CN110283064A - A kind of 9,10- anthraquinone derivative and its preparation method and application - Google Patents
A kind of 9,10- anthraquinone derivative and its preparation method and application Download PDFInfo
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Abstract
The invention discloses one kind 9,10- anthraquinone derivative, which prepares with the following method: (1) inorganic acid solution of compound A1 and azeotropic being carried out dehydration, obtain compound B-11；Compound A2 and inorganic acid are subjected to dehydration, obtain compound B2；(2) Isosorbide-5-Nitrae-benzoquinones, compound B-11 and compound B2 carry out sudden reaction in organic media, obtain 9,10- anthraquinone derivative.Provided by the invention 9, direct application of the 10- anthraquinone derivative for anthraquinone system derivative in field of organic electroluminescence, dyestuff, field of medicaments provides the selection of diversification, and also the anthracene derivative for further synthesized high-performance, high application value provides new intermediate feed；And its synthetic method is simple, reaction condition is mild, reaction raw materials convenient sources, and at low cost, organic solvent is few using type, the purity and high income of product obtained.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to one kind 9,10- anthraquinone derivative and preparation method thereof and
Using.
Background technique
Anthraquinone and its derivative are polycyclic compounds very widely used at present.On the one hand, anthraquinone analog compound has been
It is applied to organic photoelectric functional material and optical sensor etc., in field of organic electroluminescence, anthraquinone radicals has as follows
Feature: (1) two sides carbonyl in anthraquinone ring assigns that anthraquinone is good to receive electronic capability；(2) due to carbonyl participate in n →
π * electron transition has biggish Quantum geometrical phase, theoretically phosphorus easy to accomplish between the lowest triplet state and ground state of anthraquinone
The radiation transistion of light；(3) anthraquinone radicals has chemical reactivity site abundant, is easy to be chemically modified.Therefore anthraquinone
It is constructing electroluminescent organic material of new generation and is attempting it in electroluminescent device using upper, having broad prospects.Separately
On the one hand, anthraquinone is important fine chemicals, catalytic hydrogenation and the reversible property being oxidized, and it is raw to become hydrogen peroxide
Widely used working material in production.In addition, anthraquinone and its derivative are the primary raw materials for synthesizing anthraquinone based dye and intermediate,
Using anthraquinone and its derivative as raw material, sulfonated, chlorination, nitrification, cyaniding, fluorination etc., the dyestuff that can be of wide application
Intermediate, for producing anthraquinone system disperse dyes, acid dyes, reactive dye, reducing dye etc., formation chromatography is complete, performance is good
Dye class.Also, anthraquinone and its derivative are also found in recent years has inhibiting effect to tumour, also has in field of medicaments
Important application value.Therefore, anthraquinone and its derivative are studied, more polynary anthraquinone derivative is provided, in its preferably application
It is shown in semiconductor, on hydrogen peroxide industry, anthraquinone based dye and field of medicaments, there is actual value.
Anthraquinone is as a kind of important chemical raw material, but also anthraquinone derivative is very tight on international market at home
It is pretty, its production technology is improved, the yield and product purity of anthraquinone derivative are further increased, it is raw to reduce anthraquinone derivative
Cost is produced, there is far reaching significance to promoting entire chemical industry to develop.
Summary of the invention
It is an object of the invention to overcome above-mentioned technical deficiency, the purpose of first aspect present invention is, provides one kind 9,
10- anthraquinone derivative provides the anthraquinone derivative of diversification, has expanded the type of anthraquinone derivative；Second party of the present invention
The purpose in face is, provides the preparation method of one kind 9,10- anthraquinone derivative；The purpose of third aspect present invention is, provides
The application of one kind 9,10- anthraquinone derivative.
To reach above-mentioned technical purpose, technical solution of the present invention provides one kind 9,10- anthraquinone derivative, and structure is such as
Shown in general formula I:
Wherein, R1~R8Separately selected from hydrogen, deuterium, halogen, hydroxyl, nitro, itrile group, sulfenyl, substituted or unsubstituted
C1~C20Alkyl, substituted or unsubstituted C1~C20Alkoxy, substituted or unsubstituted C1~C20It is alkylthio group, substituted or unsubstituted
C6~C24Aryl, substituted or unsubstituted C5~C23Heteroaryl, substituted or unsubstituted C6~C24Amido.
Technical solution of the present invention additionally provides the preparation method of one kind 9,10- anthraquinone derivative, includes the following steps:
S1, the inorganic acid solution of compound A1 and azeotropic is subjected to dehydration, obtains compound B-11；By compound A2 with
Inorganic acid carries out dehydration, obtains compound B2；Wherein, the structural formula of A1, A2, B1 and B2 are as follows:
S2, Isosorbide-5-Nitrae-benzoquinones, compound B-11 and compound B2 carry out sudden reaction in organic media, obtain 9,10- anthracene
Quinone derivative.
Technical solution of the present invention additionally provides the application of one kind 9,10- anthraquinone derivative, 9, the 10- anthraquinone-derivative
Synthetic intermediate of the object as anthracene derivant class, cyano Anthraquinones, fluoro Anthraquinones or deuterated anthraquinone based electroluminescent material, or
The synthetic intermediate of anthraquinone derivatives.
Compared with prior art, the beneficial effect comprise that
1,9,10- anthraquinone derivative provided by the invention provides the anthraquinone derivative of diversification, has expanded anthraquinone-derivative
The type of object has opened up anthraquinone system derivative in field of organic electroluminescence, the application journey of dyestuff, field of medicaments；
2, the anthraquinone derivative of diversification provided by the invention is further synthesized high-performance, Gao Yingyong as intermediate
The anthracene derivative of value provides possibility；
3, the preparation method of 9,10- anthraquinone derivative provided by the invention is simple, and reaction condition is mild, and reaction raw materials come
Source is convenient, at low cost, and organic solvent is few using type, can utmostly reduce the pollution to environment；
4, the preparation method of 9,10- anthraquinone derivative provided by the invention is by the Precise control of technique, and unstable
The processing method of fixed synthetic intermediate can make 9, the 10- anthraquinone derivative purity finally prepared 99% or more, yield
Up to 80%, feasible approach is provided for its direct application in the industry.
Detailed description of the invention
Fig. 1 is the intermediate 2 of compound (42), 3- dimethyl -1,3-butadiene nuclear magnetic spectrum；
Fig. 2 is compound (42) nuclear magnetic spectrum；
Fig. 3 is the liquid chromatogram of compound (42).
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that embodiment described herein is only used to explain the present invention, and do not have to
It is of the invention in limiting.
The embodiment of the present invention provides one kind 9,10- anthraquinone derivative, and structure is as shown in general formula I:
Wherein, R1~R8Separately selected from hydrogen, deuterium, halogen, hydroxyl, nitro, itrile group, sulfenyl, substituted or unsubstituted
C1~C20Alkyl, substituted or unsubstituted C1~C20Alkoxy, substituted or unsubstituted C1~C20It is alkylthio group, substituted or unsubstituted
C6~C24Aryl, substituted or unsubstituted C5~C23Heteroaryl, substituted or unsubstituted C6~C24Amido；R1~R8Mutually solely
It is vertical, it can be identical or different.
In some preferred embodiments of the invention, R2、R3、R6And R7In at least one be selected from substituted or unsubstituted C1
~C20Alkyl, substituted or unsubstituted C1~C20Alkoxy, substituted or unsubstituted C1~C20Alkylthio group.
In some preferred embodiments of the invention, R1~R8Separately it is selected from hydrogen, bromine, nitro, sulfenyl or following
Group:
Wherein, * is to replace site；
And R1With R5Or R8In identical a, R4With R5Or R8In another identical or R1、R4、R5、R8It is identical；
R2With R6Or R7In identical a, R3With R6Or R7In another identical or R2、R3、R6、R7It is identical.
In some preferred embodiments of the invention, R1、R4、R5、R8It is identical, and R1、R4、R5、R8It is hydrogen.
It is further preferred that 9,10- anthraquinone derivatives are following any structure:
It is highly preferred that 9,10- anthraquinone derivatives are following any structure:
The embodiments of the present invention also provide the preparation methods of one kind 9,10- anthraquinone derivative, include the following steps:
(1) inorganic acid solution of compound A1 and azeotropic is subjected to dehydration, obtains compound B-11；By compound A2 with
Inorganic acid carries out dehydration, obtains compound B2；Wherein, the structural formula of A1, A2, B1 and B2 are as follows:
(2) Isosorbide-5-Nitrae-benzoquinones, compound B-11 and compound B2 carry out sudden reaction in organic media, obtain 9,10- anthracene
Quinone derivative.
Compound A1 and A2 may be the same or different in the present invention.In some preferred embodiments of the invention,
Compound A1 is identical as compound A2, and compound B-11 obtained and compound B2 are also identical.
In some preferred embodiments of the invention, in step (1), compound A1 and inorganic acid solution are according to 1mol:1
The inventory of~5mL carries out dehydration；Compound A2 and inorganic acid solution are dehydrated according to the inventory of 1mol:1~5mL
Reaction.
In some preferred embodiments of the invention, inorganic acid is that the hydrobromic acid that mass fraction is 47~48% is water-soluble
Liquid.
In some preferred embodiments of the invention, during compound B-11 and compound B2 are dehydration, via
Still and condensing unit collect distillate of the column top temperature at 60~130 DEG C, then through elution eluent solvent, drying and secondary point
Evaporate what 66~128 DEG C of collection of distillate obtained.
When the structural formula of 9,10- anthraquinone derivative is (42), compound B-11 and compound B2 are via still and cold
Solidifying device collects distillate of the column top temperature at 60~95 DEG C, and the fraction that secondary fractionation collects 69~70.5 DEG C obtains.
When the structural formula of 9,10- anthraquinone derivative is (115), compound B-11 and compound B2 be via still and
Condensing unit collects distillate of the column top temperature at 100~120 DEG C, and the fraction that secondary fractionation collects 112~114 DEG C obtains.
When the structural formula of 9,10- anthraquinone derivative is (147), compound B-11 and compound B2 be via still and
Condensing unit collects distillate of the column top temperature at 60-95 DEG C, and the fraction that secondary fractionation collects 66-67.5 DEG C obtains.
When the structural formula of 9,10- anthraquinone derivative is (170), compound B-11 and compound B2 be via still and
Condensing unit collects distillate of the column top temperature at 60-95 DEG C, and the fraction that secondary fractionation collects 77-79 DEG C obtains.
In some preferred embodiments of the invention, the control of dehydration temperature is 0.5~3mL/ distillating speed
min。
In some preferred embodiments of the invention, elution solvent is the hydroquinone water that mass fraction is 0.5~3%
Solution.
In some preferred embodiments of the invention, polymerization inhibitor is also added into after the completion of compound B-11 and compound B2 preparation
The closed cryo-conservation of agent, according to addition 0.1~0.5g polymerization inhibitor in every 1mol compound B-11 or compound B2.
It is highly preferred that according to 0.3g polymerization inhibitor is added in every 1mol compound B-11 or compound B2.
In some preferred embodiments of the invention, 9,10- anthraquinone is specifically prepared in step (2) with the following method
Derivative: Isosorbide-5-Nitrae-benzoquinones, compound B-11 and compound B2 are in organic media in 75~95 DEG C of progress sudden reactions, heat preservation 15
After~20h, the ice-water bath that -5~5 DEG C of reaction system use is cooling, via ethyl alcohol, petroleum ether, acetonitrile, ethyl acetate, methylene chloride
At least one of washing or recrystallization purification after.
In some preferred embodiments of the invention, in step (2), Isosorbide-5-Nitrae-benzoquinones, compound B-11 and compound B2
Molar ratio is 1:2~4:2~4.
In some preferred embodiments of the invention, in step (2), organic media is ethyl alcohol and/or dioxane.
It is highly preferred that organic media is ethyl alcohol.
The embodiments of the present invention also provide the application of one kind 9,10- anthraquinone derivative, can be used as anthracene derivant class,
The conjunction of the synthetic intermediate or anthraquinone derivatives of cyano Anthraquinones, fluoro Anthraquinones or deuterated anthraquinone based electroluminescent material
At intermediate.
Below in conjunction with specific embodiment, the present invention will be described in further detail.It should be appreciated that tool described herein
Body embodiment is only used to explain the present invention, is not intended to limit the present invention.
Experimental method in the present invention is unless otherwise specified conventional method.
Experimental material used in the present invention is that market is commercially available unless otherwise specified.
Embodiment 1:
The embodiment of the present invention 1 provides the synthetic method for 9, the 10- anthraquinone derivative that structural formula is (7), including as follows
Step:
(1) in 100mL single-necked flask, addition 3,4,4- trimethylpentane -2,3- glycol (21.93g,
150mmol), 0.5ml azeotropic hydrobromic acid (hydrobromic acid aqueous solution that mass fraction is 47~48%), loads onto a still, point
Condenser and receiving device are installed, stirring, heat temperature raising, it is 1~1.5mL/min per minute that control, which distillates speed, is received on fractional distillation column
Collect distillate, column top temperature reaches 95 DEG C of stopping distillations.Distillate liquid separation, upper layer fraction mass fraction are 1% to benzene two
Phenol aqueous solution elutes 1~3 time (upper layer fraction: aqueous solution 5mL:1mL), and 0.045g phenol is added as polymerization inhibitor (3,4,4-
Trimethylpentane -2,3- glycol: phenol 1mol:0.3g), after anhydrous calcium chloride 0.5g is dry, secondary fractionation is carried out, is collected
2- tert-butyl -1,3-butadiene 10.74g can be obtained in 72.5~74 DEG C of fraction, and yield 65%, product easily polymerize, and adds
Enter 0.045g phenol as polymerization inhibitor (by 3,4,4- trimethylpentane -2,3- glycol: phenol be 1mol:0.3g ratio),
Closed cryo-conservation；
(2) in the reaction flask of 100mL, Isosorbide-5-Nitrae-benzoquinones (1.51g, 14mmol), 2- tert-butyl -1,3- fourth two are put into
Alkene (6.17g, 56mmol), 28mL ethyl alcohol under nitrogen atmosphere, are warming up to 90~95 DEG C of heat reflux, after keeping the temperature 19h, mixture is used
Ice water cools to 0 DEG C, keeps the temperature half an hour, and filtering, filter cake obtains head product, head product methylene chloride weight with ethanol washing
0~1 time (head product: methylene chloride=2g:1mL) is crystallized, the white that 3.36g purity is 99.20% can be obtained after dry
Target compound (7), yield 73%.MALDI-TOF-MS (m/z): theoretical value, 328.2402；Actual measurement, 328.2470.
Embodiment 2:
The embodiment of the present invention 2 provides the synthetic method for 9, the 10- anthraquinone derivative that structural formula is (18), including such as
Lower step:
Structural formula is that the synthetic method of 9, the 10- anthraquinone derivative of (18) is identical as the synthetic method in embodiment 1, difference
It is, 3,4,4- trimethylpentane -2,3- glycol (21.93g, 150mmol) is replaced with into methyl heptane -2 3- in step (1),
72.5~74 DEG C of fraction temperature of 3- glycol (21.93g, 150mmol), secondary fractionation collection replace with 72~73 DEG C；Step (2)
It is middle that 2- tert-butyl -1,3-butadiene (6.17g, 56mmol) is replaced with into 2- butane group -1,3-butadiene (6.17g, 56mmol),
The target compound (18) for the white that 3.22g purity is 99.05% can be obtained with embodiment 1 in other synthesis processes, and yield is
70%.MALDI-TOF-MS (m/z): theoretical value, 328.2402；Actual measurement, 328.2445.
Embodiment 3:
The embodiment of the present invention 3 provides the synthetic method for 9, the 10- anthraquinone derivative that structural formula is (31), including such as
Lower step:
Structural formula is that the synthetic method of 9, the 10- anthraquinone derivative of (31) is identical as the synthetic method in embodiment 1, difference
It is, 3,4,4- trimethylpentane -2,3- glycol (21.93g, 150mmol) is replaced with into 3,7- dimethyl in step (1)
72.5~74 DEG C of fraction temperature of octane -2,3- glycol (26.14g, 150mmol), secondary fractionation collection replace with 77~78
℃；2- tert-butyl -1,3-butadiene (6.17g, 56mmol) is replaced with into 2- (4- methylpent alkyl)-in step (2)
1,3-butadiene (7.74g, 56mmol), for other synthesis processes with embodiment 1, it is 99.24% that 3.88g purity, which can be obtained,
The target compound (31) of white, yield 72%.MALDI-TOF-MS (m/z): theoretical value, 384.3028；Actual measurement,
384.3069。
Embodiment 4:
The embodiment of the present invention 4 provides the synthetic method for 9, the 10- anthraquinone derivative that structural formula is (42), including such as
Lower step:
Structural formula is that the synthetic method of 9, the 10- anthraquinone derivative of (42) is identical as the synthetic method in embodiment 1, difference
It is, 3,4,4- trimethylpentane -2,3- glycol (21.93g, 150mmol) is replaced with into pinacol in step (1)
72.5~74 DEG C of fraction temperature of (17.72g, 150mmol), secondary fractionation collection replace with 69~70.5 DEG C；It will in step (2)
2- tert-butyl -1,3-butadiene (6.17g, 56mmol) replace with 2,3- dimethyl -1,3-butadiene (4.60g,
56mmol), the target compound for the white that 3.05g purity is 99.80% can be obtained with embodiment 1 in other synthesis processes
(42), yield 80%.MALDI-TOF-MS (m/z): theoretical value, 272.1776；Actual measurement, 272.1754.
Embodiment 5:
The embodiment of the present invention 5 provides the synthetic method for 9, the 10- anthraquinone derivative that structural formula is (69), including such as
Lower step:
Structural formula is that the synthetic method of 9, the 10- anthraquinone derivative of (69) is identical as the synthetic method in embodiment 1, difference
It is, 3,4,4- trimethylpentane -2,3- glycol (21.93g, 150mmol) is replaced with into 2,3- dimethyl in step (1)
Octane -2,3- glycol (26.14g, 150mmol), collect 72.5~74 DEG C of fraction temperature of secondary fractionation replace with 79.5~
81℃；2- tert-butyl -1,3-butadiene (6.17g, 56mmol) is replaced with into 2- methyl -3- pentane in step (2)
Base -1,3-butadiene (7.74g, 56mmol), with embodiment 1,3.98g purity can be obtained is other synthesis processes
The target compound (69) of 99.16% white, yield 74%.MALDI-TOF-MS (m/z): theoretical value, 384.3028；
Actual measurement, 384.3014.
Embodiment 6:
The embodiment of the present invention 6 provides the synthetic method for 9, the 10- anthraquinone derivative that structural formula is (72), including such as
Lower step:
Structural formula is that the synthetic method of 9, the 10- anthraquinone derivative of (72) is identical as the synthetic method in embodiment 1, difference
It is, 3,4,4- trimethylpentane -2,3- glycol (21.93g, 150mmol) is replaced with into 3,10- diethyl in step (1)
Base -6,7- dimethyl dodecyl -6,7- glycol (42.97g, 150mmol), the fraction temperature 72.5 that secondary fractionation is collected~
74 DEG C replace with 88~90 DEG C；2- tert-butyl -1,3-butadiene (6.17g, 56mmol) is replaced with 2,3- in step (2)
(3- ethylpentane base) -1,3-butadiene (14.02g, 56mmol), other synthesis processes can be obtained with embodiment 1
The target compound (72) for the white that 6.65g purity is 99.64%, yield 78%.MALDI-TOF-MS (m/z): theoretical
Value, 608.5532；Actual measurement, 608.5540.
Embodiment 7:
The embodiment of the present invention 7 provides the synthetic method for 9, the 10- anthraquinone derivative that structural formula is (77), including such as
Lower step:
Structural formula is that the synthetic method of 9, the 10- anthraquinone derivative of (77) is identical as the synthetic method in embodiment 1, difference
It is, 3,4,4- trimethylpentane -2,3- glycol (21.93g, 150mmol) is replaced with into 2,3- diformazan in step (1)
Base-Isosorbide-5-Nitrae-dioxane -2,3- glycol (22.22g, 150mmol), 72.5~74 DEG C of fraction temperature of secondary fractionation collection
Replace with 75~76.5 DEG C；2- tert-butyl -1,3-butadiene (6.17g, 56mmol) is replaced with into 2,3- bis- in step (2)
Methylene-Isosorbide-5-Nitrae-dioxane (6.28g, 56mmol), with embodiment 1,3.58g purity can be obtained is other synthesis processes
The target compound (77) of 99.70% white, yield 77%.MALDI-TOF-MS (m/z): theoretical value, 332.1260；
Actual measurement, 332.1249.
Embodiment 8:
The embodiment of the present invention 8 provides the synthetic method for 9, the 10- anthraquinone derivative that structural formula is (86), including such as
Lower step:
Structural formula is that the synthetic method of 9, the 10- anthraquinone derivative of (86) is identical as the synthetic method in embodiment 1, difference
It is, 3,4,4- trimethylpentane -2,3- glycol (21.93g, 150mmol) is replaced with into 4,5- dihydroxy in step (1)
72.5~74 DEG C of fraction temperature of base -4- methyl valeronitrile (21.48g, 150mmol), secondary fractionation collection replace with 83~85
℃；2- tert-butyl -1,3-butadiene (6.17g, 56mmol) is replaced with into 2- third acetonitrile-base -1,3- fourth in step (2)
The mesh for the white that 3.20g purity is 99.14% can be obtained with embodiment 1 in diene (6.00g, 56mmol), other synthesis processes
It marks compound (86), yield 71%.MALDI-TOF-MS (m/z): theoretical value, 322.1681；Actual measurement, 322.1677.
Embodiment 9:
The embodiment of the present invention 9 provides the synthetic method for 9, the 10- anthraquinone derivative that structural formula is (115), including such as
Lower step:
Structural formula is that the synthetic method of 9, the 10- anthraquinone derivative of (115) is identical as the synthetic method in embodiment 1, area
It is not, 3,4,4- trimethylpentane -2,3- glycol (21.93g, 150mmol) is replaced with into 2,3- diformazan in step (1)
72.5~74 DEG C of fraction temperature of base -2,3- dihydroxy succinonitrile (21.02g, 150mmol), secondary fractionation collection replace with
112~114 DEG C；2- tert-butyl -1,3-butadiene (6.17g, 56mmol) is replaced with into 2,3- dimethoxy nitrile in step (2)
Base -1,3-butadiene (5.83g, 56mmol), with embodiment 1,3.50g purity can be obtained is other synthesis processes
The target compound (115) of 99.50% white, yield 79%.MALDI-TOF-MS (m/z): theoretical value,
316.0960；Actual measurement, 316.0972.
Embodiment 10:
The embodiment of the present invention 10 provides the synthetic method for 9, the 10- anthraquinone derivative that structural formula is (126), including
Following steps:
Structural formula is that the synthetic method of 9, the 10- anthraquinone derivative of (126) is identical as the synthetic method in embodiment 1, area
It is not, 3,4,4- trimethylpentane -2,3- glycol (21.93g, 150mmol) is replaced with into 2,3- diformazan in step (1)
72.5~74 DEG C of fraction temperature of base -2,3- dihydroxy certain herbaceous plants with big flowers dintrile (33.64g, 150mmol), secondary fractionation collection replace with
126~128 DEG C；2- tert-butyl -1,3-butadiene (6.17g, 56mmol) is replaced with into 2,3- dibutyronitrile in step (2)
Base -1,3-butadiene (10.54g, 56mmol), with embodiment 1,5.16g purity can be obtained is other synthesis processes
The target compound (126) of 99.41% white, yield 76%.MALDI-TOF-MS (m/z): theoretical value,
484.2838；Actual measurement, 484.2847.
Embodiment 11:
The embodiment of the present invention 11 provides the synthetic method for 9, the 10- anthraquinone derivative that structural formula is (145), including
Following steps:
Structural formula is that the synthetic method of 9, the 10- anthraquinone derivative of (145) is identical as the synthetic method in embodiment 1, area
It is not, 3,4,4- trimethylpentane -2,3- glycol (21.93g, 150mmol) is replaced with into 2- methyl fourth in step (1)
Alkane -1,1,1-d3-2,3- glycol (16.07,150mmol), 72.5~74 DEG C of the fraction temperature replacements that secondary fractionation is collected
It is 66~67.5 DEG C；2- tert-butyl -1,3-butadiene (6.17g, 56mmol) is replaced with into 2- (methyl-in step (2)
D3) -1,3-butadiene (10.54g, 56mmol), with embodiment 1,2.56g purity can be obtained is other synthesis processes
The target compound (145) of 99.12% white, yield 73%.MALDI-TOF-MS (m/z): theoretical value,
250.1840；Actual measurement, 250.1832.
Embodiment 12:
The embodiment of the present invention 12 provides the synthetic method for 9, the 10- anthraquinone derivative that structural formula is (147), including
Following steps:
Structural formula is that the synthetic method of 9, the 10- anthraquinone derivative of (147) is identical as the synthetic method in embodiment 1, area
It is not, 3,4,4- trimethylpentane -2,3- glycol (21.93g, 150mmol) is replaced with into 2,3- diformazan in step (1)
Base butane -1,1, Isosorbide-5-Nitrae, 4,4-d6-2,3- glycol (18.63,150mmol), the fraction temperature 72.5 that secondary fractionation is collected
~74 DEG C replace with 66~67.5 DEG C；2- tert-butyl -1,3-butadiene (6.17g, 56mmol) is replaced in step (2)
2,3- bis- (methyl-d3) -1,3-butadienes (10.54g, 56mmol), other synthesis processes can be obtained with embodiment 1
The target compound (147) for the white that 2.99g purity is 99.40%, yield 75%.MALDI-TOF-MS (m/z): theoretical
Value, 284.2530；Actual measurement, 284.2518.
Embodiment 13:
The embodiment of the present invention 13 provides the synthetic method for 9, the 10- anthraquinone derivative that structural formula is (170), including
Following steps:
Structural formula is that the synthetic method of 9, the 10- anthraquinone derivative of (170) is identical as the synthetic method in embodiment 1, area
It is not, 3,4,4- trimethylpentane -2,3- glycol (21.93g, 150mmol) is replaced with 1,1 in step (1), Isosorbide-5-Nitrae,
4,4- hexafluoro -2,3- dimethylbutane -2,3- glycol (33.92g, 150mmol), the fraction temperature that secondary fractionation is collected
72.5~74 DEG C replace with 77~79 DEG C；2- tert-butyl -1,3-butadiene (6.17g, 56mmol) is replaced in step (2)
For 2,3- bis- (trifluoromethyl) -1,3-butadiene (10.64g, 56mmol), other synthesis processes can be obtained with embodiment 1
To the target compound (170) for the white that 4.92g purity is 99.28%, yield 72%.MALDI-TOF-MS (m/z): reason
By value, 488.0646；Actual measurement, 488.0650.
Embodiment 14:
The embodiment of the present invention 14 provides the synthetic method for 9, the 10- anthraquinone derivative that structural formula is (179), including
Following steps:
Structural formula is that the synthetic method of 9, the 10- anthraquinone derivative of (179) is identical as the synthetic method in embodiment 1, area
It is not, 3,4,4- trimethylpentane -2,3- glycol (21.93g, 150mmol) is replaced with 4,4,5,5 in step (1),
6,6,6- seven fluoro- 3- methyl hexane -2,3- glycol (38.72g, 150mmol), the fraction temperature that secondary fractionation is collected
72.5~74 DEG C replace with 82~84 DEG C, replace 2- tert-butyl -1,3-butadiene (6.17g, 56mmol) in step (2)
Be 4,4,5,5,6,6,6- seven fluoro- 3- methyl alkene -1- alkene (12.44g, 56mmol), other synthesis processes with embodiment 1,
The target compound (179) for the white that 5.02g purity is 99.02%, yield 65% can be obtained.MALDI-TOF-MS
(m/z): theoretical value, 552.0770；Actual measurement, 552.0782.
The above described specific embodiments of the present invention are not intended to limit the scope of the present invention..Any basis
Any other various changes and modifications that technical concept of the invention is made should be included in the guarantor of the claims in the present invention
It protects in range.
Claims (10)
1. one kind 9,10- anthraquinone derivative, which is characterized in that its structure is as shown in general formula I:
Wherein, R1~R8Separately it is selected from hydrogen, deuterium, halogen, hydroxyl, nitro, itrile group, sulfenyl, substituted or unsubstituted C1~
C20Alkyl, substituted or unsubstituted C1~C20Alkoxy, substituted or unsubstituted C1~C20Alkylthio group, substituted or unsubstituted C6
~C24Aryl, substituted or unsubstituted C5~C23Heteroaryl, substituted or unsubstituted C6~C24Amido.
2. 9,10- anthraquinone derivative according to claim 1, which is characterized in that R2、R3、R6And R7In at least one be selected from
Substituted or unsubstituted C1~C20Alkyl, substituted or unsubstituted C1~C20Alkoxy, substituted or unsubstituted C1~C20
Alkylthio group.
3. 9,10- anthraquinone derivative according to claim 2, which is characterized in that the R1~R8Separately it is selected from
Hydrogen, bromine, nitro, sulfenyl or following groups:
Wherein, * is to replace site；
And R1With R5Or R8In identical a, R4With R5Or R8In another identical or R1、R4、R5、R8It is identical；R2With R6Or R7
In identical a, R3With R6Or R7In another identical or R2、R3、R6、R7It is identical.
4. 9,10- anthraquinone derivative according to claim 3, which is characterized in that 9, the 10- anthraquinone derivative is such as
Lower any structure:
5. a kind of preparation method of such as described in any item 9, the 10- anthraquinone derivatives of Claims 1 to 4, which is characterized in that packet
Include following steps:
S1, the inorganic acid solution of compound A1 and azeotropic is subjected to dehydration, obtains compound B-11；By compound A2 with it is inorganic
Acid carries out dehydration, obtains compound B2；Wherein, the structural formula of A1, A2, B1 and B2 are as follows:
S2, Isosorbide-5-Nitrae-benzoquinones, compound B-11 and compound B2 carry out sudden reaction in organic media, obtain 9,10- anthraquinone and spread out
Biology.
6. the preparation method of 9,10- anthraquinone derivative according to claim 5, which is characterized in that in the step S1,
Compound A1 and inorganic acid solution carry out dehydration according to the inventory of 1mol:1~5mL；Compound A2 and inorganic acid solution
Dehydration is carried out according to the inventory of 1mol:1~5mL；The inorganic acid is the hydrobromic acid water that mass fraction is 47~48%
Solution.
7. the preparation method of 9,10- anthraquinone derivative according to claim 5, which is characterized in that in the step S1,
During compound B-11 and compound B2 are dehydration, column top temperature is collected 60~130 via still and condensing unit
DEG C distillate, then collect what 66~128 DEG C of distillate obtained through elution eluent solvent, drying and secondary fractionation；It is described de-
The control of water reaction temperature is 0.5~3mL/min distillating speed；It is 0.5~3% to benzene that the elution solvent, which is mass fraction,
Diphenol aqueous solution.
8. the preparation method of 9,10- anthraquinone derivative according to claim 5, which is characterized in that have in the step S2
Body prepares 9,10- anthraquinone derivative with the following method: Isosorbide-5-Nitrae-benzoquinones, compound B-11 and compound B2 in organic media in
75~95 DEG C of progress sudden reactions, after keeping the temperature 15~20h, the ice-water bath that -5~5 DEG C of reaction system use is cooling, via ethyl alcohol, stone
To get target product after the washing of at least one of oily ether, acetonitrile, ethyl acetate, methylene chloride or recrystallization purification.
9. the preparation method of 9,10- anthraquinone derivative according to claim 5, which is characterized in that 1 in the step S2,
The molar ratio of 4- benzoquinones, compound B-11 and compound B2 is 1:2~4:2~4；The organic media is ethyl alcohol and/or dioxy six
Ring.
10. a kind of application of such as described in any item 9, the 10- anthraquinone derivatives of Claims 1 to 4, which is characterized in that described 9,
10- anthraquinone derivative is as anthracene derivant class, cyano Anthraquinones, fluoro Anthraquinones or deuterated anthraquinone based electroluminescent material
The synthetic intermediate of synthetic intermediate or anthraquinone derivatives.
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| CN114906818A (en) * | 2021-02-08 | 2022-08-16 | 中国石油化工股份有限公司 | Alkyl anthraquinone working solution, preparation method thereof and production method of hydrogen peroxide |
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| CN114906818B (en) * | 2021-02-08 | 2024-05-17 | 中国石油化工股份有限公司 | Alkyl anthraquinone working solution, preparation method thereof and hydrogen peroxide production method |
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