-diamino-anthraquinone-2, 3-disulfonic acid by nicotinic acid method | |
| US3749726A (en) | Linear alkyl-amido trans-quinacridone pigments | |
| CN106582725B (en) | A kind of preparation method and application of copper/calcium sulfate carriers catalyst | |
| US3775434A (en) | Process for preparing a 3,4,9,10-perylene-tetracarboxylic acid dianhydride pigment | |
| US2212924A (en) | Production of phthalocyanine pigments | |
| CN102924961A (en) | Preparation method for disperse red | |
| CN109535767B (en) | Preparation method of perylene pigment | |
| CN106749019B (en) | A kind of environment-friendly preparation method of 52 dyestuff of solvent red |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190301 |