CN109608429A - A kind of synthesis technology of sulfonic group rhodamine compound - Google Patents
A kind of synthesis technology of sulfonic group rhodamine compound Download PDFInfo
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Abstract
The invention discloses a kind of synthesis technologies of sulfonic group rhodamine compound, it mixes saccharin and bronsted acid catalyst, and formula (I) compound represented is reacted to obtain in heating；Formula (II) compound represented and resorcinol heat reaction under the action of bronsted acid catalyst, obtain formula (III) compound represented；Nitrogen protection and under the conditions of being protected from light, heats reaction for the above-mentioned formula (I) being prepared and formula (III) compound represented under the action of Lewis acid catalyst, obtains sulfonic group rhodamine compound shown in formula (IV)；Synthesis technology through the invention avoids the use of thionyl chloride during traditional handicraft, and operation simplifies, and production security improves, and environmental pollution is small, and reaction carries out under normal pressure, and reaction has higher selectivity.Wherein the chemical structural formula of compound shown in formula (I), formula (II), formula (III) and formula (IV) is as follows:
Description
Technical field
The present invention relates to a kind of synthesis technologies of sulfonic group rhodamine compound.
Background technique
Sulfonic group rhodamine is a kind of excellent organic dyestuff, have structure easily modify with excellent optical property,
It can be used for preparing Functional dye, be had broad application prospects in dye field.Using xanthene type rhodamine as parent, draw
The group and water-soluble group sulfonic group for entering amino substitution can reduce cloud density on dye matrix molecule, increase dye
The flexibility for expecting parent molecule, and then improves their light shines, resistance to ozone, water-resistant capacity, increases the solubility of dye molecule and steady
It is qualitative.Traditional technique for preparing sulfonic group rhodamine is but the sulphonyl fluorescence using sulphonyl fluorescein as Material synthesis
Plain price is more expensive, and unstable, and facile hydrolysis, synthetic yield is low, often generates a large amount of spent acid, and cumbersome,
And there is certain risk, greatly improve production cost.
Summary of the invention
For above-mentioned technical problem of the existing technology, the purpose of the present invention is to provide a kind of simple processes, energy consumption
The synthesis technology of sulfonic group rhodamine compound low, production cost is low, environmental pollution is small.
A kind of synthesis technology of sulfonic group rhodamine compound, it is characterised in that including following technical process:
1) saccharin and bronsted acid catalyst are mixed, heating reaction is cooled to room temperature, after reaction in reaction mixture
Solid is precipitated, is obtained by filtration solid, solid it is dry formula (I) compound represented；
2) formula (II) compound represented and bronsted acid catalyst are mixed in organic solvent, preparation forms reaction raw materials
Liquid；Under nitrogen protection, the reaction raw materials drop of above-mentioned preparation is added in resorcinol, heating reaction cools down after reaction
To room temperature, reaction mixture is post-treated to obtain formula (III) compound represented；
3) effect of nitrogen protection and under the conditions of being protected from light, formula (I) and formula (III) compound represented in Lewis acid catalyst
Lower heating reaction, is cooled to room temperature, reaction mixture is post-treated to obtain sulfonic group Luo Dan shown in formula (IV) after reaction
Bright compound；
In formula (II), formula (III) or formula (IV), R1、R2Separately it is selected from H, C1~C16Alkyl, C1~C16Substitution
Alkyl or substituted aryl；
C1~C16Substitution alkyl substituent group be one or more, each substituent group be each independently selected from alkoxy,
Hydroxyl, nitro or halogen；
Substituent group on the aromatic ring of substituted aryl is one or more, and each substituent group is each independently selected from C1~C16's
Alkyl, C1~C16Alkoxy, hydroxyl, nitro, halogen, amido, monoalkyl replace amido, dialkyl group replace amido, institute
The carbon atom number for the alkyl in amido that the amido or dialkyl group for stating monoalkyl substitution replace is 1~16.
The synthesis technology of a kind of sulfonic group rhodamine compound, it is characterised in that the aryl of the substituted aryl is
Phenyl.
The synthesis technology of a kind of sulfonic group rhodamine compound, it is characterised in that Protic Acid Catalyzed in step 1)
Agent is phosphoric acid, polyphosphoric acids, acetic acid, hydrochloric acid or the concentrated sulfuric acid；The molar ratio of saccharin and the bronsted acid catalyst be 1:3~
5, preferably 1:4~5.
The synthesis technology of a kind of sulfonic group rhodamine compound, it is characterised in that Protic Acid Catalyzed in step 2)
Agent is phosphoric acid, polyphosphoric acids, acetic acid, hydrochloric acid or the concentrated sulfuric acid；Resorcinol, formula (II) compound represented and the Bronsted acid are urged
The molar ratio of agent is 1:0.7~1.2:0.05~0.1, preferably 1:0.8~1:0.06~0.07.
A kind of synthesis technology of the sulfonic group rhodamine compound, it is characterised in that in step 3), Lewis acid catalysis
Agent is anhydrous zinc chloride, anhydrous aluminum chloride, anhydrous ferric chloride, aluminium oxide or anhydrous stannic chloride；Compound, formula described in formula (I)
(III) molar ratio of compound represented and the Lewis acid catalyst be 1:2~2.5:2~2.5, preferably 1:2~
2.1:2~2.3.
A kind of synthesis technology of sulfonic group rhodamine compound, it is characterised in that the temperature of heating reaction in step 1)
Degree is 110~150 DEG C, preferably 130~140 DEG C；The temperature of heating reaction is 40~160 DEG C in step 2), preferably 50~
150℃；The temperature of heating reaction is 140~180 DEG C, preferably 160~170 DEG C in step 3).
A kind of synthesis technology of the sulfonic group rhodamine compound, it is characterised in that in step 1) heating reaction when
Between be 1~3h, preferably 2h；The time of heating reaction is 10~15h, preferably 13h in step 2)；Heating reaction in step 3)
Time be 8~12h, preferably 10h.
A kind of synthesis technology of the sulfonic group rhodamine compound, it is characterised in that in step 2), mixed solution drop
The speed being added in resorcinol is to drip for every 2 seconds 1~2；The organic solvent is toluene, dimethylbenzene, chlorobenzene or dichloro-benzenes.
A kind of synthesis technology of the sulfonic group rhodamine compound, it is characterised in that in step 2), the step of post-processing
Suddenly are as follows: after reaction mixture is washed with water 2~3 times, be spin-dried for solvent, be then dried to obtain formula (III) compound represented.
A kind of synthesis technology of the sulfonic group rhodamine compound, it is characterised in that in step 3), the step of post-processing
Suddenly are as follows: reaction mixture is dissolved with methanol, and water is then added, and a large amount of magenta solids are precipitated, and is filtered, and filter residue and drying obtains slightly
Product, crude product are recrystallized to give sulfonic group rhodamine compound shown in formula (IV)；Recrystallization solvent for use is dehydrated alcohol, first
Alcohol, DMF or DMSO.
In the present invention, do not have to the source of compound shown in the saccharin, resorcinol and formula (II) and organic solvent
There is any special limitation, using technological means well known to those skilled in the art or commercial goods.
Compared with prior art, the invention has the advantages that: the present invention only in presence of an acid catalyst, o-methyl benzoic acid anhydride
It reacts the synthesis for realizing oxa- anthracene nucleus under solvent-free conditions with formula (III) compound represented, avoids traditional handicraft process
The use of middle thionyl chloride, operation simplify, and production security improves, and environmental pollution is small；Reaction has higher selectivity, and reaction exists
It is carried out under normal pressure, is reacted relative to conventional high-tension, be beneficial to energy conservation and reduce production cost；O-methyl benzoic acid anhydride and formula (III)
There is higher separative efficiency in the last handling process of compound represented reaction, operating procedure is simplified, and reduces product
Loss.
To sum up, the synthesis technology of functional molecular dyestuff sulfonic group rhodamine of the present invention has the characteristics that green, efficient,
Suitable for industrialized production.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but the scope of protection of the present invention is not limited thereto.
In following embodiment, the synthesis technology of the sulfonic group rhodamine compound, specific synthetic route is as follows:
Embodiment 1:
N2Under protection, 9.0g saccharin solid and the 13mL concentrated sulfuric acid (concentration 98%) are sequentially added in 50mL three-necked flask,
It after being stirred to react 2h at 140 DEG C, is cooled to room temperature, a large amount of solids is precipitated in reaction mixture, filter, filtering obtained solid is used
Ice water washing, drying obtain the o-methyl benzoic acid anhydride white solid 7.3g of structure shown in formula (I), yield 81%.
Nuclear magnetic spectrogram analysis is carried out to the obtained compound with structure shown in formula (I), as a result as follows:1HNMR
(500MHz, CDCl3) δ 8.77 (d, J=7.3Hz, 1H), 8.05 (d, J=7.3Hz, 1H), 7.76 (t, J=2.2Hz, 1H),
7.53 (t, J=8.5Hz, 1H).
The diethylamine of 4.8g and 0.3mL phosphoric acid (weight concentration 85%) are sufficiently mixed in 20mL toluene, shape is prepared
At reaction raw materials liquid；N2Under protection, the reaction raw materials liquid of above-mentioned preparation is slowly added dropwise between 9.1g with the speed of every 2 seconds 1 drops
In the mixed liquor of benzenediol and 20mL toluene, at 50 DEG C after heating reaction 10h, it is cooled to room temperature, stratification has simultaneously been isolated
Machine layer, organic layer are washed with water, and are finally spin-dried for solvent, are then dissolved in dehydrated alcohol and are recrystallized, and filtering, filter residue and drying obtains
To the violet solid compound 5.0g of structure shown in formula (III), yield 46%.
N2Under the conditions of protecting and being protected from light, first by the above-mentioned o-methyl benzoic acid anhydride 9.0g being prepared and formula (III) shownization
It closes object 8.1g and anhydrous stannic chloride 12.7g to be added in 250mL there-necked flask, then mechanic whirl-nett reaction 1h at 130 DEG C adds again
Enter compound 8.1g shown in anhydrous zinc chloride 12.7g and formula (III), is continuously heating to 160 DEG C, is stirred to react 7h, be cooled to room
Temperature, reaction mixture are dissolved with methanol, and water is added, and a large amount of red solids are precipitated, and are filtered, and filter residue is recrystallized with dehydrated alcohol,
Filter, be dried to obtain the red compound 14.1g of the structure as shown in formula (IV), yield 60%.
In the present embodiment, substituent R1And R2Indicate ethyl.
Embodiment 2
In N2Under protection, 9.0g saccharin solid and the 10.5mL concentrated sulfuric acid (concentration are sequentially added in 50mL three-necked flask
98%) it after, being stirred to react 2h at 140 DEG C, is cooled to room temperature, a large amount of solids is precipitated in reaction mixture, filter, filtering gained
Solid is washed with ice water, and drying obtains the o-methyl benzoic acid anhydride white solid 6.3g of structure shown in formula (I), yield 70%.
The diethylamine of 5.4g and 0.4mL phosphoric acid (weight concentration 85%) are sufficiently mixed in 25mL toluene, shape is prepared
At reaction raw materials liquid；N2Under protection, the reaction raw materials liquid of above-mentioned preparation is slowly added dropwise with the speed of 1 drop per second in 9.1g isophthalic
In the mixed liquor of diphenol and 20mL toluene, at 55 DEG C after heating reflux reaction 10h, it is cooled to room temperature, stratification is simultaneously isolated
Organic layer, organic layer are washed with water, and are finally spin-dried for solvent, obtain the violet solid compound 6.3g of structure shown in formula (III), produce
Rate 52%.
N2It, first will be shown in compound 9.0g shown in the above-mentioned formula (I) being prepared and formula (III) under the conditions of protecting and being protected from light
Compound 8.5g and anhydrous stannic chloride 13.0g are added in 250mL there-necked flask, mechanic whirl-nett reaction 1h at 135 DEG C, then again
Compound 8.5g shown in anhydrous stannic chloride 13.0g and formula (III) is added, is continuously heating to 160 DEG C, is stirred to react 8h, be cooled to room
Temperature, reaction mixture are dissolved with methanol, and water is added, and a large amount of red solids are precipitated, and are filtered, and filter residue is recrystallized with dehydrated alcohol,
Filter, be dried to obtain the red compound 11.5g of the structure as shown in formula (IV), yield 49%.
In the present embodiment, substituent R1And R2Indicate ethyl.
Embodiment 3
In N2Under protection, 100.0g saccharin solid and the 155mL concentrated sulfuric acid (concentration are sequentially added in 500mL three-necked flask
98%) it after, being stirred to react 3h at 145 DEG C, is cooled to room temperature, a large amount of solids is precipitated in reaction mixture, filter, filtering gained
Solid is washed with ice water, and drying obtains the o-methyl benzoic acid anhydride white solid 87.5g of structure shown in formula (I), yield 87%.
The diethylamine of 193.4g and 10.0mL phosphoric acid (weight concentration 85%) are sufficiently mixed in 400mL toluene, matched
System forms reaction raw materials liquid；N2Under protection, the reaction raw materials liquid of above-mentioned preparation is slowly added dropwise with the speed of 1 drop per second
In the mixed liquor of 300.0g resorcinol and 600mL toluene, at 50 DEG C after heating reaction 12h, it is cooled to room temperature, stratification is simultaneously
Organic layer is isolated, organic layer is washed with water, and is finally spin-dried for solvent, is dried to obtain the violet solid chemical combination of structure shown in formula (III)
Object 210.8g, yield 49%.
N2It, first will be shown in compound 85.0g shown in the above-mentioned formula (I) being prepared and formula (III) under the conditions of protecting and being protected from light
Compound 83.8g and anhydrous stannic chloride 121.0g is added in 500mL there-necked flask, mechanic whirl-nett reaction 1.5h at 135 DEG C, then
Compound 83.8g shown in anhydrous stannic chloride 121.0g and formula (III) is added, 165 DEG C is continuously heating to, is stirred to react 8h, it is cooling
To room temperature, reaction mixture is dissolved with methanol, and water is added, and a large amount of magenta solids are precipitated, and is filtered, filter residue dehydrated alcohol weight
Crystallization, filters, is dried to obtain the magenta compound 135.3g of the structure as shown in formula (IV), yield 61%.
In the present embodiment, substituent R1And R2Indicate ethyl.
Embodiment 4:
N2Under protection, 9.0g saccharin solid and the 13mL concentrated sulfuric acid (concentration 98%) are sequentially added in 50mL three-necked flask,
It after being stirred to react 2h at 140 DEG C, is cooled to room temperature, a large amount of solids is precipitated in reaction mixture, filter, filtering obtained solid is used
Ice water washing, drying obtain the o-methyl benzoic acid anhydride white solid 7.3g of structure shown in formula (I), yield 81%.
The aniline of 6.9g and 0.3mL phosphoric acid (weight concentration 85%) are sufficiently mixed in 30mL dimethylbenzene, shape is prepared
At reaction raw materials liquid；N2Under protection, the reaction raw materials liquid of above-mentioned preparation is slowly added dropwise between 9.1g with the speed of every 2 seconds 1 drops
In the mixed liquor of benzenediol and 25mL dimethylbenzene, at 140 DEG C after heating reaction 10h, it is cooled to room temperature, stratification is simultaneously isolated
Organic layer, organic layer are washed with water, and are finally spin-dried for solvent, are then dissolved in dehydrated alcohol and are recrystallized, filtering, filter residue and drying
Obtain the dark red solid compound 8.9g of structure shown in formula (III), yield 65%.
N2Under the conditions of protecting and being protected from light, first by compound o-methyl benzoic acid anhydride shown in the above-mentioned formula (I) being prepared
Compound 9.5g shown in 9.0g and formula (III) and anhydrous aluminum chloride 6.5g is added in 250mL there-necked flask, mechanical stirring at 130 DEG C
1h is reacted, compound 9.5g shown in anhydrous aluminum chloride 6.5g and formula (III) is then added, is continuously heating to 160 DEG C, stirring is anti-
7h is answered, is cooled to room temperature, reaction mixture is dissolved with methanol, and water is added, and a large amount of magenta solids are precipitated, and is filtered, and filter residue is used
Dehydrated alcohol recrystallization, filters, is dried to obtain the red compound 15.2g of the structure as shown in formula (IV), yield 60%.
In the present embodiment, substituent R1Indicate phenyl, R2Indicate H.
Embodiment 5
In N2Under protection, 9.0g saccharin solid and the 10.5mL concentrated sulfuric acid (concentration are sequentially added in 50mL three-necked flask
98%) it after, being stirred to react 2h at 140 DEG C, is cooled to room temperature, a large amount of solids is precipitated in reaction mixture, filter, filtering gained
Solid is washed with ice water, and drying obtains the o-methyl benzoic acid anhydride white solid 6.3g of structure shown in formula (I), yield 70%.
The aniline of 6.2g and 0.3mL phosphoric acid (weight concentration 85%) are sufficiently mixed in 30mL dimethylbenzene, shape is prepared
At reaction raw materials liquid；N2Under protection, the reaction raw materials liquid of above-mentioned preparation is slowly added dropwise with the speed of 1 drop per second in 9.1g isophthalic
In the mixed liquor of diphenol and 20mL dimethylbenzene, at 140 DEG C after heating reaction 10h, it is cooled to room temperature, stratification has simultaneously been isolated
Machine layer, organic layer are washed with water, and are finally spin-dried for solvent, are then dissolved in dehydrated alcohol and are recrystallized, and filtering, filter residue and drying obtains
To the dark red solid compound 7.3g of structure shown in formula (III), yield 59%.
N2It, first will be shown in compound 9.0g shown in the above-mentioned formula (I) being prepared and formula (III) under the conditions of protecting and being protected from light
Compound 9.5g and anhydrous aluminum chloride 7.0g are added in 250mL there-necked flask, mechanic whirl-nett reaction 1h at 140 DEG C, then again
Chemical combination 9.5g shown in anhydrous aluminum chloride 7.0g and formula (III) is added, is continuously heating to 160 DEG C, is stirred to react 8h, be cooled to room temperature,
Reaction mixture is dissolved with methanol, and water is added, and a large amount of magenta solids are precipitated, and is filtered, and filter residue is recrystallized with dehydrated alcohol, mistake
Filter, be dried to obtain the magenta compound 13.2g of the structure as shown in formula (IV), yield 52%.
In the present embodiment, substituent R1Indicate phenyl, R2Indicate H.
Embodiment 6
In N2Under protection, 100.0g saccharin solid and the 155mL concentrated sulfuric acid (concentration are sequentially added in 500mL three-necked flask
98%) it after, being stirred to react 3h at 145 DEG C, is cooled to room temperature, a large amount of solids is precipitated in reaction mixture, filter, filtering gained
Solid is washed with ice water, and drying obtains the o-methyl benzoic acid anhydride white solid 86.5g of structure shown in formula (I), yield 86%.
The aniline of 241.0g and 7.1mL phosphoric acid are sufficiently mixed in 400mL dimethylbenzene, preparation forms reaction raw materials liquid；
N2Under protection, the reaction raw materials liquid of above-mentioned preparation is slowly added dropwise with the speed of 1 drop per second in 300.0g resorcinol and 600mL
In the mixed liquor of dimethylbenzene, at 165 DEG C after heating reaction 12h, it is cooled to room temperature, stratification simultaneously isolates organic layer, organic
Layer is washed with water, and is finally spin-dried for solvent, is then dissolved in dehydrated alcohol and is recrystallized, and filters, and filter residue and drying obtains formula (III)
The dark red solid compound 316.4g of shown structure, yield 66%.
N2It, first will be shown in compound 85.0g shown in the above-mentioned formula (I) being prepared and formula (III) under the conditions of protecting and being protected from light
Compound 85.5g and anhydrous aluminum chloride 61.4g is added in 500mL there-necked flask, mechanic whirl-nett reaction 1.5h at 130 DEG C, then
Compound 85.5g shown in anhydrous aluminum chloride 61.4g and formula (III) is added, 165 DEG C is continuously heating to, is stirred to react 9h, it is cooling
To room temperature, reaction mixture is dissolved with methanol, and water is added, and a large amount of red solids are precipitated, and is filtered, and filter residue is tied again with dehydrated alcohol
Crystalline substance filters, is dried to obtain the red compound 100.5g of the structure as shown in formula (IV), yield 42%.
In the present embodiment, substituent R1Indicate phenyl, R2Indicate H.
Embodiment 7:
N2Under protection, 9.0g saccharin solid and the 13mL concentrated sulfuric acid (concentration 98%) are sequentially added in 50mL three-necked flask,
It after being stirred to react 2h at 140 DEG C, is cooled to room temperature, a large amount of solids is precipitated in reaction mixture, filter, filtering obtained solid is used
Ice water washing, drying obtain the o-methyl benzoic acid anhydride white solid 7.3g of structure shown in formula (I), yield 81%.
By the 2,6- dimethylaniline of 10.0g and 2.7g polyphosphoric acids (with P2O5Meter, concentration 84%) it is sufficiently mixed in 30mL
In o-dichlorohenzene, preparation forms reaction raw materials liquid；N2Under protection, by the reaction raw materials liquid of above-mentioned preparation with the speed of every 2 seconds 1 drops
It is slowly added dropwise in the mixed liquor of 9.1g resorcinol and 20mL o-dichlorohenzene, at 155 DEG C after heating reaction 10h, is cooled to room
Temperature, stratification simultaneously isolate organic layer, and organic layer is washed with water, and is finally spin-dried for solvent, obtains the purple of structure shown in formula (III)
Color oily compound 8.0g, yield 46%.
Nuclear magnetic spectrogram analysis is carried out to the obtained compound with structure shown in formula (III), as a result as follows:1H NMR
(500MHz, DMSO) δ 9.52 (s, 1H), 7.75 (d, J=7.3Hz, 1H), 7.06 (t, J=2.2Hz, 1H), 6.93-6.56 (m,
J=7.3Hz, 3H), 6.36 (d, J=4.5Hz, 1H), 6.06 (d, J=7.1Hz, 1H), 5.46 (s, 1H), 2.06 (s, 6H)
N2Under the conditions of protecting and being protected from light, first by the above-mentioned o-methyl benzoic acid anhydride 9.0g being prepared and formula (III) shownization
It closes object 10.4g and anhydrous zinc chloride 6.7g to be added in 250mL there-necked flask, mechanic whirl-nett reaction 1h, then adds at 130 DEG C
Compound 10.4g shown in anhydrous zinc chloride 6.7g and formula (III), is continuously heating to 160 DEG C, is stirred to react 7h, be cooled to room temperature,
Reaction mixture is dissolved with methanol, and water is added, and a large amount of magenta solids are precipitated, and is filtered and dry, is recrystallized with dehydrated alcohol,
Obtain the magenta compound 16.8g of the structure as shown in formula (IV), yield 60%.
Nuclear magnetic spectrogram analysis is carried out to the obtained compound with structure shown in formula (IV), as a result as follows:
1H NMR(500MHz,DMSO)δ11.29(s,1H),9.89(s,1H),8.20–7.90(m,2H),7.76–7.57
(m,2H),7.46–7.11(m,6H),6.93(s,1H),6.85–6.74(m,1H),6.43–5.74(m,4H),3.34(s,6H),
2.50(s,6H)。
In the present embodiment, substituent R1Indicate 2,6- 3,5-dimethylphenyl, R2Indicate H.
Embodiment 8
In N2Under protection, 9.0g saccharin solid and the 10.5mL concentrated sulfuric acid (concentration are sequentially added in 50mL three-necked flask
98%) it after, being stirred to react 2h at 140 DEG C, is cooled to room temperature, a large amount of solids is precipitated in reaction mixture, filter, filtering gained
Solid is washed with ice water, and drying obtains the o-methyl benzoic acid anhydride white solid 6.3g of structure shown in formula (I), yield 70%.
By the 2,6- dimethylaniline of 11.0g and 1.8g polyphosphoric acids (with P2O5Meter, concentration 84%) it is sufficiently mixed in 30mL
In o-dichlorohenzene, preparation forms reaction raw materials liquid；N2Under protection, by the reaction raw materials liquid of above-mentioned preparation with the speed of 1 drop per second
It is slowly added dropwise in the mixed liquor of 9.1g resorcinol and 20mL o-dichlorohenzene, at 160 DEG C after heating reaction 1h, is cooled to room
Temperature, stratification simultaneously isolate organic layer, and organic layer is washed with water, and is finally spin-dried for solvent, obtains the purple of structure shown in formula (III)
Color oily compound 7.5g, yield 43%.
N2It, first will be shown in compound 9.0g shown in the above-mentioned formula (I) being prepared and formula (III) under the conditions of protecting and being protected from light
Compound 10.9g and anhydrous zinc chloride 6.98g are added in 250mL there-necked flask, mechanic whirl-nett reaction 1h at 135 DEG C, then
Compound 10.9g shown in anhydrous zinc chloride 6.98g and formula (III) is added, 160 DEG C is continuously heating to, is stirred to react 8h, it is cooling
To room temperature, reaction mixture is dissolved with methanol, and water is added, and a large amount of magenta solids are precipitated, and is filtered and dry, is obtained such as formula
(IV) the magenta compound 15.4g of structure shown in, yield 55%.
In the present embodiment, substituent R1Indicate 2,6- 3,5-dimethylphenyl, R2Indicate H.
Embodiment 9
In N2Under protection, 100.0g saccharin solid is sequentially added in 500mL three-necked flask and the 149.7mL concentrated sulfuric acid is (dense
98%) degree, after being stirred to react 3h at 145 DEG C, is cooled to room temperature, a large amount of solids is precipitated in reaction mixture, filter, and filters institute
It obtains solid to be washed with ice water, dries, obtain the o-methyl benzoic acid anhydride white solid 85.5g of structure shown in formula (I), yield
85%.
By the 2,6- dimethylaniline of 300.0g and 92.3g polyphosphoric acids (with P2O5Meter, concentration 84%) it is sufficiently mixed
In 400mL o-dichlorohenzene, preparation forms reaction raw materials liquid；N2Under protection, by the reaction raw materials liquid of above-mentioned preparation with 1 drop per second
Speed is slowly added dropwise in the mixed liquor of 300.0g resorcinol and 600mL o-dichlorohenzene, cold at 165 DEG C after heating reaction 5h
But to room temperature, stratification simultaneously isolates organic layer, and organic layer is washed with water, and is finally spin-dried for solvent, obtains knot shown in formula (III)
The purple oily compound 248.2g of structure, yield 47%.
N2It, first will be shown in compound 85.0g shown in the above-mentioned formula (I) being prepared and formula (III) under the conditions of protecting and being protected from light
Compound 103.3g and anhydrous zinc chloride 54.4g is added in 500mL there-necked flask, mechanic whirl-nett reaction 1.5h at 135 DEG C, then
Compound 103.3g shown in anhydrous zinc chloride 54.4g and formula (III) is added, 165 DEG C is continuously heating to, is stirred to react 8h, it is cooling
To room temperature, reaction mixture is dissolved with methanol, and water is added, and a large amount of magenta solids are precipitated, and is filtered and dry, is obtained such as formula
(IV) the magenta compound 172.4g of structure shown in, yield 65%.
In the present embodiment, substituent R1Indicate 2,6- 3,5-dimethylphenyl, R2Indicate H.
Content described in this specification is only to enumerate to inventive concept way of realization, and protection scope of the present invention is not answered
When the concrete form for being seen as limited by embodiment and being stated.
Claims (10)
1. a kind of synthesis technology of sulfonic group rhodamine compound, it is characterised in that including following technical process:
1) saccharin and bronsted acid catalyst are mixed, heating reaction is cooled to room temperature after reaction, is precipitated in reaction mixture
Solid, is obtained by filtration solid, solid it is dry formula (I) compound represented；
2) formula (II) compound represented and bronsted acid catalyst are mixed in organic solvent, preparation forms reaction raw materials liquid；
Under nitrogen protection, the reaction raw materials drop of above-mentioned preparation is added in resorcinol, heating reaction is cooled to room after reaction
Temperature, reaction mixture is post-treated to obtain formula (III) compound represented；
3) nitrogen protection and under the conditions of being protected from light, formula (I) and formula (III) compound represented add under the action of Lewis acid catalyst
Thermal response is cooled to room temperature after reaction, and reaction mixture is post-treated to obtain sulfonic group rhodamine shown in formula (IV)
Close object；
In formula (II), formula (III) or formula (IV), R1、R2Separately it is selected from H, C1~C16Alkyl, C1~C16Substitution alkane
Base or substituted aryl；
C1~C16Substitution alkyl substituent group be one or more, each substituent group be each independently selected from alkoxy, hydroxyl,
Nitro or halogen；
Substituent group on the aromatic ring of substituted aryl is one or more, and each substituent group is each independently selected from C1~C16Alkane
Base, C1~C16Alkoxy, hydroxyl, nitro, halogen, amido, monoalkyl replace amido, dialkyl group replace amido, it is described
The carbon atom number for the alkyl in amido that the amido or dialkyl group that monoalkyl replaces replace is 1 ~ 16.
2. a kind of synthesis technology of sulfonic group rhodamine compound as described in claim 1, it is characterised in that the substitution virtue
The aryl of base is phenyl.
3. a kind of synthesis technology of sulfonic group rhodamine compound as described in claim 1, it is characterised in that in step 1), matter
Sub- acid catalyst is phosphoric acid, polyphosphoric acids, acetic acid, hydrochloric acid or the concentrated sulfuric acid；Saccharin and the bronsted acid catalyst feed intake mole
Than for 1:3 ~ 5, preferably 1: 4 ~ 5.
4. a kind of synthesis technology of sulfonic group rhodamine compound as described in claim 1, it is characterised in that in step 2, matter
Sub- acid catalyst is phosphoric acid, polyphosphoric acids, acetic acid, hydrochloric acid or the concentrated sulfuric acid；Resorcinol, formula (II) compound represented and described
The molar ratio of bronsted acid catalyst is 1:0.7 ~ 1.2:0.05 ~ 0.1, preferably 1:0.8 ~ 1:0.06 ~ 0.07.
5. a kind of synthesis technology of sulfonic group rhodamine compound as described in claim 1, it is characterised in that in step 3),
Lewis acid catalyst is anhydrous zinc chloride, anhydrous aluminum chloride, anhydrous ferric chloride, aluminium oxide or anhydrous stannic chloride；Formula (I) is described
Compound, formula (III) compound represented and the Lewis acid catalyst molar ratio be 1:2 ~ 2.5:2 ~ 2.5,
Preferably 1:2 ~ 2.1:2 ~ 2.3.
6. a kind of synthesis technology of sulfonic group rhodamine compound as described in claim 1, it is characterised in that add in step 1)
The temperature of thermal response is 110 ~ 150 DEG C, preferably 130 ~ 140 DEG C；The temperature that reaction is heated in step 2 is 40 ~ 160
DEG C, preferably 50 ~ 150 DEG C；The temperature that reaction is heated in step 3) is 140 ~ 180 DEG C, preferably 160 ~ 170 DEG C.
7. a kind of synthesis technology of sulfonic group rhodamine compound as described in claim 1, it is characterised in that add in step 1)
The time of thermal response is 1 ~ 3h, preferably 2h；The time that reaction is heated in step 2 is 10 ~ 15h, preferably 13h；In step 3)
The time of heating reaction is 8 ~ 12h, preferably 10h.
8. a kind of synthesis technology of sulfonic group rhodamine compound as described in claim 1, it is characterised in that in step 2, mix
Closing solution and being added drop-wise to the speed in resorcinol is to drip for every 2 seconds 1 ~ 2；The organic solvent is toluene, dimethylbenzene, chlorobenzene or dichloro
Benzene.
9. a kind of synthesis technology of sulfonic group rhodamine compound as described in claim 1, it is characterised in that in step 2, after
The step of processing are as follows: after reaction mixture is washed with water 2 ~ 3 times, be spin-dried for solvent, be then dried to obtain chemical combination shown in formula (III)
Object.
10. a kind of synthesis technology of sulfonic group rhodamine compound as described in claim 1, it is characterised in that in step 3),
The step of post-processing are as follows: reaction mixture is dissolved with methanol, and water is then added, and a large amount of magenta solids are precipitated, and is filtered, and filter residue is dry
Dry to obtain crude product, crude product is recrystallized to give sulfonic group rhodamine compound shown in formula (IV)；Recrystallization solvent for use is nothing
Water-ethanol, methanol, DMF or DMSO.
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