CN109897026A - A kind of new synthetic method of thioxanthones compound - Google Patents
A kind of new synthetic method of thioxanthones compound Download PDFInfo
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- CN109897026A CN109897026A CN201910263312.4A CN201910263312A CN109897026A CN 109897026 A CN109897026 A CN 109897026A CN 201910263312 A CN201910263312 A CN 201910263312A CN 109897026 A CN109897026 A CN 109897026A
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Abstract
The invention discloses a kind of new synthetic methods of thioxanthones compound, belong to synthesis technical field.This method step are as follows: sequentially add alkali and 0-chloro-benzoic acid in a solvent, stirring brings it about neutralization reaction, and after neutralization reaction no longer heat release, alkyl benzenethiol is added dropwise into reaction system, 8~12h of etherification reaction is kept the temperature after being warming up to 120~220 DEG C；Room temperature is cooled to after etherification reaction, tail gas absorption is opened, maintains reaction system pressure -0.03 to -0.08Mpa, the concentrated sulfuric acid is added dropwise into ether-based liquid, dehydrating agent is added dropwise to remove the water generated in cyclization reaction to reaction system in reaction process in 3~7h of insulation reaction at a temperature of 20~60 DEG C；Water is added into the reaction solution after reaction, stirs, stratification, upper organic layer obtains target product thioxanthones compound after removing solvent, recrystallization.The total recovery of product of the present invention is high, and by-product is the sulfuric acid solution of sulfur-bearing potassium hydrogen phthalate, and easy to handle recycling is environmentally friendly.
Description
Technical field
The present invention relates to a kind of new synthetic methods of thioxanthones compound, belong to synthesis technical field.
Background technique
Thioxanthones compound has excellent optical performance, biological medicine, in terms of have it is extensive
Purposes, such as synthetic intermediate as ultraviolet photocureable material makees in Raolical polymerizable as DNA fluorescence probe
For initiator etc., this to be particularly important the research of its synthetic method.
The Chinese invention patent of Publication No. CN102250060A discloses one kind with a diethylbenzene, dithio-salicylic acid
For raw material, using the method that sulfuric acid prepares 2,4- diethyl thioxanthone as solvent, as shown in formula I, primary raw material used in this method
Dithio-salicylic acid preparation process is complicated, at high cost, and chemical property is active, easily reacts with water vapor in air, oxygen,
It is not easy to maintain；The additional amount of the solvent concentrated sulfuric acid is 5 times or more of reaction substrate quality in reaction process, and can generate a large amount of two
Sulfur oxide and Waste Sulfuric Acid, sulfur dioxide and Waste Sulfuric Acid are the unfriendly substance of environment and are difficult to handle.
The Chinese invention patent of Publication No. CN201711414350 discloses a kind of with 2,4- diethylbenzene thiophenol and adjacent
6-chlorophenyl nitrile is the preparation method that raw material generates 2,4- diethyl thioxanthone, and as shown in formula II, although this method avoids dioxy
Change the generation of sulphur, but the yield of product lower (85%) and also need to use a large amount of sulfuric acid, and has in by-product a large amount of
Ammonium hydrogen sulfate generate, and the Waste Sulfuric Acid of sulfur acid hydrogen ammonium can not be handled at present, and which has limited the industrialized productions of the technique.
Summary of the invention
For the problems of the prior art, the present invention provides a kind of new synthetic methods of thioxanthones compound, should
Method using with general formula V alkyl benzenethiol and 0-chloro-benzoic acid as raw material, etherificate is brought it about by one kettle way and cyclization is anti-
The thioxanthones compound with general formula III should be synthesized, intermediate process steps are reduced, the total recovery of product is increased to
93% or more, in addition, this method by-product is the sulfuric acid solution of sulfur-bearing potassium hydrogen phthalate, easy to handle recycling is environmentally friendly.
The general structure of thioxanthones compound is as shown in formula III synthesized by the present invention, wherein R1、R2Are as follows: H, C1-
The alkyl of C4；
The general structure of raw material alkyl benzenethiol of the present invention is as shown in formula V, wherein R1、R2Are as follows: H, C1-C4
Alkyl；
Synthetic reaction according to the present invention is as shown in formula VI:
To realize the above technical purpose, the technical scheme is that
A kind of new synthetic method of thioxanthones compound, step are as follows:
(1) sequentially add alkali and 0-chloro-benzoic acid in a solvent, stirring brings it about neutralization reaction, when neutralization reaction no longer
After heat release, alkyl benzenethiol is added dropwise into reaction system, 8~12h of etherification reaction is kept the temperature after being warming up to 120~220 DEG C；
(2) be cooled to room temperature after etherification reaction, open tail gas absorption, maintain reaction system pressure -0.03 to -
The concentrated sulfuric acid is added dropwise into ether-based liquid by 0.08Mpa, 3~7h of insulation reaction at a temperature of 20~60 DEG C, to reactant in reaction process
Dehydrating agent is added dropwise to remove the water generated in cyclization reaction in system；
(3) water is added into the reaction solution after step (2) reaction, stirs, stratification, upper organic layer is molten through removing
Target product thioxanthones compound is obtained after agent, recrystallization.
Preferably, the dehydrating agent is any one in chlorosulfonic acid, oleum and sulfur trioxide.
Preferably, the alkali, alkyl benzenethiol, 0-chloro-benzoic acid the mass ratio of the material be (2~3): 1:1.
Preferably, the alkali, alkyl benzenethiol, 0-chloro-benzoic acid the mass ratio of the material be (2.1~2.3): 1:1.
Preferably, the mass ratio of the material of the concentrated sulfuric acid and 0-chloro-benzoic acid is (2.5~5): 1.
Preferably, the mass ratio of the material of the concentrated sulfuric acid and 0-chloro-benzoic acid is (3~3.5): 1.
Preferably, reaction system pressure maintains -0.05~0.07Mpa in step (2).
Preferably, the solvent is one or more of toluene, dimethylbenzene, diethylbenzene, diisopropylbenzene (DIPB) mixture.
Preferably, the alkali is any one in potassium hydroxide, sodium hydroxide and lithium hydroxide.
Preferably, etherification reaction temperature is 160~190 DEG C in step (1)；In step (2) cyclization reaction temperature be 30~
50℃。
From the above, it can be seen that compared with the prior art, the present invention has following advantages:
(1) present invention selects 0-chloro-benzoic acid to react for raw material and alkyl benzenethiol, can make that reaction system is added
For the concentrated sulfuric acid not only as the catalyst of cyclization reaction, it is extra in the salt and system of etherification reaction generation to can be also used for neutralizing
Alkali (as shown in formula VII and formula VIII), on the one hand can make the hydrogen chloride in potassium chloride be replaced out, the hydrogen chloride of generation is matched
It closes reduced pressure to remove from system, may advantageously facilitate the progress of cyclization reaction, improve the yield of product, on the other hand,
Can make by-product is the sulfuric acid solution of sulfur-bearing potassium hydrogen phthalate, and easy to handle recycling is environmentally friendly.
KCl+H2SO4→KHSO4+HCl↑ (Ⅶ)
KOH+H2SO4→KHSO4+H2O (Ⅷ)
It is (2) of the invention by the way that the water generated during suitable dehydrating agent elimination reaction is added during cyclization reaction,
The progress of reaction can be greatly promoted, the dosage of sulfuric acid can also be greatly reduced while improving reaction rate and yield.
Specific embodiment
Below by examples of implementation, the characteristics of the present invention is further explained, but claim of the invention is not done any
It limits.
Examples 1 to 4:
(1) into 5000ml four-hole boiling flask be added 1000ml between diethylbenzene, sequentially add hydrogen-oxygen in diethylbenzene
Change potassium and 0-chloro-benzoic acid, stirring brings it about neutralization reaction, after neutralization reaction no longer heat release, 2 is added dropwise into reaction system,
4 ,-diethylbenzene thiophenol keeps the temperature etherification reaction 10h after being warming up to 160 DEG C；
(2) it is cooled to room temperature after etherification reaction, opens tail gas absorption, maintain reaction system pressure in -0.05Mpa,
The concentrated sulfuric acid is added dropwise into ether-based liquid, chlorosulfonic acid is added dropwise to reaction system in reaction process in the insulation reaction 4.5h at a temperature of 40 DEG C
To remove the water generated in cyclization reaction；
(3) 1000ml water, stirring, stratification, upper organic layer removing are added into the reaction solution after step (2) reaction
Yellow powder solid, as target product 2 are obtained after solvent, recrystallizing methanol, 4- diethyl thioxanthone is computed to obtain product
As shown in table 2, the sulfuric acid solution of lower layer's potassium acid sulfate is through hydrogen-oxygen for yield (yield=actual product amount/theory product volume * 100%)
Potassium hydrogen sulfate solution is obtained after changing potassium solution neutralisation treatment, can be used as and sold outside by-product；
Potassium hydroxide used, 0-chloro-benzoic acid, 2,4 ,-diethylbenzene thiophenol, the concentrated sulfuric acid and chlorine sulphur in above-mentioned synthesis process
The dosage of acid is as shown in table 1.
Embodiment 5:
Dehydrating agent in embodiment 1 is changed to oleum, other conditions are same as Example 1, using with embodiment 1
Identical method synthesis target product 2,4- diethyl thioxanthone, product yield are as shown in table 2.
Embodiment 6:
(1) into 5000ml four-hole boiling flask be added 1000ml toluene, sequentially added in toluene 2.2mol lithium hydroxide and
1mol 0-chloro-benzoic acid, stirring bring it about neutralization reaction, after neutralization reaction no longer heat release, are added dropwise into reaction system
1mol2,4- thiophenol dimethyl benzene keep the temperature etherification reaction 12h after being warming up to 120 DEG C；
(2) it is cooled to room temperature after etherification reaction, opens tail gas absorption, maintain reaction system pressure in -0.03Mpa,
The 3mol concentrated sulfuric acid is added dropwise into ether-based liquid, the insulation reaction 7h at a temperature of 20 DEG C is added dropwise in reaction process to reaction system
1.08mol chlorosulfonic acid is to remove the water generated in cyclization reaction；
(3) 1000ml water, stirring, stratification, upper organic layer removing are added into the reaction solution after step (2) reaction
Yellow powder solid, as target product 2 are obtained after solvent, recrystallizing methanol, 4- dimethyl thioxanthone is computed to obtain product
Yield is as shown in table 2；The sulfuric acid solution of lower layer's lithium sulfate obtains lithium sulfate solution after lithium hydroxide solution neutralisation treatment, can make
To be sold outside by-product.
Embodiment 7:
(1) 1000ml diisopropylbenzene (DIPB) is added into 5000ml four-hole boiling flask, 2.2mol hydrogen is sequentially added in diisopropylbenzene (DIPB)
Sodium oxide molybdena and 1mol 0-chloro-benzoic acid, stirring brings it about neutralization reaction, after neutralization reaction no longer heat release, into reaction system
1mol4- isopropylbenzene thiophenol is added dropwise, etherification reaction 8h is kept the temperature after being warming up to 190 DEG C；
(2) it is cooled to room temperature after etherification reaction, opens tail gas absorption, maintain reaction system pressure in -0.07Mpa,
The 3mol concentrated sulfuric acid is added dropwise into ether-based liquid, the insulation reaction 1h at a temperature of 60 DEG C is added dropwise in reaction process to reaction system
1.08mol chlorosulfonic acid is to remove the water generated in cyclization reaction；
(3) 1000ml water, stirring, stratification, upper organic layer removing are added into the reaction solution after step (2) reaction
Yellow powder solid, as target product 4- isopropyl thioxanthone are obtained after solvent, recrystallizing methanol, are computed to obtain product receipts
Rate is as shown in table 2；The sulfuric acid solution of lower layer's sodium bisulfate obtains sodium bisulfate after sodium hydroxide solution neutralisation treatment, can
It is sold outside as by-product.
Comparative example 1:
Dehydrating agent in embodiment 1 is changed to anhydrous sodium sulfate, other conditions are same as Example 1, using with implementation
The identical method of example 1 synthesis target product 2,4- diethyl thioxanthone, product yield are as shown in table 2.
Comparative example 2:
Dehydrating agent in embodiment 1 is changed to chloroacetic chloride, other conditions are same as Example 1, using with 1 phase of embodiment
Same method synthesis target product 2,4- diethyl thioxanthone, product yield are as shown in table 2.
Comparative example 3:
Dehydrating agent is not added during cyclization reaction, other conditions are same as Example 1, using side same as Example 1
Method synthesis target product 2,4- diethyl thioxanthone, product yield are as shown in table 2.
Comparative example 4~6:
Change potassium hydroxide used, 0-chloro-benzoic acid, 2,4 ,-diethylbenzene thiophenol, the concentrated sulfuric acid and chlorine sulphur in synthesis process
The dosage of acid, is specifically shown in Table 1, and other conditions are same as Example 1, synthesizes target using method same as Example 1
Product 2,4- diethyl thioxanthone, product yield are as shown in table 2.
Table 1
Table 2
| Yield (%) | |
| Embodiment 1 | 94.3 |
| Embodiment 2 | 94.1 |
| Embodiment 3 | 93.9 |
| Embodiment 4 | 93.8 |
| Embodiment 5 | 94.0 |
| Embodiment 6 | 94.4 |
| Embodiment 7 | 94.2 |
| Comparative example 1 | 80.2 |
| Comparative example 2 | 92.8 |
| Comparative example 3 | 77.2 |
| Comparative example 4 | 90.5 |
| Comparative example 5 | 90.8 |
| Comparative example 6 | 92.2 |
It is understood that being merely to illustrate the present invention above with respect to specific descriptions of the invention and being not limited to this
Technical solution described in inventive embodiments.Those skilled in the art should understand that still can be carried out to the present invention
Modification or equivalent replacement, to reach identical technical effect；As long as meet use needs, all protection scope of the present invention it
It is interior.
Claims (10)
1. a kind of new synthetic method of thioxanthones compound, which is characterized in that step are as follows:
(1) alkali and 0-chloro-benzoic acid are sequentially added in a solvent, and stirring brings it about neutralization reaction, when neutralization reaction no longer heat release
Afterwards, alkyl benzenethiol is added dropwise into reaction system, 8~12h of etherification reaction is kept the temperature after being warming up to 120~220 DEG C；
(2) be cooled to room temperature after etherification reaction, open tail gas absorption, maintain reaction system pressure -0.03 to -
The concentrated sulfuric acid is added dropwise into ether-based liquid by 0.08Mpa, 3~7h of insulation reaction at a temperature of 20~60 DEG C, to reactant in reaction process
Dehydrating agent is added dropwise to remove the water generated in cyclization reaction in system；
(3) water is added into the reaction solution after step (2) reaction, stirs, stratification, upper organic layer is through removing solvent, again
Target product thioxanthones compound is obtained after crystallization.
2. the new synthetic method of thioxanthones compound as described in claim 1, which is characterized in that the dehydrating agent is chlorine
Any one in sulfonic acid, oleum and sulfur trioxide.
3. the new synthetic method of thioxanthones compound as described in claim 1, which is characterized in that the alkali, alkylbenzene
Thiophenol, 0-chloro-benzoic acid the mass ratio of the material be (2~3): 1:1.
4. the new synthetic method of thioxanthones compound as claimed in claim 3, which is characterized in that the alkali, alkylbenzene
Thiophenol, 0-chloro-benzoic acid the mass ratio of the material be (2.1~2.3): 1:1.
5. the new synthetic method of thioxanthones compound as described in claim 1, which is characterized in that the concentrated sulfuric acid and neighbour
The mass ratio of the material of chlorobenzoic acid is (2.5~5): 1.
6. the new synthetic method of thioxanthones compound as claimed in claim 5, which is characterized in that the concentrated sulfuric acid and neighbour
The mass ratio of the material of chlorobenzoic acid is (3~3.5): 1.
7. the new synthetic method of thioxanthones compound as described in claim 1, which is characterized in that reaction in step (2)
System pressure maintains -0.05~0.07Mpa.
8. the new synthetic method of thioxanthones compound as described in claim 1, which is characterized in that the solvent is first
One or more of benzene, dimethylbenzene, diethylbenzene, diisopropylbenzene (DIPB) mixture.
9. the new synthetic method of thioxanthones compound as described in claim 1, which is characterized in that the alkali is hydroxide
Any one in potassium, sodium hydroxide and lithium hydroxide.
10. the new synthetic method of thioxanthones compound as described in claim 1, which is characterized in that etherificate in step (1)
Reaction temperature is 160~190 DEG C；Cyclization reaction temperature is 30~50 DEG C in step (2).
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101570534A (en) * | 2008-04-28 | 2009-11-04 | 大丰市天生化学工业有限公司 | Preparation process of 2-isopropylthioxanthone |
| CN101817812A (en) * | 2010-05-11 | 2010-09-01 | 天津久日化学工业有限公司 | Preparation method of 2-isopropyl thioxanthone and derivatives thereof |
-
2019
- 2019-04-02 CN CN201910263312.4A patent/CN109897026A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101570534A (en) * | 2008-04-28 | 2009-11-04 | 大丰市天生化学工业有限公司 | Preparation process of 2-isopropylthioxanthone |
| CN101817812A (en) * | 2010-05-11 | 2010-09-01 | 天津久日化学工业有限公司 | Preparation method of 2-isopropyl thioxanthone and derivatives thereof |
Non-Patent Citations (2)
| Title |
|---|
| 何开宇等: "光引发剂ITX生产工艺的研究", 《甘肃科技》 * |
| 胡新龙: "2,4-二乙基苯硫酚及硫杂蒽酮类化合物的合成工艺研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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