CN1861585A - Process of preparing 3-substituted 5-azo substituting group substituted-[1,3,4]-thia-dizole-2-thione - Google Patents
Process of preparing 3-substituted 5-azo substituting group substituted-[1,3,4]-thia-dizole-2-thione Download PDFInfo
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- CN1861585A CN1861585A CN 200510043533 CN200510043533A CN1861585A CN 1861585 A CN1861585 A CN 1861585A CN 200510043533 CN200510043533 CN 200510043533 CN 200510043533 A CN200510043533 A CN 200510043533A CN 1861585 A CN1861585 A CN 1861585A
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Abstract
A process for preparing 3N-substituent-5-azo substituent substituted-[1,3,4]- thiadiazole-2-thione features the reaction between the monosubstituted or bisubstituted derivative of diphyenyl (or dinaphthyl) thiocarbazone and CO2 at a temp lower than 100 deg.C for the time shorter than 12 hr. Said product can be used for herbicide, bactericide, insecticide, dye, combustion inhibitor, additive of lubricating oil, antioxidant of rubber, etc.
Description
Technical field:
The present invention relates to prepare the novel method of 3N-replacement-5-azo-group replacement-[1,3,4]-thiadiazoles-2-thioketones.
Background technology:
Thiadiazoles is the aromaticity heterocycle that contains 2 nitrogen-atoms and 1 sulphur atom, and its derivative has extremely strong biological activity and pharmacologically active, has been widely used in aspects such as agricultural chemicals, medicine, life science and chemical industry.Aspect agricultural chemicals,, obtained very big development because it has multiple biological activitys such as weeding, sterilization, expelling parasite, plant-growth regulator and the disease-resistant function of inducing plant.Industrial, thiadiazoles is widely used as dyestuff, fireproofing agent, lubricating oil additive, rubber antioxidants, stablizer and photograph medication.At present, people synthetic are 2 mostly, 3-replacement-[1,3,4]-thiadiazoles, [1,2,3]-thiadiazoles-4-thio-ketone derivative, 2, and 4-replacement-[1,3,4]-thiadiazoles-5-thioketones and 4,5-replacement-thiadiazoles-2-thioketones, and also reaction yield is all not high.And 3, the synthetic method of 5-replacement-[1,3,4]-thiadiazoles-2-thioketones is not appeared in the newspapers, and 3N-replacement-5-azo-group replacement-[1,3,4]-thiadiazoles-2-thioketones synthetic method is blank especially.
Goal of the invention:
Purpose of the present invention then is to fill up 3N-replacement-5-azo-group replacement-[1,3,4]-thiadiazoles-2-thioketones synthetic method still to belong to the barren situation, propose a kind of under mild conditions, the novel method of " one kettle way " produced in high yields 3N-replacement-5-azo-group replacement-[1,3,4]-thiadiazoles-2-thioketones.The inventive method operation is simple, convenient post-treatment, and target product productive rate height is easy to purify.
Summary of the invention:
Content of the present invention is 3N-replacement-5-azo replacement-[1,3,4]-thiadiazoles-2-thioketones shown in preparation following formula (1)～(4).Specific implementation process is as follows: (phenylbenzene sulfo-carbazone list replaces or disubstituted derivative 1. to take by weighing a certain amount of reactant 1, perhaps dinaphthyl sulfo-carbazone list replaces or disubstituted derivative) 2. reactant 1 is dissolved in boiling point and is lower than in 100 ℃ the organic solvent, quantity of solvent was as the criterion after the 3. above-mentioned system deoxygenation to soak reactant 1 and to have more 20%, added dithiocarbonic anhydride (CS
2), the ratio of control reactant 1 and the amount of substance of dithiocarbonic anhydride is 4. to use 30%～50% the NaOH or the alcohol sodium alcohol solution of the KOH aqueous solution or 30% in 1: 1.25～1: 1.5, regulating above system and be alkalescence 5. keeps system in 20～80 ℃ under arbitrary temperature, continue to stir 5～12 hours 6. above-mentioned system cool to room temperature, the precipitation that reaction is generated washes with water, dry being lower than under 100 ℃ the condition, obtain target product.
Used phenylbenzene sulfo-carbazone list replacement or disubstituted derivative or dinaphthyl sulfo-carbazone list replace or disubstituted derivative is meant in the inventive method: as shown in the formula the sulfo-carbazone derivative shown in (5)～(8), these materials all can obtain according to literature method is synthetic.
Boiling point is lower than 100 ℃ organic solvent and is meant: acetonitrile, and acetone, trichloromethane, ethanol, tetracol phenixin and other boiling points are lower than 100 ℃ organic solvent.
The maintenance system continues to stir and was meant in 5～12 hours in 20～80 ℃ under arbitrary temperature: the maintenance system is under being higher than 20 ℃, being lower than arbitrary temperature of 80 ℃, and churning time at least 5 hours is no more than 12 hours.
Description of drawings
X1 represents methyl CH in formula (1)～(4)
3, ethyl CH
3CH
2, methoxyl group OCH
3, oxyethyl group OCH
3CH
2, chlorine atom Cl, bromine atoms Br, fluorine atom F or nitro NO
2X2 represents methyl CH
3, ethyl CH
3CH
2, methoxyl group OCH
3, oxyethyl group OCH
3CH
2, chlorine atom Cl, bromine atoms Br, fluorine atom F or nitro NO
2
X1 represents methyl CH in formula (5)～(8)
3, ethyl CH
3CH
2, methoxyl group OCH
3, oxyethyl group OCH
3CH
2, chlorine atom Cl, bromine atoms Br, fluorine atom F or nitro NO
2X2 represents methyl CH
3, ethyl CH
3CH
2, methoxyl group OCH
3, oxyethyl group OCH
3CH
2, chlorine atom Cl, bromine atoms Br, fluorine atom F or nitro NO
2
Provided concrete embodiment of the present invention below, they are to the further specifying of reaction method of the present invention, rather than limiting the scope of the invention:
Synthesizing of embodiment 1:3N-naphthyl-5-naphthylazo-[1,3,4]-thiadiazoles-2-thioketones
Reaction equation is as follows:
In the 250mL three-necked flask that thermometer, reflux condensing tube and stirring magneton are housed, add 2.8g (8.0mmol) two-α naphthyl sulfo-carbazone and 80mL acetonitrile, fully stirring is dissolved solid fully.After the system deoxygenation, add 0.8g (10.5mmol) dithiocarbonic anhydride, and with 50% aqueous sodium hydroxide solution (adding 8.0mmolNaOH altogether), the conditioned reaction system makes its pH=13-14, and hierarchy of control temperature stirs 5h under 45-50 ℃, precipitation becomes pale brown look by redness, and cool to room temperature filters, pale brown look precipitation washes with water, be lower than 100 ℃ of oven dry down, obtain brown xanchromatic 3N-naphthyl-5-naphthylazo-[1,3,4]-and thiadiazoles-2-thioketones crystal, output 2.9g (yield 91.1%).Fusing point 206-207 ℃.
The physics and the spectral response curve of gained compound are as follows:
Fusing point: 178-180 ℃.
Ultimate analysis: theoretical value C
22H
14N
4S
2: C, 66.30; H, 3.54; N, 14.06; Measured value: C, 66.18; H, 3.48; N, 14.01.
Infrared spectra: 3054 (m), 2922 (m), 1835 (m), 1627 (m), 1510 (m), 1372 (m), 1251 (vs), 1219 (vs), 1081 (m), 805 (m), 773 (s) cm
-1
Embodiment 2:3N-rubigan-5-is synthetic to chlorobenzene azo-group-[1,3,4]-thiadiazoles-2-thioketones
Reaction equation is as follows:
In the 250mL three-necked flask that thermometer, reflux condensing tube and stirring magneton are housed, add 2.6g (8.0mmol) two rubigan sulfo-carbazone and 80mL acetonitrile, fully stirring is dissolved solid fully.After the system deoxygenation, add 0.8g (10.5mmol) dithiocarbonic anhydride, and make its pH=13-14 with 50% aqueous sodium hydroxide solution (adding 8.0mmolNaOH altogether) conditioned reaction system, hierarchy of control temperature stirs 5h under 45-50 ℃, generate red precipitate, cool to room temperature, filter, red precipitate washes with water, is lower than 100 ℃ of oven dry down, obtain red 3N-rubigan-5-to chlorobenzene azo-group-[1,3,4]-and thiadiazoles-2-thioketones crystal, output 2.6g (yield 88.6%).
The physics and the spectral response curve of gained compound are as follows:
Fusing point: 178-180 ℃.
Ultimate analysis: theoretical value C
14H
8N
4S
2Cl
2: C, 45.78%; H, 2.20%; N, 15.25.Measured value: C, 45.59%; H, 2.03%; N, 15.04%.
Infrared spectra: 3320 (s), 2918 (m), 2832 (m), 1654 (m), 1502 (m), 1451 (m), 1253 (vs), 1220 (vs), 1049 (m), 779 (m), 550 (m) cm
-1
Synthesizing of the adjacent phenmethyl of the embodiment 3:3N--adjacent tolylazo base of 5--[1,3,4]-thiadiazoles-2-thioketones
Reaction equation is as follows:
In the 250mL three-necked flask that thermometer, reflux condensing tube and stirring magneton are housed, add 2.25g (8.0mmol) neighbour, the neighbour ' dimethylbenzene sulfo-carbazone and 80mL acetonitrile, fully stirring is dissolved solid fully.After the system deoxygenation, add 0.8g (10.5mmol) dithiocarbonic anhydride, and make its pH=13-14 with 50% aqueous sodium hydroxide solution (adding 8.0mmol NaOH altogether) conditioned reaction system, hierarchy of control temperature stirs 12h under 45-50 ℃, generate red precipitate, cool to room temperature, filter, red precipitate washes with water, is lower than 100 ℃ of oven dry down, obtain the adjacent phenmethyl of red 3N--adjacent tolylazo base-[1 of 5-, 3,4]-and thiadiazoles-2-thioketones crystal, output 2.35g (yield 90.1%).
The physics and the spectral response curve of gained compound are as follows:
Fusing point: 139-140 ℃.
Ultimate analysis: theoretical value C
16H
14N
4S
2: C, 58.90%; H, 4.29%; N, 17.18.Measured value: C, 58.26%; H, 4.15%; N, 17.15%.
Infrared spectra: 3427 (s), 2922 (m), 2852 (m), 1635 (m), 1522 (m), 1451 (m), 1253 (vs), 1221 (vs), 1057 (m), 770 (m), 535 (m) cm
-1
Claims (4)
1. method for preparing 3N-replacement-5-azo-group replacement-[1,3,4]-thiadiazoles-2-thioketones that (1)～(4) formula represents
X1 represents methyl CH in formula (1)～(4)
3, ethyl CH
3CH
2, methoxyl group OCH
3, oxyethyl group OCH
3CH
2, chlorine atom Cl, bromine atoms Br, fluorine atom F or nitro NO
2X2 represents methyl CH
3, ethyl CH
3CH
2, methoxyl group OCH
3, oxyethyl group OCH
3CH
2, chlorine atom Cl, bromine atoms Br, fluorine atom F or nitro NO
2
It is characterized in that under normal pressure single replacement of single replacement of phenylbenzene sulfo-carbazone or disubstituted derivative or dinaphthyl sulfo-carbazone or disubstituted derivative and dithiocarbonic anhydride (CS
2) reaction, the ratio of the amount of substance of reactant is 1: 1.25～1: 1.5; The solvent that reacts used is that boiling point is lower than 100 ℃ organic solvent, and solvent volume was to soak reactant and 20% the amount of having more is as the criterion; During reaction, the alcohol sodium alcohol solution regulation system of the NaOH with 30%～50% or the KOH aqueous solution or 30% is an alkalescence; Under 20～80 ℃ of temperature, stirred 5～12 hours; The sedimentation and filtration that generates is washed with water to nearly neutrality, being lower than 100 ℃ of oven dry down, promptly obtains product.
2. replace or disubstituted derivative as the single of the phenylbenzene sulfo-carbazone in the method as described in the right 1, shown in its feature following (5)～(6) formula:
X1 represents methyl CH in formula (5)～(6)
3, ethyl CH
3CH
2, methoxyl group OCH
3, oxyethyl group OCH
3CH
2, chlorine atom Cl, bromine atoms Br, fluorine atom F or nitro NO
2X2 represents methyl CH
3, ethyl CH
3CH
2, methoxyl group OCH
3, oxyethyl group OCH
3CH
2, chlorine atom Cl, bromine atoms Br, fluorine atom F or nitro NO
2
3. replace or disubstituted derivative as the single of the dinaphthyl sulfo-carbazone in the method as described in the right 1, shown in its feature following (7)～(8) formula
X1 represents methyl CH in formula (7)～(8)
3, ethyl CH
3CH
2, methoxyl group OCH
3, oxyethyl group OCH
3CH
2, chlorine atom Cl, bromine atoms Br, fluorine atom F or nitro NO
2X2 represents methyl CH
3, ethyl CH
3CH
2, methoxyl group OCH
3, oxyethyl group OCH
3CH
2, chlorine atom Cl, bromine atoms Br, fluorine atom F or nitro NO
2
4. as the organic solvent in the method as described in the right 1, its feature can for: acetonitrile, acetone, ethanol, trichloromethane, tetracol phenixin and other boiling points be at the organic solvent below 100 ℃, and solvent volume is as the criterion with the amount of soaking reactant and 20% the amount of having more.
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|---|---|---|---|
| CN 200510043533 CN1861585A (en) | 2005-05-12 | 2005-05-12 | Process of preparing 3-substituted 5-azo substituting group substituted-[1,3,4]-thia-dizole-2-thione |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757405A (en) * | 2012-07-25 | 2012-10-31 | 山东理工大学 | Vanilline derivative containing thiadiazole, preparation method and purpose thereof |
| CN107674042A (en) * | 2017-09-28 | 2018-02-09 | 河南科技大学 | A kind of method of ultrasonic wave uninanned platform containing triazole and thiazole ring to Win4692 |
-
2005
- 2005-05-12 CN CN 200510043533 patent/CN1861585A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757405A (en) * | 2012-07-25 | 2012-10-31 | 山东理工大学 | Vanilline derivative containing thiadiazole, preparation method and purpose thereof |
| CN102757405B (en) * | 2012-07-25 | 2014-04-16 | 山东理工大学 | Vanilline derivative containing thiadiazole, preparation method and purpose thereof |
| CN107674042A (en) * | 2017-09-28 | 2018-02-09 | 河南科技大学 | A kind of method of ultrasonic wave uninanned platform containing triazole and thiazole ring to Win4692 |
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