CN106905210B - A kind of preparation method of cartap intermediate - Google Patents
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- C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
- C07C331/02—Thiocyanates
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Abstract
The present invention relates to a kind of preparation methods of cartap intermediate, belong to heterocyclic compound technical field.In organic solvent, 1,3- dithiocyano -2- halogenopropanes are obtained by the reaction with rhodanate in 1,2,3- tri- halogenopropane at a certain temperature；In polar organic solvent, in the presence of a base, 1,3- dithiocyano -2- halogenopropanes and dimethylamine are subjected to nucleophilic substitution, reaction solution obtains 2- dimethylamino -1,3- dithiocyano propane after the operations such as extraction, drying, concentration, purification after reaction.The application is applied to the synthesis of cartap intermediate, both avoids the generation for generating isomers, improves reaction synthetic ratio, and is avoided using hypertoxic Cymag, has many advantages, such as to react that green, easy to operate, synthetic ratio is high very well.
Description
Technical field
The present invention relates to a kind of preparation methods of cartap intermediate, belong to heterocyclic compound technical field.
Background technology
Cartap is the root of straight ladybell toxin insecticides, has many advantages, such as that insecticidal spectrum is wide, good disinsection effect, can effectively prevent half
Wing mesh, the various pests such as Diptera and nematode.Currently, there are mainly two types of the synthetic methods of cartap：
One is Cymag route, first obtains key intermediate 2- dimethylamino -1,3- dithiocyano propane, then to it
It is hydrolyzed and cartap is obtained by the reaction, shown in specific route such as formula (1).
The route generates the cyanide wastewater of severe toxicity, the processing cost of waste water is high, makes this due to the use of hypertoxic Cymag
The green difference and cost of synthetic method are higher.
The second is rhodanate route, is carried out by 1- dimethylaminos -2,3- dichloropropane and rhodanate (such as NaSCN)
Nucleophilic substitution, the reaction are easy to get positive structure body 2- dimethylamino -1,3- dithiocyanos propane (positive structure body) and isomers
The product of the mixture of 1- dimethylamino -2,3- dithiocyano propane (isomers), isomers conversion gained does not have bioactivity,
Shown in specific route such as formula (2).
In above-mentioned route, rhodanate route generates unwanted isomers and isLead to the yield of product
Drop；Although the invalid isomersIt can recycle by Crystallization Separation and participate in reaction, positive structure body can be partially converted intoReach dynamic equilibrium to positive structure body and isomers, but be the increase in operating procedure, reduces combined coefficient.
Based on this, the application is made.
Invention content
For the drawbacks described above present in existing synthesis route, the application provides a kind of environmentally protective, combined coefficient
The preparation method of high cartap synthetic intermediate.
To achieve the above object, the technical solution that the application takes is as follows：
A kind of preparation method of cartap intermediate, includes the following steps：
(1) in organic solvent, 1,2,3- tri- halogenopropane reacts at a certain temperature with rhodanate, adds after reaction
Enter water and ethyl acetate, water phase is concentrated under reduced pressure to give structural formula after being extracted with ethyl acetate and isBis- sulphur cyanogen of 1,3-
Base -2- halopropane crude products；
(2) in polar organic solvent, in the presence of base, crude product obtained by step (1) is reacted with dimethylamine, reaction knot
Appropriate saturated sodium bicarbonate aqueous solution and the NaOH aqueous solutions of 1mol/L, water phase acetic acid second is added to reaction mixture in Shu Hou
Ester or dichloromethane extract, and are dried again with anhydrous sodium sulfate after organic phase saturated common salt water washing, through being concentrated under reduced pressure to give knot
Structure formula is2- dimethylamino -1,3- dithiocyano propane crude products, crude product is through being recrystallized to give high-purity
2- dimethylamino -1,3- dithiocyano propane.
Shown in the reaction equation of the above process such as formula (3).
, in formula, X=Br, Cl.
It is further to be used as preferably：
In step (1), the organic solvent is non-protonic solvent, and more preferably, the organic solvent is N,
Dinethylformamide (DMF), dimethyl sulfoxide (DMSO), acetonitrile (CH3CN), any one of tetrahydrofuran (THF).
In step (1), described 1,2,3- tri- halogenopropanes are 1,2,3- trichloropropanes or 1,2,3- tribromopropanes.
In step (1), the rhodanate is sodium sulfocyanate (NaSCN), potassium rhodanide (KSCN) or ammonium thiocyanate
(NH4SCN)；It is controlled in reaction process-SCN is excessive, 1,2,3- tri- halogenopropane：-The molar ratio of SCN is 1：2-2.5, more preferably
, 1,2,3- tri- halogenopropane：-The molar ratio of SCN is 1：2.1625.Rhodanate is excessive in reaction process, both may insure
The positive of reaction carries out, while guaranteed 1,2,3- tri- halogenopropanes reaction is abundant, and its main chain is incorporated in full into centre
In the finished product of body, be conducive to improve raw material availability and finished product synthetic ratio.
In step (1), the reaction temperature is room temperature to 100 DEG C.It is furthermore preferred that the reaction temperature is 50-80 DEG C,
Reaction time 4h.
In step (2), the polar organic solvent is n,N-Dimethylformamide (DMF) or acetonitrile (CH3CN)。
In step (2), the alkali is K2CO3Or Na2CO3。
In step (2), the dimethylamine is dimethylamine hydrochloride or dimethylamine agueous solution；Dimethylamine and crude product it is anti-
Answer 70-80 DEG C of temperature, reaction time 8h；Dimethylamine keeps excessive in reaction feeds intake, 1,2,3- tri- halogenopropane：-SCN：Two
The molar ratio of methylamine is 1：2-2.5：1.2-1.8；It is furthermore preferred that 1,2,3- tri- halogenopropane：-SCN：The molar ratio of dimethylamine is
1：2.1625：1.4875；Correspondingly, such as using crude product as the benchmark that feeds intake, then crude product 1,3- dithiocyano -2- halopropanes with
The molar ratio of dimethylamine is controlled 1:1.1-1.5, it is furthermore preferred that the molar ratio of 1,3- dithiocyano -2- halopropanes and dimethylamine
It is 1:1.2；Under alkaline condition, whether reversible reaction, diformazan can all occur for dimethylamine hydrochloride or dimethylamine agueous solution
Amine is excessive, just can ensure that the forward direction of reaction quickly carries out, the production of by-product is reduced and utmostly avoid, to improve centre
The purity of body 2- dimethylamino -1,3- dithiocyano propane.
In step (2), the solvent used in the recrystallization is ethyl acetate and petroleum ether.
Above-mentioned preparation method detailed process is as follows：
(1) a certain amount of 1,2,3- tri- halopropanes and rhodanate are weighed in round-bottomed flask, a certain amount of polarity is added
Solvent, reaction mixture stir that the reaction was complete to 1,2,3- tri- halopropane at a certain temperature.It is added after the reaction was complete certain
The water and ethyl acetate of amount, water phase are extracted with ethyl acetate twice.Organic phase is washed after merging with saturation NaCl aqueous solutions, anhydrous
Na2SO4It is dry, it is concentrated under reduced pressure, obtains 1,3- dithiocyano -2- halogenopropane crude products and carry out next step nucleophilic substitution.
(2) a certain amount of above-mentioned 1,3- dithiocyanos -2- halopropanes, dimethylamine hydrochloride (or dimethylamine agueous solution) are weighed
With carbonate in round-bottomed flask, a certain amount of solvent is added.Reaction mixture is stirred at a certain temperature to bis- sulphur cyanogen of 1,3-
The reaction was complete for base -2- halopropanes.Water and ethyl acetate is added to reaction mixture, organic phase, water phase acetic acid second are taken after layering
Ester is extracted twice.Merge organic phase and washed 3-4 times with saturation NaCl aqueous solutions, through anhydrous Na2SO4It is dry, it is concentrated under reduced pressure to give
2- dimethylamino -1,3- dithiocyano propane crude products.The crude product is through column chromatography or is recrystallized to give the 2- diformazans of high-purity
Amino -1,3- dithiocyano propane.
Compared with the preparation method of conventional cartap intermediate, the operation principle of the application and have the beneficial effect that：
(1) the application makes 1,2,3- as starting material with 1,2,3- tri- halogenopropane in organic solvent there are under atmosphere
Three halogenopropanes are directly reacted with rhodanate, reaction temperature control at 100 DEG C hereinafter, first obtain crude product 1, bis- sulphur cyanogen of 3-
Base -2- halogenopropanes, 1, the 3- dithiocyano -2- halogenopropanes are whether compared with 1- dimethylamino -2,3- dichloropropanes, also
With 1,2,3- tri- halogenopropanes are compared, and reactivity is stronger, and reaction selectivity is more direct, when its with dimethylamine in the application
When the lower progress nucleophilic displacement of fluorine that imposes a condition, higher 2- dimethylaminos -1, the 3- dithiocyano propane of purity can be directly obtained, is reacted
Starting material is simple and easy to get, and cheap, and reaction can be carried out fully, and synthetic ratio is high.
(2) the application has mainly used organic solvent, 1,2,3- tri- halogenopropanes, thiocyanic acid in entire reaction process
The substances such as salt, dimethylamine, involved substance are substance that is nontoxic, easily removing, are not had in reaction process such as hypertoxic cyaniding
The use of sodium, reaction green is good, and entire reaction is carried out under organic solvent atmosphere, reaction temperature at 100 DEG C hereinafter,
Reaction condition is mild, and synthesis cost is low.
(3) two-step reaction is related only in entire reaction process：The first step is tri- halogenopropanes of 1,2,3- and thiocyanic acid
Reactant salt obtains 1,3- dithiocyano -2- halogenopropanes, and second step is that 1,3- dithiocyano -2- halogenopropanes are reacted with dimethylamine
2- dimethylamino -1,3- dithiocyano propane is obtained, there was only 1,3- dithiocyano -2- halogenopropanes, one centre in reaction process
Product, and the invalid intermediate such as not will produce isomers, solve the problems, such as that former technique generates invalid isomers, improve 2- diformazans
The quality of amino -1,3- dithiocyano propane.
Description of the drawings
Fig. 1 is crude product 1,3- dithiocyano -2- N-Propyl Bromides in the application1H-NMR spectrum；
Fig. 2 is crude product 1,3- dithiocyano -2- N-Propyl Bromides in the application13135 spectrogram of C-NMR and DEPT；
Fig. 3 is the application synthetic intermediate 2- dimethylamino -1,3- dithiocyano propane1H-NMR spectrum；
Fig. 4 is the application synthetic intermediate 2- dimethylamino -1,3- dithiocyano propane13135 He of C-NMR and DEPT
90 spectrograms of DEPT.
Specific implementation mode
In entire reaction process, reaction is broadly divided into two steps, and the first step is 1,2,3- tri- halogenopropanes and rhodanate
1,3- dithiocyano -2- halogenopropanes are obtained by the reaction, in this process, mainly play influence to reaction effect is 1,2,3-
The rate of charge and reaction process condition of three halogenopropanes and rhodanate, by the measurement of parallel laboratory test we have found that：When 1,2,
Tri- halogenopropanes of 3-：-The molar ratio of SCN is 1：2-2.5, i.e.,-When SCN excess, reaction rate is most fast, the by-product in reaction process
Object such as 1- thiocyanogens -2,3- dibromopropane, 1,2,3- trithio dicyanopropane contents are relatively low, especially when 1,2,3- tri- halogenated third
Alkane：-The molar ratio of SCN is 1：When 2.1625, by-product is minimum, crude product yield highest, and 1-3 carries out specific with reference to embodiments
The elaboration of scheme；Second step is that two sulphur of 2- dimethylaminos -1,3- is obtained by the reaction with dimethylamine in 1,3- dithiocyano -2- halogenopropanes
The throwing amount of dicyanopropane, dimethylamine equally keeps excessive, with 1,2,3- tri- halogenopropane or 1,3- dithiocyano -2- halogenopropanes
As feeding intake, benchmark is controlled, by the measurement of parallel laboratory test we have found that：When tri- halogenopropanes of 1,2,3-：-SCN：Diformazan
The molar ratio of amine is 1：2-2.5：1.2-1.8 is or, work as crude product 1, the molar ratio control of 3- dithiocyano -2- halopropanes and dimethylamine
System is 1:1.1-1.5, when, it is ensured that the steady positive progress of reaction, especially when 1,2,3- tri- halogenopropane：-SCN：Diformazan
The molar ratio of amine is 1：2.1625：1.4875, alternatively, when the molar ratio of 1,3- dithiocyano -2- halopropanes and dimethylamine is 1:
When 1.2, finished product synthetic yield highest 4 and 5 is specifically addressed with reference to embodiments.
Embodiment 1
DMF (10mL), 1,2,3- tribromopropanes (0.94mL, 8mmol) and NaSCN are sequentially added to 50mL round-bottomed flasks
(1.4g, 17.3mmol).Water (50mL) and ethyl acetate (200mL), layering is added in reaction mixture after being stirred 4 hours at 70 DEG C
After take organic phase, water phase to be extracted twice with ethyl acetate (50mL).Through being saturated NaCl aqueous solutions (50mL) after organic phase is merged
Washing 3 times, anhydrous Na2SO4It is dry, it is concentrated under reduced pressure, three nucleophilic substitution products, weight and production is obtained after column chromatography for separation
Rate is respectively：1,3- dithiocyano -2- N-Propyl Bromides (1.6g, 6.8mmol, 85% yield), 1- thiocyanogen -2,3- dibromopropanes
(0.16g, 0.62mmol, 8% yield), 1,2,3- trithio dicyanopropane (0.086g, 0.4mmol, 5% yield).Bis- sulphur of 1,3-
Cyano -2- N-Propyl Bromides, 1- thiocyanogen -2,3- dibromopropanes, 1,2,3- trithio dicyanopropanes structure and1H-NMR,13C-NMR,
The data of DEPT 135 are as follows：
(1) 1,3- dithiocyanos -2- N-Propyl Bromides：
Structural formula：
1H-NMR(acetone-d6, 400MHz) and ppm 4.59-4.53 (m, 1H), 3.81 (dd, J=14.4Hz, 5.2Hz,
2H), 3.63 (dd, J=14.4,7.6Hz, 2H)；
13C-NMR(acetone-d6,100MHz)ppm 113.1,52.3,39.8；
Dept 135(acetone-d6,100MHz)ppm 113.1(C),52.3(CH),39.8(CH2)。
(2) 1- thiocyanogens -2,3- dibromopropanes：
Structural formula：
1H-NMR(acetone-d6, 400MHz) and ppm 4.68-4.62 (m, 1H), 4.05 (dd, J=11.2Hz, 5.2Hz,
1H), 3.99 (dd, J=11.2Hz, 6.4Hz, 1H), 3.77 (dd, J=14.4Hz, 5.2Hz, 1H), 3.59 (dd, J=
14.4Hz,8.0Hz,1H)；
13C-NMR(acetone-d6,100MHz)ppm 112.9,51.7,39.7,37.0；
Dept 135(acetone-d6,100MHz)ppm 112.9(C),51.7(CH),39.7(CH2),37.0(CH2)。
(3) 1,2,3- trithios dicyanopropane：
Structural formula：
1H-NMR(acetone-d6, 400MHz) and ppm 3.96-3.89 (m, 1H), 3.72 (dd, J=14.4Hz, 5.6Hz,
2H), 3.47 (dd, J=14.4,8.4Hz, 2H)；
13C-NMR(acetone-d6,100MHz)ppm 113.0,110.9,51.1,37.5。
Embodiment 2
DMSO (10mL), 1,2,3- tribromopropanes (0.94mL, 8mmol) and KSCN are sequentially added to 50mL round-bottomed flasks
(1.68g, 17.3mmol).Water (50mL) and ethyl acetate (200mL) is added after being stirred 4 hours at 70 DEG C in reaction mixture, point
Organic phase, water phase is taken to be extracted twice with ethyl acetate (50mL) after layer.Through being saturated NaCl aqueous solutions after organic phase is merged
(50mL) is washed 3 times, anhydrous Na2SO4It is dry, it is concentrated under reduced pressure, is obtained after column chromatography for separation：1,3- dithiocyano -2- N-Propyl Bromides
(1.56g, 6.6mmol, 83% yield), 1- thiocyanogens -2,3- dibromopropane (0.171g, 0.66mmol, 8% yield), 1,2,
3- trithios dicyanopropane (0.118g, 0.55mmol, 7% yield).
Embodiment 3
CH is sequentially added to 50mL round-bottomed flasks3CN (40mL), 1,2,3- trichloropropanes (1.89mL, 16.0mmol) and
NH4SCN (2.63g, 34.6mmol).Water (50mL) and ethyl acetate is added after flowing back 4 hours at 80 DEG C in reaction mixture
(200mL) takes organic phase, water phase to be extracted twice with ethyl acetate (50mL) after layering.Through being saturated NaCl after organic phase is merged
Aqueous solution (50mL) washs 3 times, anhydrous Na2SO4It is dry, it is concentrated under reduced pressure, crude product ethyl acetate and petroleum ether carry out column chromatography
Obtain 1,3- dithiocyano -2- N-Propyl Bromides (3g, 12.7mmol, 79% yield).
Embodiment 4
CH is sequentially added to 50mL round-bottomed flasks31,3- dithiocyanos-the 2- synthesized in CN (10mL), embodiment 1,2 or 3
N-Propyl Bromide (0.2g, 0.85mmol), dimethylamine hydrochloride (83.3mg, 1.02mmol) and potassium carbonate (354mg, 2.56mmol).
Water (50mL) and ethyl acetate (100mL) is added after being stirred 8 hours at 80 DEG C in reaction mixture, and organic phase, water phase are taken after layering
It is extracted twice with ethyl acetate (50mL).It is washed 3 times after organic phase is merged through being saturated NaCl aqueous solutions (50mL), it is anhydrous
Na2SO4It is dry, it is concentrated under reduced pressure, column chromatography obtains 2- dimethylamino -1,3- dithiocyano propane (136mg, 0.68mmol, 80%
Yield), structure and1H-NMR,13C-NMR data are as follows：
(1) 2- dimethylaminos -1,3- dithiocyano propane：
Structure：
1H-NMR(CDCl3,400MHz)ppm 3.37-3.29(m,2H),3.17-3.08(m,3H),2.32(s,6H)；
13C-NMR(CDCl3,100MHz)ppm 112.2,62.4,39.8,34.1。
Dept 135(CDCl3,100MHz)ppm 112.2(C),62.4,39.8 34.1(CH2)；
Dept 90(CDCl3,100MHz)ppm 62.4(CH),39.8(CH3)；
MS (m/z) 202 (M+H, 62), 318 (100).
Embodiment 5
DMF (20mL), 1,2,3- tribromopropanes (0.94mL, 8mmol) and NH are sequentially added to 50mL round-bottomed flasks4SCN
(1.4g, 17.3mmol).Reaction mixture stirs to 1,2,3- tribromopropanes that the reaction was complete at 50 DEG C.Reaction solution is cooled to room
Potassium carbonate (4.4g), dimethylamine hydrochloride (972mg) is added to reaction solution in Wen Hou, and mixed liquor continues stirring 8 hours at 70 DEG C
Water (50mL) and ethyl acetate (100mL) is added, organic phase, water phase is taken to be extracted twice with ethyl acetate (50mL) after layering.It will
Organic phase is washed 4 times after merging through being saturated NaCl aqueous solutions (50mL), anhydrous Na2SO4It is dry, be concentrated under reduced pressure, with ethyl acetate and
Petroleum ether is recrystallized to give 2- dimethylamino -1,3- dithiocyanos propane (1.2g, 6.0mmol, 75% yield).
The above content is the preferred embodiments of combination the invention to further detailed made by provided technical solution
Describe in detail bright, and it cannot be said that the invention specific implementation is confined to these above-mentioned explanations, for the affiliated technology of the invention
For the those of ordinary skill in field, without departing from the concept of the premise of the invention, several simple deductions can also be made
Or replace, it all shall be regarded as belonging to the protection domain of the invention.
Claims (10)
1. a kind of preparation method of cartap intermediate, it is characterised in that include the following steps：
（1）In organic solvent, 1,2,3- tri- halogenopropane is directly reacted with rhodanate, and reaction end is obtained by extraction structural formula and is
1,3- dithiocyano -2- halopropane crude products；
（2）In the presence of base, in polar organic solvent, by step（1）Gained crude product is reacted with dimethylamine, is waited for anti-
It should terminate, post-processing obtains 2- dimethylamino -1,3- dithiocyano propane；
The step（1）The molar ratio of tri- halogenopropanes of middle 1,2,3- and rhodanate is 1:2-2.5；The step（2）In it is thick
The molar ratio of product and dimethylamine is 1:1.1-1.5.
2. a kind of preparation method of cartap intermediate as described in claim 1, it is characterised in that：Step（1）In, it is described
Organic solvent is non-protonic solvent.
3. a kind of preparation method of cartap intermediate as claimed in claim 1 or 2, it is characterised in that：Described is organic molten
Agent is any one of n,N-Dimethylformamide, dimethyl sulfoxide, acetonitrile, tetrahydrofuran.
4. a kind of preparation method of cartap intermediate as described in claim 1, it is characterised in that：Tri- halogen of 1,2,3-
It is 1,2,3- trichloropropanes or 1,2,3- tribromopropanes for propane.
5. a kind of preparation method of cartap intermediate as described in claim 1, it is characterised in that：The rhodanate is
Sodium sulfocyanate, potassium rhodanide or ammonium thiocyanate.
6. a kind of preparation method of cartap intermediate as described in claim 1, it is characterised in that：Step（1）In, described 1,
The reaction temperature of tri- halogenopropanes of 2,3- and rhodanate is room temperature to 100 DEG C.
7. a kind of preparation method of cartap intermediate as described in claim 1, it is characterised in that：Step（2）In, it is described
Polar organic solvent is n,N-Dimethylformamide or acetonitrile.
8. a kind of preparation method of cartap intermediate as described in claim 1, it is characterised in that：Step（2）In, it is described
Alkali is K2CO3Or Na2CO3。
9. a kind of preparation method of cartap intermediate as described in claim 1, it is characterised in that：The dimethylamine is two
Methylamine hydrochloride or dimethylamine agueous solution.
10. a kind of preparation method of cartap intermediate as described in claim 1, which is characterized in that step（2）In, it is described
Post-processing refer to：After reaction, suitable saturated sodium bicarbonate aqueous solution and NaOH aqueous solutions is added to reaction mixture,
Water phase ethyl acetate or dichloromethane extract, and are dried again with anhydrous sodium sulfate after organic phase saturated common salt water washing, through subtracting
2- dimethylamino -1,3- dithiocyano propane crude products are obtained after pressure concentration, crude product is through column chromatography or is recrystallized to give high-purity
Spend 2- dimethylamino -1,3- dithiocyano propane.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101103725A (en) * | 2007-07-23 | 2008-01-16 | 江苏天容集团股份有限公司 | Cartap environment-friendly type preparing method |
| CN101519371A (en) * | 2008-05-18 | 2009-09-02 | 杭州宇龙化工有限公司 | Preparation method of cartap hydrochloride intermediate, i.e., 2-N, N-dimethyl-1, 3-dithio-cyano propane |
-
2017
- 2017-01-21 CN CN201710048393.7A patent/CN106905210B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101103725A (en) * | 2007-07-23 | 2008-01-16 | 江苏天容集团股份有限公司 | Cartap environment-friendly type preparing method |
| CN101519371A (en) * | 2008-05-18 | 2009-09-02 | 杭州宇龙化工有限公司 | Preparation method of cartap hydrochloride intermediate, i.e., 2-N, N-dimethyl-1, 3-dithio-cyano propane |
Non-Patent Citations (1)
| Title |
|---|
| 1,3-二氰硫基-2-N,N-二甲氨基丙烷制备研究;吴孝兰，等;《上海化工》;20101231;第35卷(第12期);第5-8页 * |
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