CN110204508A - 2,5- bis- replaces -1,2,4 thiadiazoles -3(2H)-thioketones, derivative and its synthetic method - Google Patents
2,5- bis- replaces -1,2,4 thiadiazoles -3(2H)-thioketones, derivative and its synthetic method Download PDFInfo
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- CN110204508A CN110204508A CN201910623005.2A CN201910623005A CN110204508A CN 110204508 A CN110204508 A CN 110204508A CN 201910623005 A CN201910623005 A CN 201910623005A CN 110204508 A CN110204508 A CN 110204508A
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- oxime
- phenyl
- rouge
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
- C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
- C07D285/08—1,2,4-Thiadiazoles; Hydrogenated 1,2,4-thiadiazoles
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- Organic Chemistry (AREA)
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
Abstract
The invention mainly relates to the synthetic methods that one kind 2,5- bis- replaces -3 (2H)-thioketones of -1,2,4 thiadiazoles and its derivative.The present invention is under alkali promotion, and in oxygen atmosphere, realization oxime lipoid substance, phenyl isothiocyanate class compound and one pot of elemental sulfur generate the technical solution that one kind 2,5- bis- replaces -3 (2H)-thioketones of -1,2,4 thiadiazoles and its derivative.Molecular structure stabilized is made, chemical property excellent product and its addition product replace the synthesis of -3 (2H)-thioketone of -1,2,4 thiadiazoles to provide a new path without transition metal-catalyzed in this method for 2,5- bis-.Have the characteristics that reaction system is simple, reaction condition is mild, consersion unit is less, experimental implementation is easy, yield is medium on the upper side.
Description
Technical field
The present invention relates to one kind 2,5- bis- to replace -3 (2H)-thioketones of -1,2,4 thiadiazoles, derivative and its synthetic method, belongs to
In organic synthesis field.
Background technique
2,5- bis- substitution -3 (2H)-thioketones of -1,2,4 thiadiazoles and derivative can be used as various organic syntheses, analytical reagent,
Fuel additive, lubricant additive, the intermediate of other drugs compound, the flotation collector of mineral, the flash rusting in coating
With the raw material of corrosion inhibitor.About the method for the such compound of synthesis, there are synthesis step complexity so far, and atom passes through
Ji property is poor, often needs to the preparatory functionalization of starting material.
Summary of the invention
Therefore, the purpose of the present invention is to provide one kind 2,5- bis- to replace -3 (2H)-thioketones of -1,2,4 thiadiazoles and its derivative
Object.
It is yet another object of the invention to provide one kind 2,5- bis- to replace -3 (2H)-thioketones of -1,2,4 thiadiazoles and its derivative
Synthetic method, with simple, the easy to operate advantage of reaction condition.
To which one kind 2,5- bis- of the invention replaces -3 (2H)-thioketones of -1,2,4 thiadiazoles and its derivative, its general formula
For Formulas I:
Wherein
R1Selected from hydrogen atom, halogen radical, ether, phenyl, straight chained alkyl, branched alkyl；
R2Selected from hydrogen atom, halogen radical, ether, straight chained alkyl, branched alkyl.
The present invention also provides the sides that a kind of synthesis 2,5- bis- replaces -3 (2H)-thioketones of -1,2,4 thiadiazoles and its derivative
Method, without transition metal-catalyzed, comprising the following steps:
(I) oxime lipoid substance, phenyl isothiocyanate class compound, elemental sulfur, alkali and organic are added in reaction vessel
Solvent；
(II) reactant is sufficiently mixed, heats and is reacted under oxygen atmosphere；
(III) purifying obtains product.
Preferably, method of the invention, the oxime lipoid substance are selected from C6-C12Fragrant ketoxime rouge, general formula II.
Wherein
R1Selected from hydrogen atom, halogen radical, ether, phenyl, straight chained alkyl, branched alkyl.
Preferably, method of the invention, the oxime lipoid substance are selected from: acetophenone oxime rouge, 4- methyl acetophenone oxime rouge,
4- methoxyacetophenone oxime rouge, 4- tert-butylacetophenone oxime rouge, 4- phenylacetophenone oxime rouge, 4- bromoacetophenone oxime rouge.
Preferably, method of the invention, the phenyl isothiocyanate class compound, general formula III:
Wherein
R2Selected from hydrogen atom, halogen radical, ether, straight chained alkyl, branched alkyl.
Preferably, method of the invention, the phenyl isothiocyanate class compound are selected from: phenyl isothiocyanate, 4- first
Base phenyl isothiocyanate, 4- methoxyphenyl isothiocyanates, 4- tert-butyl-phenyl isothiocyanates, the different sulphur cyanogen of 4- chlorphenyl
Acid esters,.
Preferably, method of the invention, the alkali are selected from: Li2CO3, Cs2CO3, Na2CO3, NaHCO3, K2CO3, KHCO3,
KSCN, K3PO4, K2HPO4, CH3COONa, Et3One of N or a variety of.
Preferably, method of the invention, the atmosphere of the reaction vessel are as follows: oxygen atmosphere；Oxime lipoid substance and different sulphur
The molar ratio 1.0: 2.0-3.0: 2.0-4.0: 0.5-1 of phenyl-cyanate class compound and elemental sulfur and alkali, reaction temperature 110
℃-130℃；A length of 8h-14h when reaction.
Preferably, method of the invention, the organic solvent are as follows: DMSO, PhCl, DMA, THF, Toluene, Isosorbide-5-Nitrae-
One of Dioxane, Cyclohexane.
The present invention compared with prior art caused by the utility model has the advantages that
(I) present invention is not necessarily to transition metal, in the presence of alkali, in oxygen atmosphere, realizes oxime lipoid substance and different sulphur
Phenyl-cyanate class compound and elemental sulfur are converted into one kind 2,5- bis- and replace -3 (2H)-thioketones of -1,2,4 thiadiazoles and its derivative
Technical solution, reaction raw materials are cheap and easy to get, and need not move through pretreatment, and the Atom economy of reaction is high；(II) in alkali
Under effect, in oxygen atmosphere, realize that oxime lipoid substance and phenyl isothiocyanate class compound and elemental sulfur are converted into one kind 2,
5- bis- replaces the technical solution of -3 (2H)-thioketones of -1,2,4 thiadiazoles and its derivative, it has reaction system simple, reacts item
The features such as part is mild, and materials are from a wealth of sources, and product utilization value is high, and market business prospect is expected；(III) in the work of alkali
Under, in oxygen atmosphere, realize that oxime lipoid substance and phenyl isothiocyanate class compound and elemental sulfur are converted into one kind 2,5-
Two replace the technical solution of -3 (2H)-thioketones of -1,2,4 thiadiazoles and its derivative, using the synthesis mesh of one pot of directly selecting property
Product and high income are marked, the predicament of existing multi-step synthetic methods bring human, financial, and material resources huge waste is overcome, has been saved a large amount of
Development time and production cycle.The present invention 2,5- bis- replaces -3 (2H)-thioketones of -1,2,4 thiadiazoles, derivative and its synthesis side
Method can be used for the multiple fields such as medicine, material；It is particularly suitable for one kettle way efficient selective synthesis 2,5- bis- and replaces -1,2,4 thiophenes two
The research and development of azoles -3 (2H)-thioketone.
Detailed description of the invention
In order to prove product of the invention, the present invention provides the nucleus magnetic hydrogen spectrum figure and nuclear-magnetism carbon spectrogram of section Example.
The nuclear magnetic spectrogram of 4 product of Fig. 1 a and 1b embodiment.
The nuclear magnetic spectrogram of 6 product of Fig. 2 a and 2b embodiment.
Wherein a is hydrogen spectrogram, and b is carbon spectrogram.
Fig. 3 is the chemical principle equation of the application.
Specific embodiment
In conjunction with the accompanying drawings, the present invention is further explained in detail.These attached drawings are simplified schematic diagram, only with
Illustration illustrates basic structure of the invention, therefore it only shows the composition relevant to the invention.
Embodiment 1-10
Step 1: by oxime lipoid substance (specific substance is shown in Table 1) and phenyl isothiocyanate class compound, (specific substance is shown in
Table 1) it is added in reaction vessel, respectively by elemental sulfur (specific substance is shown in Table 1), alkali (specific substance is shown in Table 1) and organic solvent (tool
1) body substance, which is shown in Table, to be added in reaction vessel.
Step 2: reaction vessel is evenly heated (such as oil bath heating) to temperature described in table 1, oxime lipoid substance and
Phenyl isothiocyanate class compound is reacted in a solvent, and continues the time described in table 1；Need this reaction gas illustrated
Atmosphere selects oxygen reaction.
Step 3: purification step.
Table 1: oxime lipoid substance and phenyl isothiocyanate class compound, elemental sulfur, alkali, You Jirong in embodiment 1-10
Agent, (oxime lipoid substance, phenyl isothiocyanate class compound, elemental sulfur and alkali) molar ratio, reaction temperature and reaction time.
* the molar ratio of oxime lipoid substance, phenyl isothiocyanate class compound, elemental sulfur and alkali.
Substance in reaction vessel after step 3 is subjected to conversion ratio detection and carries out nuclear magnetic resonance, the knot of section Example
Fruit is as follows:
The nuclear magnetic data of 4 product of embodiment is as follows:
1H NMR (400MHz, Chloroform-d) δ 8.19-8.13 (m, 2H), 7.51-7.44 (m, 4H), 7.25-7.20
(m, 1H), 7.17 (dd, J=8.4,1.2Hz, 2H), 1.36 (s, 9H)；13C NMR (100MHz, Chloroform-d) δ 165.8,
159.2,153.7,153.3,129.9,129.9,128.8,125.6,125.2,119.0,34.9,31.2.
The nuclear magnetic data of 6 product of embodiment is as follows:
1H NMR (400MHz, Chloroform-d) δ 8.17-8.12 (m, 2H), 7.62-7.57 (m, 2H), 7.50-7.44
(m, 2H), 7.26-7.22 (m, 1H), 7.16 (dd, J=8.4,1.1Hz, 2H)；13C NMR (100MHz, Chloroform-d) δ
165.0,158.1,152.9,131.5,131.4,130.6,129.9,125.9,125.0,119.0.
The conversion ratio and product of 2 embodiment 1-10 of table reaction
Taking the above-mentioned ideal embodiment according to the present invention as inspiration, through the above description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property range is not limited to the contents of the specification, it is necessary to which the technical scope thereof is determined according to the scope of the claim.
Claims (9)
1. one kind 2,5- bis- replaces -3 (2H)-thioketones of -1,2,4 thiadiazoles and its derivative, its general formula is Formulas I:
Wherein
R1Selected from hydrogen atom, halogen radical, ether, phenyl, straight chained alkyl, branched alkyl；
R2Selected from hydrogen atom, halogen radical, ether, straight chained alkyl, branched alkyl.
2. the side that a kind of synthesis 2,5- bis- described in claim 1 replaces -3 (2H)-thioketones of -1,2,4 thiadiazoles and its derivative
Method, which is characterized in that using copper-containing compound as catalyst, comprising the following steps:
(I) oxime lipoid substance, phenyl isothiocyanate class compound, elemental sulfur, alkali and organic solvent are added in reaction vessel；
(II) reactant is sufficiently mixed, heats and is reacted under oxygen atmosphere；
(III) purifying obtains product.
3. according to the method described in claim 2, it is characterized in that, the oxime lipoid substance is selected from C6-C12Fragrant ketoxime
Rouge, general formula II.
Wherein
R1Selected from hydrogen atom, halogen radical, ether, phenyl, straight chained alkyl, branched alkyl.
4. according to the method described in claim 3, it is characterized in that, the oxime lipoid substance is selected from: acetophenone oxime rouge, 4- first
Benzoylformaldoxime oxime rouge, 4- methoxyacetophenone oxime rouge, 4- tert-butylacetophenone oxime rouge, 4- phenylacetophenone oxime rouge, 4- chlorobenzene second
Ketoxime rouge.
5. according to the method in claim 2 or 3, which is characterized in that the phenyl isothiocyanate class compound, general formula are
III:
Wherein
R2Selected from hydrogen atom, halogen radical, ether, straight chained alkyl, branched alkyl.
6. according to the method described in claim 5, it is characterized in that, the phenyl isothiocyanate class compound is selected from: phenyl is different
Thiocyanates, 4- aminomethyl phenyl isothiocyanates, 4- methoxyphenyl isothiocyanates, 4- tert-butyl-phenyl isothiocyanates,
4- chlorophenyl isothiocyanate.
7. according to the described in any item methods of claim 2-6, which is characterized in that the alkali is selected from: Li2CO3, Cs2CO3,
Na2CO3, NaHCO3, K2CO3, KHCO3, KSCN, K3PO4, K2HPO4, CH3COONa, Et3One of N or a variety of.
8. the method according to claim 2, which is characterized in that the atmosphere of the reaction vessel are as follows: oxygen atmosphere
It encloses；The molar ratio 1.0: 2.0-3.0: 2.0-4.0 of oxime lipoid substance and phenyl isothiocyanate class compound and elemental sulfur and alkali:
0.5-1, reaction temperature are 110 DEG C -130 DEG C；A length of 8h-14h when reaction.
9. according to the described in any item methods of claim 2-8, which is characterized in that the organic solvent are as follows: DMSO, PhCl,
DMA, THF, Toluene, Isosorbide-5-Nitrae-Dioxane, one of Cyclohexane.
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| CN201910623005.2A CN110204508A (en) | 2019-07-06 | 2019-07-06 | 2,5- bis- replaces -1,2,4 thiadiazoles -3(2H)-thioketones, derivative and its synthetic method |
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| CN201910623005.2A CN110204508A (en) | 2019-07-06 | 2019-07-06 | 2,5- bis- replaces -1,2,4 thiadiazoles -3(2H)-thioketones, derivative and its synthetic method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113083514A (en) * | 2021-04-20 | 2021-07-09 | 山东理工大学 | Double-ligand type oxadiazole thioketone collecting agent and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3269896A (en) * | 1960-04-07 | 1966-08-30 | J R Geigey A G | Method and compositions for controlling pests |
| CN111978312A (en) * | 2020-09-18 | 2020-11-24 | 黄淮学院 | 5-aryl-1, 3, 4-thiadiazole/1, 3, 4-oxadiazole-2-amine compound and preparation method and application thereof |
| CN112321583A (en) * | 2020-12-02 | 2021-02-05 | 安徽理工大学 | Synthesis method of 1,2, 4-thiadiazole compound |
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2019
- 2019-07-06 CN CN201910623005.2A patent/CN110204508A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3269896A (en) * | 1960-04-07 | 1966-08-30 | J R Geigey A G | Method and compositions for controlling pests |
| CN111978312A (en) * | 2020-09-18 | 2020-11-24 | 黄淮学院 | 5-aryl-1, 3, 4-thiadiazole/1, 3, 4-oxadiazole-2-amine compound and preparation method and application thereof |
| CN112321583A (en) * | 2020-12-02 | 2021-02-05 | 安徽理工大学 | Synthesis method of 1,2, 4-thiadiazole compound |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113083514A (en) * | 2021-04-20 | 2021-07-09 | 山东理工大学 | Double-ligand type oxadiazole thioketone collecting agent and preparation method and application thereof |
| CN113083514B (en) * | 2021-04-20 | 2022-05-27 | 山东理工大学 | Double-ligand type oxadiazole thioketone collecting agent and preparation method and application thereof |
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