CN108727270A - A kind of preparation method of 2- thiocarbamoyl imidazoles alkane -4,5- diketone - Google Patents
A kind of preparation method of 2- thiocarbamoyl imidazoles alkane -4,5- diketone Download PDFInfo
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- CN108727270A CN108727270A CN201810453375.1A CN201810453375A CN108727270A CN 108727270 A CN108727270 A CN 108727270A CN 201810453375 A CN201810453375 A CN 201810453375A CN 108727270 A CN108727270 A CN 108727270A
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- ammonium thiocyanate
- diketone
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- diethy
- thiocarbamoyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/96—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation methods of 2- thiocarbamoyl imidazoles alkane -4,5- diketone, include the following steps：It weighs ammonium thiocyanate to be added in diethy-aceto oxalate, is fixed on heat collecting type constant-temperature heating magnetic stirring apparatus and heats, air setting；Generation yellow solution, cooling to generate solid, filtering obtains yellow solid after water washing, drying.It has used ammonium thiocyanate to substitute the thiocarbamide used originally in this method, has on the one hand reduced production cost, on the other hand use ammonium thiocyanate as raw materials for production, be that resource has been saved to the utilization of recycling product.Synthesis cost can be reduced for enterprise, economized on resources.The invention is applied to environmental protection field, not only economized on resources but also reduces environmental pollution, and environmental protection while can also obtain certain economic benefit, with important social and economic implications.
Description
Technical field
The present invention relates to a kind of preparation methods of 2- thiocarbamoyl imidazoles alkane -4,5- diketone.
Background technology
According to statistics, coke annual output in China's surpasses 400,000,000 tons.Therefore, China is every year in coking, gas purification and to coking
A large amount of coking wastewater can be all generated in the removal process of product.In coking wastewater containing cyanide, ammonia nitrogen, phenolic compound,
The heterocyclic compound etc. of polycyclic aromatic hydrocarbon and some nitrogenous, oxygen, sulphur has big pollutant concentration height, coloration, strong toxicity, difficult drop
The features such as solving big object proportion, complicated components, is typical poisonous and hardly-degradable wastewater.Coking wastewater, which has become, works as this life
Very important one of the problem of environmental pollution in boundary, if it is unprocessed or deal with improperly just by its it is outer arrange, not only polluted-water and
Soil endangers biological growth, destroys ecological environment, and its pollutant The book of Changes is crossed food chain and is enriched in human body, directly threatens
To the health of the mankind, therefore we must be handled coking wastewater.
Currently, coal chemical enterprise extensive use HPF Wet-type oxidation sweetening technical finesse waste liquids, with hydroquinone, bicyclic phthalein cyanogen
It is catalyst to buy six ichthyodins and ferrous sulfate, and using ammonia as alkali source, which can generate two kinds of inorganic salts, sulphur in sweetening process
Ammonium cyanate and ATS (Ammonium thiosulphate).Ammonium thiocyanate production quantity is 520,000 tons, and ATS (Ammonium thiosulphate) production quantity is 200,000 tons.Ammonium thiocyanate can
For pesticide and medicine and other fields, ATS (Ammonium thiosulphate) can be used for producing composite fertilizer.However, ammonium thiocyanate whole world annual requirement is only
Only 60,000 tons, still there is a large amount of ammonium thiocyanate to be not used to be commercialized, causes the waste of resource.
2- thiocarbamoyl imidazole alkane -4,5- diketone is a kind of pharmaceutical intermediate [Zankowska-Jasi ń ska W, Borowiec
H,Golus J, Kolasa A,Zaleska B,&Krzywosiński L,et al.(1990).Synthesis and
pharmacological investigations of 3-(aminoalkylene)-1-aryl-2-thioxo-4,5-
imidazolidinedione and 2,4,5-imidazolidine-trione derivatives.Polish Journal
OfPharmacology&spharmacy, 42 (1), 49], can prepare hypnotic [N.,Capan,G.,Günay,
N.S.,Ozkirimli,S.,M.,&Ozbey,S.,et al.(1999).Synthesis and hypnotic
activity of new 4-thiazolidinone and 2-thioxo-4,5-imidazolidinedione
derivatives.Cheminform,31(6),343-347；Ozkirimli,S.,&Hamali, O.(1995).Synthesis
and hypnotic activity of some 2-thioxo-4,5-imidazolidinedione derivatives.
Farmaco, 26 (28), 65-67], fungicide [Mihalcea, F., Barbuceanu, S.F., Draghici, C., Enache-
Preoteasa, C.,Cristea,C.,&Saramet,I.,et al.(2012).Synthesis and
characterization of new heter℃yclic compounds from 2-thioxo-4,5-
imidazolidinedione class and their evaluation for antimicrobial
Activity.Revista de Chimie-Bucharest-OriginalEdition-, 63 (5), 475-480] and it is anticonvulsion
Drug [Ulusoy, N., Ozkirimli, S., &G ü rsu, E. (2005) .Synthesis and preliminary
anticonvulsant activity evaluation of new 2-thioxo-4,5-imidazolidinedione
derivatives.Bollettino Chimico Farmaceutico,138(138), 516-520].Present method is to make
It is that raw material prepares 2- thiocarbamoyl imidazole alkane -4,5- diketone with thiocarbamide.Thiocarbamide is a kind of important industrial chemicals, generally by needing lime
Nitrogen method is prepared [Li Zhongbo, the research of (2005) new Process for Producing Thiourea from Urea, University Of Tianjin, master's thesis].Due to work
Skill is complicated, and cost is higher.
The present invention replaces thiocarbamide to produce pharmaceutical intermediate 2- thiocarbamoyl imidazole alkane -4,5- diketone using ATS (Ammonium thiosulphate), realizes
The by-product resource of coke-oven plant's sewage disposal achievees the purpose that turn waste into wealth.Due to the use of the thio miaows of 2- of this method production
Oxazolidine -4,5- diketone is at low cost, and therefore, the method for the present invention can be used by enterprise, has broad prospect of application.
Invention content
Ammonium thiocyanate is widely present in coking wastewater, is a kind of product of relative low price.But the prior art pair
The application of ammonium thiocyanate is limited.In view of the deficiencies of the prior art, we by ammonium thiocyanate by substituting thiocarbamide and oxalic acid two
Ethyl ester directly synthesizes 2- thiocarbamoyl imidazole alkane -4,5- diketone.A kind of new application of ammonium thiocyanate is provided, the resource of coking wastewater is pushed
Change.
The above-mentioned purpose of the present invention is achieved by following technical solution：
A kind of preparation method of 2- thiocarbamoyl imidazoles alkane -4,5- diketone, includes the following steps：
It weighs ammonium thiocyanate to be added in diethy-aceto oxalate, is fixed on heat collecting type constant-temperature heating magnetic stirring apparatus and adds
Heat, air setting；Generation yellow solution, cooling to generate solid, filtering obtains yellow solid after water washing, drying.
Preferably, in above-mentioned preparation method, ammonium thiocyanate：The molar ratio of diethy-aceto oxalate is：1:0.9~1.1.
Preferably, in above-mentioned preparation method, the heating polycondensation time is 2~8 hours.
Preferably, in above-mentioned preparation method, heating temperature is 137~147 DEG C.
Compared with prior art, advantage is for the invention：Ammonium thiocyanate has been used to substitute the thiocarbamide used originally in this method,
On the one hand production cost is reduced, on the other hand uses ammonium thiocyanate as raw materials for production, is the utilization to recycling product, saved
About resource.Synthesis cost can be reduced for enterprise, economized on resources.The invention is applied to environmental protection field, both saves
Resource reduces environmental pollution again, and environmental protection while can also obtain certain economic benefit, has important society and economy
Meaning.
Description of the drawings
Fig. 1 is the structural formula of the compounds of this invention 2- thiocarbamoyl imidazole alkane -4,5- diketone；
Fig. 2 is the synthetic route of prepare compound 2- thiocarbamoyl imidazoles alkane -4,5- diketone of the present invention；
Fig. 3 is the infrared absorpting light spectra of the compounds of this invention 2- thiocarbamoyl imidazole alkane -4,5- diketone.
Specific implementation mode
It is specific with reference to the accompanying drawings and examples to introduce essentiality content of the present invention, but the guarantor of the present invention is not limited with this
Protect range.
Embodiment 1：
Under nitrogen protection, ammonium thiocyanate (38.0g, 0.50mol), diethy-aceto oxalate are added into the there-necked flask of 250mL
(73.1g, 0.50mol), electromagnetic agitation simultaneously heat reaction at 140 DEG C, stop heating after 4 hours, wait for that it is cooled to room temperature, add
Water washing, filtering, drying obtain yellow solid 2- thiocarbamoyl imidazole alkane -4,5- diketone (59.6g, 91.6%).
MS(+ESI):M/z=131.3 [M+1]+；calcd.for C3H2N2O2S[M+1]+:
131.1.Elem.Anal.Calcd. For C3H2N2O2S(130.1):C,27.69；H,1.55；N,21.53；S,
24.64.Found:C,27.64,H,1.58,N,21.49； S,24.68.IR(KBr):υ=3385and 3191 (N-H)；1666
(C=O)；1642 (S=N)
Embodiment 2.
Under nitrogen protection, ammonium thiocyanate (38.0g, 0.50mol), diethy-aceto oxalate are added into the there-necked flask of 250mL
(65.8g, 0.45mol), electromagnetic agitation simultaneously heat reaction at 140 DEG C, stop heating after 4 hours, wait for that it is cooled to room temperature, add
Water washing, filtering, drying obtain yellow solid 2- thiocarbamoyl imidazole alkane -4,5- diketone (50.0g, 85.4%).
Embodiment 3.
Under nitrogen protection, ammonium thiocyanate (38.0g, 0.50mol), diethy-aceto oxalate are added into the there-necked flask of 250mL
(80.4g, 0.55mol), electromagnetic agitation simultaneously heat reaction at 140 DEG C, stop heating after 4 hours, wait for that it is cooled to room temperature, add
Water washing, filtering, drying obtain yellow solid 2- thiocarbamoyl imidazole alkane -4,5- diketone (55.9g, 85.9%).
From embodiment 1-3 it is found that working as ammonium thiocyanate：The molar ratio of diethy-aceto oxalate is：1:When 0.9~1.1, reaction yield
It is higher.It will be according to ammonium thiocyanate：The molar ratio of diethy-aceto oxalate is：1:1, it is expanded on further in embodiment.
Embodiment 4.
Under nitrogen protection, ammonium thiocyanate (38.0g, 0.50mol), diethy-aceto oxalate are added into the there-necked flask of 250mL
(73.1g, 0.50mol), electromagnetic agitation simultaneously heat reaction at 140 DEG C, stop heating after 8 hours, wait for that it is cooled to room temperature, add
Water washing, filtering, drying obtain yellow solid 2- thiocarbamoyl imidazole alkane -4,5- diketone (59.1g, 90.8%).
Embodiment 5.
Under nitrogen protection, ammonium thiocyanate (38.0g, 0.50mol), diethy-aceto oxalate are added into the there-necked flask of 250mL
(73.1g, 0.50mol), electromagnetic agitation simultaneously heat reaction at 140 DEG C, stop heating after 2 hours, wait for that it is cooled to room temperature, add
Water washing, filtering, drying obtain yellow solid 2- thiocarbamoyl imidazole alkane -4,5- diketone (57.3g, 88.2%).
From embodiment 1,4,5 it is found that at 2~8 hours between when reacted, reaction yield is stablized.It will be small according to the reaction time 4
When be expanded on further in embodiment.
Embodiment 6.
Under nitrogen protection, ammonium thiocyanate (38.0g, 0.50mol), diethy-aceto oxalate are added into the there-necked flask of 250mL
(73.1g, 0.50mol), electromagnetic agitation simultaneously heat reaction at 137 DEG C, stop heating after 4 hours, wait for that it is cooled to room temperature, add
Water washing, filtering, drying obtain yellow solid 2- thiocarbamoyl imidazole alkane -4,5- diketone (58.9g, 90.5%).
Embodiment 7.
Under nitrogen protection, ammonium thiocyanate (38.0g, 0.50mol), diethy-aceto oxalate are added into the there-necked flask of 250mL
(73.1g, 0.50mol), electromagnetic agitation simultaneously heat reaction at 147 DEG C, stop heating after 4 hours, wait for that it is cooled to room temperature, add
Water washing, filtering, drying obtain yellow solid 2- thiocarbamoyl imidazole alkane -4,5- diketone (59.8g, 91.9%).
From embodiment 1,6,7 it is found that when reaction temperature is at 137~147 DEG C, reaction yield is stablized.
The effect of above-described embodiment is specifically to introduce the essentiality content of the present invention, but those skilled in the art should know
Protection scope of the present invention should not be confined to the specific embodiment by road.
Claims (4)
1. a kind of preparation method of 2- thiocarbamoyl imidazoles alkane -4,5- diketone, which is characterized in that include the following steps：
It weighs ammonium thiocyanate to be added in diethy-aceto oxalate, is fixed on heat collecting type constant-temperature heating magnetic stirring apparatus and heats,
Air setting；Generate yellow solution, cooling to generate solid, filtering, water washing, it is dry after yellow solid to get.
2. preparation method according to claim 1, it is characterised in that：Ammonium thiocyanate：The molar ratio of diethy-aceto oxalate is：1:
0.9~1.1.
3. preparation method according to claim 1, it is characterised in that：It is 2~8 hours to heat the polycondensation time.
4. preparation method according to claim 1, it is characterised in that：Heating temperature is 137~147 DEG C.
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| CN201810453375.1A CN108727270B (en) | 2018-05-14 | 2018-05-14 | Preparation method of 2-thioimidazolidine-4, 5-diketone |
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| CN201810453375.1A CN108727270B (en) | 2018-05-14 | 2018-05-14 | Preparation method of 2-thioimidazolidine-4, 5-diketone |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496133A (en) * | 2016-10-19 | 2017-03-15 | 青岛云天生物技术有限公司 | The preparation method of ticagrelor midbody |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496133A (en) * | 2016-10-19 | 2017-03-15 | 青岛云天生物技术有限公司 | The preparation method of ticagrelor midbody |
Non-Patent Citations (4)
| Title |
|---|
| ALIREZA SAMZADEH-KERMANI，等: "Heteropolyacid catalyzed formation of thioparabanic acid derivatives", 《MONATSH CHEM》 * |
| LAURSEN, P. H.等: "Pyrimidines VII: Cyclization of Ethyl Oxalate and Ethyl a-Oxalylpropionate with Urea and Certain of Its Analogs", 《JOURNAL OF ORGANIC CHEMISTRY》 * |
| 张雪，等: "2-苯氨基咪唑啉-5-酮衍生物的合成及抗肿瘤活性", 《中国药物化学杂志》 * |
| 林峰,等: "三嗪环的生产工艺综述", 《广东化工》 * |
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