CN109206379A - A kind of synthetic method of metribuzin - Google Patents
A kind of synthetic method of metribuzin Download PDFInfo
- Publication number
- CN109206379A CN109206379A CN201811293479.7A CN201811293479A CN109206379A CN 109206379 A CN109206379 A CN 109206379A CN 201811293479 A CN201811293479 A CN 201811293479A CN 109206379 A CN109206379 A CN 109206379A
- Authority
- CN
- China
- Prior art keywords
- metribuzin
- carbonohydrazides
- synthetic method
- solvent
- methyl mercapto
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
- C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
- C07D253/06—1,2,4-Triazines
- C07D253/065—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members
- C07D253/07—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members with hetero atoms, or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D253/075—Two hetero atoms, in positions 3 and 5
Abstract
The present invention relates to a kind of synthetic methods of metribuzin, and by methyl mercapto carbonohydrazides and 3, under the effect of the catalyst, reaction generates the metribuzin to 3- dimethyl butyrate ketone acid, wherein the structural formula of the methyl mercapto carbonohydrazides are as follows:
Description
Technical field
Present invention relates particularly to a kind of synthetic methods of metribuzin.
Background technique
Metribuzin is a kind of efficient herbicide, English common name: metribuzin, other titles: metribuzin, Sai Ke with
And Beyer94337, it is interior suction selective herbicide, is mainly also can absorb by root absorption, stem, leaf.It is miscellaneous to annual broad-leaved
Grass and part gramineae weed have good preventive effect.Metribuzin is that one kind can be used for soybean, tomato, potato, clover, fruit
Garden and other crops prevent and kill off efficient, the less toxic dry land herbicide of a variety of broadleaf weeds and certain gramineae weeds, are China masters
Want one of herbicide kind.
The final key reaction that its in prior art synthesizes is first cyclization, then carries out methylation reaction, reactional equation
Formula is as follows, and wherein methylation reaction yield is generally in 80-85%.It reacts and contains more organic matter and salt in the waste water generated.
Wastewater treatment is costly, difficulty is big, causes the significant wastage of raw material.
Summary of the invention
The object of the present invention is to provide a kind of synthetic methods of metribuzin that synthetic route is short.
In order to solve the above technical problems, the present invention adopts the following technical scheme:
It is an object of the present invention to provide a kind of synthetic methods of metribuzin, by methyl mercapto carbonohydrazides and 3,3- dimethyl
Under the effect of the catalyst, reaction generates the metribuzin to batanone acid, wherein the structural formula of the methyl mercapto carbonohydrazides
Are as follows:
Reaction equation of the invention are as follows:
Preferably, described to react in the presence of a solvent, wherein the solvent is water, carbon atom number is 1~6
Monohydric alcohol, one or more of the dihydric alcohol that carbon atom number is 2~6 mixed solvent.
It is further preferred that the solvent is water, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, cyclohexanol, second
The mixed solvent of one or more of glycol, 1,3- propylene glycol, 1,4- butanediol.
It is further preferable that the solvent is the mixed solvent of one or more of water, methanol, ethylene glycol.
Most preferably, the solvent is water.
It is further preferred that the mass ratio that feeds intake of the methyl mercapto carbonohydrazides and the solvent is 1:1~1.5.
Preferably, the reaction carries out at 50~200 DEG C.
It is further preferred that the reaction carries out at 70~155 DEG C.
It is further preferable that the reaction carries out at 80~120 DEG C.
Preferably, the time of the reaction is 1~5h.
It is further preferred that the time of the reaction is 3~5h.
Preferably, the catalyst is sodium acetate, potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide
One of or it is a variety of.
It is further preferred that the catalyst is one of sodium acetate, potassium carbonate, sodium hydroxide or a variety of.
Preferably, the methyl mercapto carbonohydrazides, 3, the 3- dimethyl butyrate ketone acid and the catalyst feed intake
Mass ratio is 1:0.3~2:0.05~0.3.
It is further preferred that the methyl mercapto carbonohydrazides, 3, the 3- dimethyl butyrate ketone acid and the catalyst
Feed intake mass ratio be 1:0.5~1:0.05~0.2.
According to a kind of specific embodiment, the methyl mercapto carbonohydrazides and the catalyst are added in reactor,
Then solvent is added, is warming up to 80~150 DEG C, 3, the 3- dimethyl butyrate ketone acid is added portionwise, then at 50~200 DEG C
1~5h is reacted, it is after reaction, post-treated to obtain the metribuzin.
Preferably, the methyl mercapto carbonohydrazides the preparation method comprises the following steps: by thiocarbohydrazide and chloromethanes in alkali and solvent
In the presence of, the methyl mercapto carbonohydrazides for being made described is reacted at 30~40 DEG C.
It is further preferred that the alkali is one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide
Or it is a variety of.
It is further preferred that the solvent is one of water, methanol, ethyl alcohol, toluene, hexamethylene or a variety of.
It is further preferred that the mass ratio that feeds intake of the thiocarbohydrazide and the chloromethanes is 1:0.5~0.6.
It is further preferred that the mass ratio that feeds intake of the thiocarbohydrazide and the alkali is 1:0.4~0.5.
It is further preferred that the mass ratio that feeds intake of the thiocarbohydrazide and the solvent is 1:0.9~1.1.
According to a kind of preferred and specific embodiment, the specific preparation step of the methyl mercapto carbonohydrazides are as follows: will be described
Thiocarbohydrazide and the alkali be added in the solvent, be warming up to 30~35 DEG C, start to be passed through the chloromethanes gas
Body, it is 25~30g/h that control, which is passed through speed, after being passed through, is warming up to 35~40 DEG C, insulation reaction, after reaction, after
Processing obtains the methyl mercapto carbonohydrazides.
Due to the implementation of above technical scheme, the present invention has the advantage that compared with prior art
The present invention is compared with existing method, and cyclization reaction mild condition, the reaction time is short, high income, good product quality, drop
Low three wastes discharge amount improves production capacity and economic benefit.
Specific embodiment
The present invention is described in further details below in conjunction with specific embodiment.It should be understood that these embodiments are for saying
The bright basic principles, principal features and advantages of the present invention, and the present invention is not limited by the following examples.It is used in the examples
Implementation condition can do further adjustment according to specific requirement, and the implementation condition being not specified is usually the condition in routine experiment.
Following percentage is mass percent.
Embodiment 1, methyl mercapto for carbonohydrazides synthesis
By thiocarbohydrazide 100g and sodium hydroxide 45g, solvent toluene 100g is added, is warming up to 30-35 DEG C, starts to be passed through
55g methyl chloride gas, duration of ventilation 2h.After chloromethanes finishes, 35-40 DEG C of heat preservation 3h, sampling analysis, thiocarbohydrazide is less than
1%, reaction terminates.It is filtered to remove solid insoluble, distillation removing toluene and the chloromethanes for having neither part nor lot in reaction, methyl mercapto is for kappa
Hydrazine purity is greater than 97%.
The synthesis of embodiment 2, metribuzin
Methyl mercapto in embodiment 1 is added in four-hole bottle for carbonohydrazides 140g and potassium carbonate 28g, isopropanol 150g is added,
80 DEG C of heating, is added 3,3- acid dimethyl diketone 130g in three batches, finishes rear 80-85 DEG C of heat preservation 5h, sampling analysis reaction knot
Beam.70-75 DEG C is filtered to remove insoluble matter while hot, cools the filtrate to 20-25 DEG C, and drying obtains 97% or more piperazine of purity after filtering
Humulone 196.5g, yield 91.8%.
The synthesis of embodiment 3, metribuzin
Methyl mercapto in embodiment 1 is added in four-hole bottle for carbonohydrazides 140g and potassium carbonate 28g, water 150g, heating is added
95 DEG C, 3,3- acid dimethyl diketone 130g is added in three batches, finishes rear 95-100 DEG C of heat preservation 4h, sampling analysis reaction terminates.
It is cooled to 30-35 DEG C, drying obtains 97% or more metribuzin 202.7g of purity, yield 94.7% after filtering.
The synthesis of embodiment 4, metribuzin
Methyl mercapto in embodiment 1 is added in four-hole bottle for carbonohydrazides 140g and anhydrous sodium acetate 18g, water 150g is added,
95 DEG C of heating, is added 3,3- acid dimethyl diketone 130g in three batches, finishes rear 95-100 DEG C of heat preservation 3h, sampling analysis reaction knot
Beam.It is cooled to 30-35 DEG C, drying obtains 97% or more metribuzin 204g of purity, yield 95.3% after filtering.
The synthesis of embodiment 5, metribuzin
Methyl mercapto in embodiment 1 is added in four-hole bottle for carbonohydrazides 140g and sodium hydroxide 10g, water 150g is added, rises
95 DEG C of temperature, is added 3,3- acid dimethyl diketone 130g in three batches, finishes rear 95-100 DEG C of heat preservation 1h, sampling analysis reaction knot
Beam.It is cooled to 30-35 DEG C, drying obtains 97% or more metribuzin 191g of purity, yield 89.3% after filtering.
The synthesis of embodiment 6, metribuzin
Methyl mercapto in embodiment 1 is added in four-hole bottle for carbonohydrazides 140g and sodium hydroxide 10g, cyclohexanol is added
150g heats up 150 DEG C, 3,3- acid dimethyl diketone 130g is added in three batches, finishes rear 150-155 DEG C of heat preservation 1h, sampling point
Analysis reaction terminates.It is cooled to 80-85 DEG C, divides water.Continue to be cooled to 20-25 DEG C after point water, filtering drying obtain purity 97% with
Upper metribuzin 183g, yield 85.5%.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention, it is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of synthetic method of metribuzin, it is characterised in that: by methyl mercapto carbonohydrazides and 3,3- dimethyl butyrate ketone acid is being catalyzed
Under the action of agent, reaction generates the metribuzin, wherein the structural formula of the methyl mercapto carbonohydrazides are as follows:
2. the synthetic method of metribuzin according to claim 1, it is characterised in that: it is described reaction in the presence of the solvent into
Row, wherein the solvent is water, carbon atom number is 1~6 monohydric alcohol, carbon atom number are one of 2~6 dihydric alcohol
Or several mixed solvent.
3. the synthetic method of metribuzin according to claim 2, it is characterised in that: the solvent is water, methanol, second
One or more of alcohol, normal propyl alcohol, isopropanol, n-butanol, cyclohexanol, ethylene glycol, 1,3- propylene glycol, 1,4- butanediol mix
Bonding solvent.
4. the synthetic method of metribuzin according to claim 2, it is characterised in that: the methyl mercapto carbonohydrazides with it is described
Solvent feed intake mass ratio be 1:1~1.5.
5. the synthetic method of metribuzin according to claim 1, it is characterised in that: it is described reaction at 50~200 DEG C into
Row.
6. the synthetic method of metribuzin according to claim 5, it is characterised in that: it is described reaction at 70~155 DEG C into
Row.
7. the synthetic method of metribuzin according to claim 1, it is characterised in that: the catalyst is sodium acetate, carbon
One of sour potassium, sodium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide are a variety of.
8. the synthetic method of metribuzin according to claim 1, it is characterised in that: the methyl mercapto carbonohydrazides, described
3,3- dimethyl butyrate ketone acid and the catalyst feed intake mass ratio be 1:0.3~2:0.05~0.3.
9. the synthetic method of metribuzin according to any one of claim 1 to 9, it is characterised in that: by the first sulphur
Base carbonohydrazides and the catalyst are added in reactor, and solvent is then added, is warming up to 80~150 DEG C, are added portionwise described
3,3- dimethyl butyrate ketone acid, 1~5h is then reacted at 50~200 DEG C, it is after reaction, post-treated to obtain the piperazine
Humulone.
10. the synthetic method of metribuzin according to claim 1, it is characterised in that: the system of the methyl mercapto carbonohydrazides
Preparation Method are as follows: by thiocarbohydrazide and chloromethanes in the presence of alkali and solvent, the first for being made described is reacted at 30~40 DEG C
Sulfenyl carbonohydrazides.
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| CN201811293479.7A CN109206379A (en) | 2018-11-01 | 2018-11-01 | A kind of synthetic method of metribuzin |
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| CN201811293479.7A CN109206379A (en) | 2018-11-01 | 2018-11-01 | A kind of synthetic method of metribuzin |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4151355A (en) * | 1974-12-21 | 1979-04-24 | Bayer Aktiengesellschaft | Process for the preparation of 6-tert.-butyl-3-mercapto-4-amino-1,2,4-triazin-5(4H)-one |
| US4175188A (en) * | 1977-07-22 | 1979-11-20 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Process for the production of 1,2,4-triazin-5-one derivatives |
| CN105218472A (en) * | 2015-09-28 | 2016-01-06 | 江苏七洲绿色化工股份有限公司 | A kind of preparation method of triazone |
-
2018
- 2018-11-01 CN CN201811293479.7A patent/CN109206379A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4151355A (en) * | 1974-12-21 | 1979-04-24 | Bayer Aktiengesellschaft | Process for the preparation of 6-tert.-butyl-3-mercapto-4-amino-1,2,4-triazin-5(4H)-one |
| US4175188A (en) * | 1977-07-22 | 1979-11-20 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Process for the production of 1,2,4-triazin-5-one derivatives |
| CN105218472A (en) * | 2015-09-28 | 2016-01-06 | 江苏七洲绿色化工股份有限公司 | A kind of preparation method of triazone |
Non-Patent Citations (1)
| Title |
|---|
| ARUN KUMAR MAHATO ET AL.,: "Design, Synthesis and Glucose-6-Phosphatase Inhibitory Activity of Diaminoguanidine Analogues of 3-Guanidinopropionic Acid and Amino Substituted (Pyridin-2-Yl)thiourea Derivatives", 《J. PHARM. SCI. & RES.》 * |
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