CN110015998A - A kind of synthetic method of 1,5-bis(p-nitrosulfonamido)-1,5-diazacyclooctane-3,7-dione - Google Patents

Abstract

The invention discloses a method for synthesizing 1,5-bis(p-nitrosulfonamido)-1,5-diazacyclooctane-3,7-dione, which is an important compound for synthesizing energetic materials The intermediate belongs to the technical field of organic synthesis. The technical route is as follows: 1. After 4-nitrobenzenesulfonamide and potassium carbonate are uniformly mixed in an organic solvent, an appropriate amount of 1,3-dibromo-2 acetone is added to stir, and the reaction is carried out under certain conditions, to the crude product Extraction and drying gave product A. 2. After 3-chloro-2-(chloromethyl)prop-1-ene is fully dissolved in the acetone solution, sodium iodide is added, the reaction is refluxed for a period of time, the product is extracted, washed repeatedly, dried and concentrated After that, a white solid is obtained, which is the product B. 3, the obtained compounds A and B are in an organic solvent, fully dissolving and reacting for a period of time, feeding a certain amount of ozone gas, and then extracting, washing and drying it to obtain the target product 1,5-two ( p-nitrosulfonamido)-1,5-diazacyclooctane-3,7-dione. The invention has the advantages of simple operation, mild conditions, easily available raw materials, wide application range of substrates and the like, and has potential industrial application value.

Description

A kind of 1,5-bis(p-nitrosulfonamido)-1,5-diazacyclooctane-3,7-dione method of synthesis

technical field

The invention belongs to the technical field of organic synthesis, and in particular relates to a synthetic method of an intermediate---1,5-bis(p-nitrosulfonamido)-1,5-diazacyclooctane-3,7-dione .

Background technique

Heterocyclic nitramines substituted with geminal difluoroamino groups have the properties of high energy and high density, and can be used as oxidants for rocket solid propellant fuels. One of the high-energy and high-density energetic materials is 1,5-dinitro-3,3,7,7-tetrakis(difluoroamino)-1,5-diazaoctane (HNFX), which has been It has attracted extensive attention in related fields. The intermediate compound for the synthesis of high-energy and high-density energetic material HNFX is 1,5-bis(p-nitrosulfonamido)-1,5-diazacyclooctane-3,7-dione.

So far, the protocol for synthesizing 1,5-bis(p-nitrosulfonamido)-1,5-diazacyclooctane-3,7-dione is to combine 4-nitrobenzenesulfonamide with epoxy Using chloropropane as the starting material, 1,5-bis(p-nitrosulfonamido)-1,5-diazacyclooctane-3,7-diol was synthesized by binary condensation into a ring. 1,5-bis(p-nitrosulfonamido)-1,5-diazacyclooctane-3,7-diol was used as raw material to synthesize geminal difluoroamino-substituted heterocyclic nitroxide through Swern oxidation reaction. The active intermediate 1,5-bis(p-nitrosulfonamido)-1,5-diazacyclooctane-3,7-dione is widely used in the research of amine compounds. When this method is used to synthesize diols, many by-products make the yield very low, and the Swern oxidation reaction needs to be carried out at ultra-low temperature (about -78°C), so it is more difficult to scale up the reaction.

Therefore, it is particularly necessary to develop a simple, convenient and safe process suitable for large-scale production of 1,5-bis(p-nitrosulfonamido)-1,5-diazacyclooctane-3,7-dione .

SUMMARY OF THE INVENTION

In order to solve the above technical problems, the present invention provides a synthetic 1,5-bis(p-nitrosulfonamido)-1,5-diazaheterocycle with few by-products, high yield, simple reaction route and mild reaction conditions Process for octane-3,7-dione compounds.

1,5-bis(p-nitrosulfonamido)-1,5-diaza-3-pentanone can be obtained by reacting 4-nitrobenzenesulfonamide with 1,3-dibromo-2-acetone. It reacts with 3-iodo-2-iodomethylpropene in the atmosphere of ozone to obtain the target product, and through the adjustment of parameters, the synthesis route is simple, the reaction conditions are mild, the by-products are few, and the yield is high; the overall reaction route is simple, The raw materials are easily available, the reaction conditions are mild, the by-products are few, and the yield is high, which is the intermediate 1,5-bis(p-nitrosulfonamido)-1,5-diazacyclooctane-3,7-dione A synthetic method with great reference value is provided.

The technical scheme provided by the present invention is as follows:

A method for synthesizing 1,5-bis(p-nitrosulfonamido)-1,5-diazacyclooctane-3,7-dione, comprising the following steps:

Dissolve 1,5-bis(p-nitrosulfonamido)-3-pentanone and 3-iodo-2-iodomethylpropene in organic solvent A, reaction time t ₁ ; then feed into ozone to continue the reaction, the reaction Time _t2 is obtained.

The above-mentioned organic solvent A is selected from N,N-dimethylformamide, N,N-dimethylacetamide, xylene or toluene.

The above reaction time _t1 is 5-24h; the reaction time _t2 is 0.5-5h.

The synthetic method of above-mentioned 1,5-two (p-nitrosulfonamido)-3-pentanone, comprises the following steps:

(1) 4-nitrobenzenesulfonamide is dissolved in organic solvent B, adding anhydrous potassium carbonate and stirring to dissolve; then add 1,3-dibromo-2 acetone and continue heating and stirring reaction to obtain crude product;

(2) The crude product is extracted with organic solvent C and distilled water, and the organic layer is dewatered and dried with anhydrous sodium sulfate to obtain the product.

In the above step (1), the organic solvent B is selected from N,N-dimethylformamide, N,N-dimethylacetamide or toluene.

In the above step (1), K ₂ CO ₃ was added and the stirring time was 30-60 min; 1,3-dibromo-2 acetone was added and the stirring was continued for 5-24 h, and the stirring temperature was 25°C-50°C.

In the above-mentioned step (3), the organic solvent C is chloroform or dichloromethane.

The molar ratio of the above-mentioned 4-nitrobenzenesulfonamide, K ₂ CO ₃ and 1,3-dibromo-2 acetone is 2-2.5:2.5-3.5:1.

The synthetic method of above-mentioned 3-iodo-2-iodomethyl propylene, comprises the following steps:

3-Chloro-2-chloromethylpropene was dissolved in acetone solution, an appropriate amount of sodium iodide was added, the reaction was refluxed, and then the reaction was cooled to room temperature, and the residue was extracted, washed, dried and concentrated to obtain a white solid, is the product.

Beneficial effects of the present invention:

(1) Using 1,5-bis(p-nitrosulfonamido)-1,5-diaza-3-pentanone and 3-iodo-2-iodomethylpropene to react in an atmosphere of ozone to obtain the target product, and through the control of parameters, the synthetic route is simple, the reaction conditions are mild, the by-products are few, and the yield is high;

(2) Synthesis of 1,5-bis(p-nitrosulfonamido)-1,5 _- bis in organic solution of K2CO3 using ₄ -nitrobenzenesulfonamide and 1,3-dibromo-2acetone Nitrogen-3-pentanone is used as the basis for the subsequent reaction. The raw materials of this reaction are abundant and readily available, the synthetic route is simple, and the reaction conditions are mild;

(3) The overall reaction route is simple, the raw materials are readily available, the reaction conditions are mild, the by-products are few, and the yield is high, which is the intermediate 1,5-bis(p-nitrosulfonamido)-1,5-diazacyclooctane Alkane-3,7-dione provides a valuable synthetic method.

Description of drawings

Fig. 1 is the nuclear magnetic spectrum of 1,5-bis(p-nitrosulfonamido)-1,5-diaza-3-pentanone prepared in Example 1;

Fig. 2 is the nuclear magnetic spectrum of 3-iodo-2-iodomethylpropene prepared by embodiment 1;

3 is the nuclear magnetic spectrum of 1,5-bis(p-nitrosulfonamido)-1,5-diazacyclooctane-3,7-dione prepared in Example 1.

Detailed ways

The present invention will be further described below with reference to specific embodiments, but the content of the present invention is not limited thereto at all.

For the convenience of description, 1,5-bis(p-nitrosulfonamido)-1,5-diaza-3-pentanone is set as compound A; 3-iodo-2-iodomethylpropene is set as compound B.

A method for synthesizing 1,5-bis(p-nitrosulfonamido)-1,5-diazacyclooctane-3,7-dione, comprising the following steps:

Dissolve 1,5-bis(p-nitrosulfonamido)-1,5-diaza-3-pentanone and 3-iodo-2-iodomethylpropene in organic solvent A, reaction time t ₁ ; then Ozone is introduced to continue the reaction, and the reaction time is t ₂ .

The above-mentioned organic solvent A is selected from N,N-dimethylformamide, N,N-dimethylacetamide, xylene or toluene.

The above reaction time _t1 is 5-24h; the reaction time _t2 is 0.5-5h.

A method for synthesizing 1,5-bis(p-nitrosulfonamido)-1,5-diaza-3-pentanone, comprising the following steps:

(1) 4-nitrobenzenesulfonamide is dissolved in organic solvent B, adding anhydrous potassium carbonate and stirring to dissolve; then add 1,3-dibromo-2 acetone and continue heating and stirring reaction to obtain crude product;

(2) The crude product is extracted with organic solvent C and distilled water, and the organic layer is dewatered and dried with anhydrous sodium sulfate to obtain the product.

In the above step (1), the organic solvent B is selected from N,N-dimethylformamide, N,N-dimethylacetamide or toluene.

In the above step (1), K ₂ CO ₃ was added and the stirring time was 30-60 min; 1,3-dibromo-2 acetone was added and the stirring was continued for 5-24 h, and the stirring temperature was 25°C-50°C.

In the above-mentioned step (3), the organic solvent C is chloroform or dichloromethane.

The molar ratio of the above-mentioned 4-nitrobenzenesulfonamide, K ₂ CO ₃ and 1,3-dibromo-2 acetone is 2-2.5:2.5-3.5:1.

The synthetic method of 3-iodo-2-iodomethylpropene, comprises the following steps:

3-Chloro-2-chloromethylpropene was dissolved in acetone solution, an appropriate amount of sodium iodide was added, the reaction was refluxed for 3-24 h, then the reaction was cooled to room temperature, the residue was extracted with hexane, washed, dried and concentrated, A white solid is obtained, which is the product.

The synthetic route is as follows:

Example 1

(1) 4-nitrobenzenesulfonamide (2.895mmol) was placed in a 50mL round-bottom flask at room temperature, DMF (25mL) solution was added, and K ₂ CO ₃ (4.053mmol) was stirred for 30min to obtain a homogeneous solution. , 1,3-dibromo-2acetone (1.158mmol) was added, and stirring was continued for 5h at room temperature. After the reaction, the crude product was extracted with chloroform solution and distilled water respectively, and the organic layer was dewatered and dried with anhydrous sodium sulfate (Na ₂ SO ₄ ) to obtain compound A, ¹ H NMR (400MHz, CDCl ₃ )δ8 .28(d, J=8.7Hz, 4H), 8.12(s, 2H), 8.04(d, J=8.7Hz, 4H), 3.67(s, 4H). The NMR spectrum is shown in Figure 1.

(2) 3-Chloro-2-(chloromethyl)prop-1-ene (4.00 mmol) was dissolved in acetone (10 mL) solution, sodium iodide (9.2 mmol) was added, and the reaction was refluxed for 10 h. The reaction was cooled to room temperature, the residue was extracted with hexane solution and distilled water, the organic layer was washed with saturated sodium sulfite (Na ₂ SO ₃ ) (10 mL) and brine solution, dried and concentrated to obtain a white solid, which was compound B, ¹ H NMR (400MHz, CDCl ₃ )δ5.32(s, 2H), 4.10(s, 4H). The nuclear magnetic spectrum is shown in Figure 2.

(3) In DMF, after the obtained compound A and compound B were reacted for 5 hours, the ozone gas was introduced to continue the reaction for 3 hours, and then the target product was obtained by extraction, washing and drying. ¹ H NMR (400MHz, DMSO) δ8.41 (d, J=7.9Hz, 4H), 8.15 (d, J=8.3Hz, 4H), 4.25 (s, 8H). The nuclear magnetic spectrum is shown in Figure 3.

Example 2

(1) Nitrobenzenesulfonamide (2.663 mmol) was added to DMF (25 mL) solution at room temperature, then K ₂ CO ₃ (3.474 mmol) was added and stirred for 45 minutes, and then 1,3-dibromo-2-acetone ( 1.158 mmol) stirring was continued for 16 hours. The crude product was extracted again using chloroform and water. The organic layer was dried using anhydrous sodium sulfate.

(2) 3-Chloro-2-(chloromethyl)prop-1-ene (4.00 mmol) was dissolved in acetone (10 mL) solution, sodium iodide (9.20 mmol) was added, and the reaction was refluxed for 15 hours. The reaction was then cooled, the residue was extracted with hexanes and water, the organic layer was washed with saturated Na2SO3 _{( 10} mL) and brine, dried and concentrated. The product was obtained as a white solid.

(3) In DMF, after the obtained compound A and compound B are reacted for 24 hours, ozone gas is introduced to continue the reaction for 0.5 hours, and then the target product is obtained by extraction, washing and drying.

Example 3

(1) Nitrobenzenesulfonamide (2.432 mmol) was added to DMF (25 mL) solution at room temperature, then K ₂ CO ₃ (2.895 mmol) was added and stirred for 60 minutes, and then 1,3-dibromo-2-acetone ( 1.158 mmol) stirring was continued for 24 hours. The crude product was extracted again using chloroform and water. The organic layer was dried using anhydrous sodium sulfate.

(2) 3-Chloro-2-(chloromethyl)prop-1-ene (4.00 mmol) was dissolved in acetone (10 mL) solution, sodium iodide (9.20 mmol) was added, and the reaction was refluxed for 24 hours. The reaction was then cooled, the residue was extracted with hexanes and water, the organic layer was washed with saturated Na2SO3 _{( 10} mL) and brine, dried and carefully concentrated. The product was obtained as a white solid.

(3) in DMF, after the obtained compound A and compound B are reacted for 16h, the ozone gas is introduced to continue the reaction for 5h, and then extraction, washing and drying are performed to obtain the target product

The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited to this. Any modifications made by any person skilled in the art within the technical scope disclosed by the present invention are equivalent Substitutions and improvements, etc., should all be included within the protection scope of the invention.

Claims (9)

1. one kind 1,5- bis- (to nitro sulfoamido) -1,5- diazo-cyclooc-tane -3,7- diketone synthetic method, feature exist In, comprising the following steps:

(to nitro the sulfoamido) -1,5- of 1,5- bis- phenodiazine-propione and the iodo- 2- iodomethyl propylene of 3- are dissolved in organic solvent A In, reaction time t₁；Then passing to ozone, the reaction was continued, reaction time t₂To obtain the final product.

2. according to the method described in claim 1, it is characterized by: the organic solvent A be selected from n,N-Dimethylformamide, N, N- dimethyl acetamide, dimethylbenzene or toluene.

3. according to the method described in claim 1, it is characterized by: the reaction time t₁For 5-24h；Reaction time t₂For 0.5-5h。

4. the synthetic method of 1,5-, bis- (to nitro sulfoamido) -1,5- phenodiazine-propione described in claim 1, feature It is, comprising the following steps:

(1) 4- nitrobenzene sulfonamide is dissolved in organic solvent B, Anhydrous potassium carbonate stirring and dissolving is added；Then 1,3- bis- is added Bromo- 2 acetone continues heating stirring and reacts to obtain crude product；

(2) crude product is extracted using organic solvent C and distilled water, and water removal is carried out to organic layer with anhydrous sodium sulfate and is done It is dry, obtain product.

5. according to the method described in claim 4, it is characterized by: organic solvent B is selected from N, N- dimethyl in the step (1) Formamide, DMAC N,N' dimethyl acetamide or toluene.

6. according to the method described in claim 4, it is characterized by: K is added in the step (1)₂CO₃Mixing time is 30- 60min；Bromo- 2 acetone of 1,3- bis- is added to continue to stir 5-24h, whipping temp is 25 DEG C -50 DEG C.

7. according to the method described in claim 4, it is characterized by: organic solvent C is chloroform or two in the step (3) Chloromethanes.

8. according to the method described in claim 4, it is characterized by: the 4- nitrobenzene sulfonamide, K₂CO₃, 1,3- bis- bromo- 2 third The molar ratio of ketone is 2-2.5:2.5-3.5:1.

9. the synthetic method of the iodo- 2- iodomethyl propylene of 3- described in claim 1, which comprises the following steps:

The chloro- 2- chloromethyl propylene of 3- is dissolved in acetone soln, suitable sodium iodide is added, reacted reflux then will be anti- It should be cooled to room temperature, residue obtains white solid, as product through extraction, washing, drying and concentration.