CN103232403B - A kind of preparation method of nitrogen heterocyclic - Google Patents
A kind of preparation method of nitrogen heterocyclic Download PDFInfo
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- CN103232403B CN103232403B CN201310168780.6A CN201310168780A CN103232403B CN 103232403 B CN103232403 B CN 103232403B CN 201310168780 A CN201310168780 A CN 201310168780A CN 103232403 B CN103232403 B CN 103232403B
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Abstract
The invention discloses a kind of preparation method of nitrogen heterocyclic.It comprises the steps: (1) diethylenetriamine or triethylene tetramine and methylsulfonyl chloride react and generate Toluidrin; (2) Toluidrin with there is the compound of structure as Suo Shi chemical formula (a) in two phase reaction, and under 90 DEG C to reflux conditions, obtain Toluidrin nitrogen heterocyclic through benzyl triethyl ammonium amine compound and-5 composite catalyzing cyclizations of 15-hat; (3) Toluidrin nitrogen heterocyclic is carried out piptonychia alkylsulfonyl, then remake the process that methylates;
Description
Technical field
The present invention relates to a kind of preparation method of nitrogen heterocyclic, belong to organic chemistry filed.
Background technology
Nitrogen heterocyclic has ring texture, and outside atom carbon atom on ring, the compound also containing nitrogen-atoms.Nitrogen heterocyclic is important organic compound, is widely used in medicine, agricultural chemicals, the fields such as material.Zhejiang Kaipu Chemical Co., Ltd. is recently by Isosorbide-5-Nitrae, and 7-trimethylammonium-Isosorbide-5-Nitrae, 7-7-triazacyclononane and Isosorbide-5-Nitrae, 7,10-tetramethyl--Isosorbide-5-Nitrae, 7,10-tetraazacyclododecanand is successfully applied to organic synthesis as a metal ion species intercalating agent.
Existing Isosorbide-5-Nitrae, 7-trimethylammonium-Isosorbide-5-Nitrae; 7-7-triazacyclononane and Isosorbide-5-Nitrae, 7,10-tetramethyl--1; the synthesis of 4,7,10-tetraazacyclododecanand needs first to react with amine and Tosyl chloride to generate para toluene sulfonamide usually, then through cyclization, take off alkylsulfonyl, methylating prepares.Tosyl chloride price is large compared with high, molecular weight, and it does not participate in nitrogen heterocyclic framework construction in this preparation technology, thus causes this preparation technology's Atom economy poor, and cost is higher.Therefore find a kind of alternative materials of Tosyl chloride to preparing Isosorbide-5-Nitrae, 7-trimethylammonium-Isosorbide-5-Nitrae, 7-7-triazacyclononane and Isosorbide-5-Nitrae, 7,10-tetramethyl--Isosorbide-5-Nitrae, 7,10-tetraazacyclododecanand is significant.
Nineteen eighty-three Louisiana State University professor's Newkome triethylene tetramine and methylsulfonyl chloride react and generate Toluidrin, react with sodium ethylate again and generate Toluidrin sodium salt, with the sodium salt and 6 generated, 6 '-two-(chloromethyl)-2,2 '-dipyridyl carries out ring-closure reaction and generates dipyridyl nitrogen heterocyclic.Though this method avoids the use of Tosyl chloride, but after needing first to prepare Toluidrin sodium salt, then carry out ring-closure reaction, operate more complicated.Substitute Tosyl chloride with methylsulfonyl chloride and prepare Isosorbide-5-Nitrae, 7-trimethylammonium-Isosorbide-5-Nitrae, 7-7-triazacyclononane and Isosorbide-5-Nitrae, 7,10-tetramethyl--Isosorbide-5-Nitrae, 7,10-tetraazacyclododecanand does not also have successful examples to report.Substitute Tosyl chloride with methylsulfonyl chloride, do not need again first to synthesize Toluidrin sodium salt, carry out ring-closure reaction again and prepare nitrogen heterocyclic and do not have report.Therefore develop one methylsulfonyl chloride and substitute Tosyl chloride, do not need first to synthesize Toluidrin sodium salt, can directly carry out ring-closure reaction and prepare 1,4,7-trimethylammonium-Isosorbide-5-Nitrae, 7-7-triazacyclononane and 1,4,7,10-tetramethyl--Isosorbide-5-Nitrae, the technique of 7,10-tetraazacyclododecanand has great significance.
Summary of the invention
The object of this invention is to provide a kind of preparation method of new nitrogen heterocyclic.
For achieving the above object, the technical solution used in the present invention is: the preparation method of nitrogen heterocyclic of the present invention comprises the steps:
A preparation method for nitrogen heterocyclic, is characterized in that, comprises the steps:
(1) diethylenetriamine or triethylene tetramine and methylsulfonyl chloride react and generate Toluidrin;
(2) Toluidrin with there is the compound of structure as Suo Shi chemical formula (a) in two phase reaction, and under 90 DEG C to reflux conditions, obtain Toluidrin nitrogen heterocyclic through benzyl triethyl ammonium amine compound and-5 composite catalyzing cyclizations of 15-hat,
Wherein, X represents bromine, iodine or sulphonate;
(3) Toluidrin nitrogen heterocyclic is carried out piptonychia alkylsulfonyl, then remake the process that methylates.
Further, the compound of the present invention's structure as Suo Shi chemical formula (a) is glycol dibromide, 1,2-ethylidene periodide, 1,2-di-alcohol two p-toluenesulfonic esters, 1,2-di-alcohol bis-mesylate, 1,2-di-alcohol DAADBSA ester or 1,2-di-alcohol two triflate.
Further, " two-phase " in two phase reaction of the present invention is organic phase and aqueous phase.
Further, the solvent of organic phase of the present invention is toluene or dimethylbenzene.
Further, benzyl triethyl ammonium amine compound of the present invention is benzyltriethylammoinium chloride, benzyl triethyl ammonium bromide, benzyl triethyl ammonium ammonium iodide or benzyltriethylammonium hydroxide.
Further, in step of the present invention (3), Toluidrin nitrogen heterocyclic is carried out piptonychia alkylsulfonyl and be in concentrated sulfuric acid, carry out under 180 DEG C of conditions.
Compared with prior art, the invention has the beneficial effects as follows: the present invention substitutes Tosyl chloride with methylsulfonyl chloride, can effectively reduce costs, generated sulphonamide can be made again to have certain reactive behavior.And be preced with-5 compound actions by benzyl triethyl ammonium amine compound and 15-and strengthen amide group reactive behavior further, make Toluidrin can with the compound with structure as Suo Shi chemical formula (a) direct one step to form the loop.Thus carry out ring and reaction again after not needing first to prepare Toluidrin sodium salt, decrease reactions steps, saved production cost, improve production efficiency.The present invention's methylsulfonyl chloride substitutes Tosyl chloride, does not need first to prepare Toluidrin sodium salt, can directly carry out ring-closure reaction and prepare Isosorbide-5-Nitrae, 7-trimethylammonium-1,4,7-7-triazacyclononane and Isosorbide-5-Nitrae, 7,10-tetramethyl--1,4,7,10-tetraazacyclododecanand, and productive rate is not less than prior art.
Embodiment
Embodiment 1:1,4,7,10-tetramethyl--Isosorbide-5-Nitrae, the preparation of 7,10-tetraazacyclododecanand
Add 5000g pyridine as alkali and solvent at reaction flask, and add 260g triethylene tetramine, be cooled to 0-5 degree, stir, slowly drip 600g methylsulfonyl chloride, be warmed up to room temperature, be evaporated to dry after 15 hours.After adding 2000g deionized water, regulate PH to 4-5 with concentrated hydrochloric acid, filter, filter cake 1000g water washing post-drying obtains product four methylsulfonyl triethylene tetramine 660g.
218g tetra-methylsulfonyl triethylene tetramine, 15g benzyltriethylammoinium chloride, 40g15-hat-5,42g sodium hydroxide, 1000g water and 1000g toluene is added at reaction flask, slowly be warmed up to 90 degree, insulation reaction half an hour, slowly add 103g1 under stirring, 2-di-alcohol bis-mesylate; After adding, be incubated 90 DEG C of reactions after 10 hours, drop to room temperature, then stir 6 hours; Filter, solid product 500g water washing post-drying obtains product Isosorbide-5-Nitrae, 7,10-, tetra-methylsulfonyls-Isosorbide-5-Nitrae, 7,10-tetraazacyclododecanand 206g.
In reaction flask, add the 400g vitriol oil and 160g1,4,7,10-, tetra-methylsulfonyls-Isosorbide-5-Nitrae, 7,10-tetraazacyclododecanand, be warmed up to 180 DEG C, insulation reaction obtains vitriol oil mixed solution in 10 hours.800mL30% aqueous sodium hydroxide solution, 600g37% formaldehyde and 600g88% formic acid is added after vitriol oil mixed solution is down to room temperature.Be warmed up to 90 DEG C, insulation reaction cools to 0 DEG C in 14 hours again, and stir and add 1000g50% sodium hydroxide solution, add 300g ethyl acetate, stir 15 minutes, stratification, water layer is with adding 300g extraction into ethyl acetate.Merge organic layer, filter after adding 100g anhydrous sodium sulfate drying.Filtrate is concentrated into dry.Rectifying obtains Isosorbide-5-Nitrae again, 7,10-tetramethyl--Isosorbide-5-Nitrae, 7,10-tetraazacyclododecanand 59g.
1H-NMR(400MHz,CDCl
3):2.50(S,16H);2.22(S,12H).
13C-NMR(100MHz,CDCl
3):43.2,53.9.
Embodiment 2:1,4,7,10-tetramethyl--Isosorbide-5-Nitrae, the preparation of 7,10-tetraazacyclododecanand
Add 5000g pyridine as alkali and solvent at reaction flask, and add 260g triethylene tetramine, be cooled to 0-5 degree, stir, slowly drip 600g methylsulfonyl chloride, be warmed up to room temperature, be evaporated to dry after 15 hours.After adding 2000g deionized water, regulate PH to 4-5 with concentrated hydrochloric acid, filter, filter cake 1000g water washing post-drying obtains product four methylsulfonyl triethylene tetramine 660g.
218g tetra-methylsulfonyl triethylene tetramine, 19g benzyl triethyl ammonium ammonium iodide, 40g15-hat-5,42g sodium hydroxide, 1000g water and 1000g toluene is added at reaction flask.Slowly be warming up to backflow, insulation reaction half an hour.Slowly 120g1 is added, 2-monobromethane under stirring.After adding, be incubated 90 DEG C of reactions after 10 hours, drop to room temperature, then stir 6 hours.Filter, solid product 500g water washing post-drying obtains product Isosorbide-5-Nitrae, 7,10-, tetra-methylsulfonyls-Isosorbide-5-Nitrae, 7,10-tetraazacyclododecanand 199g.
In reaction flask, add the 400g vitriol oil and 160g1,4,7,10-, tetra-methylsulfonyls-Isosorbide-5-Nitrae, 7,10-tetraazacyclododecanand, be warmed up to 180 DEG C, insulation reaction obtains vitriol oil mixed solution in 10 hours.Vitriol oil mixed solution adds 800mL30% aqueous sodium hydroxide solution, 600g37% formaldehyde and 600g88% formic acid after being down to room temperature.Be warmed up to 90 DEG C, insulation reaction cools to 0 DEG C in 14 hours again, and stir and add 1000g50% sodium hydroxide solution, add 300g ethyl acetate, stir 15 minutes, stratification, water layer is with adding 300g extraction into ethyl acetate.Merge organic layer, filter after adding 100g anhydrous sodium sulfate drying.Filtrate is concentrated into dry.Rectifying obtains Isosorbide-5-Nitrae again, 7,10-tetramethyl--Isosorbide-5-Nitrae, 7,10-tetraazacyclododecanand 52g.
Embodiment 3:1,4,7-trimethylammonium-Isosorbide-5-Nitrae, the preparation of 7-7-triazacyclononane
Add 5000g pyridine and 180g diethylenetriamine at reactor, be cooled to 0-5 DEG C, stir, slowly drip 600g methylsulfonyl chloride, be warmed up to room temperature, be evaporated to dry after 15 hours.After adding 2000g deionized water, regulate PH to 4-5 with concentrated hydrochloric acid, filter, filter cake 1000g water washing post-drying obtains product N, two (2-methanesulfonamidoethyl) the Toluidrin 555g of N-.
160gN is added, two (2-methanesulfonamidoethyl) Toluidrin of N-, 14g benzyltriethylammonium hydroxide, 40g15-hat-5,42g sodium hydroxide, 1000g water and 1000g dimethylbenzene in reaction flask.Slowly be warmed up to 90 DEG C, insulation reaction half an hour.Slowly 175g1 is added, 2-di-alcohol two p-toluenesulfonic esters under stirring.After adding, be incubated 90 DEG C of reactions after 10 hours, drop to room temperature, then stir 6 hours.Filter, solid product 500g water washing post-drying obtains product Isosorbide-5-Nitrae, 7-trimesyl-Isosorbide-5-Nitrae, 7-7-triazacyclononane 153g.
In reaction flask, add the 400g vitriol oil and 120g1,4,7-trimesyl-Isosorbide-5-Nitrae, 7-7-triazacyclononane, is warmed up to 180 DEG C, and insulation reaction obtains vitriol oil mixed solution in 10 hours.Vitriol oil mixed solution adds 800mL30% aqueous sodium hydroxide solution, 450g37% formaldehyde and 450g88% formic acid after being down to room temperature.Be warmed up to 90 DEG C, insulation reaction cools to 0 DEG C in 14 hours again, and stir and add 1000g50% sodium hydroxide solution, add 300g ethyl acetate, stir 15 minutes, stratification, water layer is with adding 300g extraction into ethyl acetate.Merge organic layer, filter after adding 100g anhydrous sodium sulfate drying.Filtrate is concentrated into dry.Rectifying obtains Isosorbide-5-Nitrae again, 7-trimethylammonium-Isosorbide-5-Nitrae, 7-7-triazacyclononane 39g.
1HNMR(400MHz,CDCl
3):2.66(S,12H);2.36(S,9H).
13C-NMR(100MHz,CDCl
3):46.7,57.0.
Embodiment 4:1,4,7-trimethylammonium-Isosorbide-5-Nitrae, the preparation of 7-7-triazacyclononane
160gN is added, two (2-methanesulfonamidoethyl) Toluidrin of N-, 16g benzyl triethyl ammonium bromide, 40g15-hat-5,42g sodium hydroxide, 1000g water and 1000g dimethylbenzene at reaction flask.Slowly be warming up to backflow, insulation reaction half an hour.Slowly 134g1 is added, 2-ethylidene periodide under stirring.After adding, be incubated 90 DEG C of reactions after 10 hours, drop to room temperature, then stir 6 hours.Filter, solid product 500g water washing post-drying obtains product Isosorbide-5-Nitrae, 7-trimesyl-Isosorbide-5-Nitrae, 7-7-triazacyclononane 146g.
In reaction flask, add the 400g vitriol oil and 120g1,4,7-trimesyl-Isosorbide-5-Nitrae, 7-7-triazacyclononane, is warmed up to 180 DEG C, and insulation reaction obtains vitriol oil mixed solution in 10 hours.Vitriol oil mixed solution adds 800mL30% aqueous sodium hydroxide solution, 450g37% formaldehyde and 450g88% formic acid after being down to room temperature.Be warmed up to 90 DEG C, insulation reaction cools to 0 DEG C in 14 hours again, and stir and add 1000g50% sodium hydroxide solution, add 300g ethyl acetate, stir 15 minutes, stratification, water layer is with adding 300g extraction into ethyl acetate.Merge organic layer, filter after adding 100g anhydrous sodium sulfate drying.Filtrate is concentrated into dry.Rectifying obtains Isosorbide-5-Nitrae again, 7-trimethylammonium-Isosorbide-5-Nitrae, 7-7-triazacyclononane 34g.
Embodiment 5:1,4,7-trimethylammonium-Isosorbide-5-Nitrae, the preparation of 7-7-triazacyclononane
160gN is added, two (2-methanesulfonamidoethyl) Toluidrin of N-, 16g benzyl triethyl ammonium bromide, 40g15-hat-5,42g sodium hydroxide, 1000g water and 1000g toluene at reaction flask.Slowly be warmed up to 90 DEG C, insulation reaction half an hour.Slowly 154g1 is added, 2-di-alcohol two triflate under stirring.After adding, be incubated 90 DEG C of reactions after 10 hours, drop to room temperature, then stir 6 hours.Filter, solid product 500g water washing post-drying obtains product Isosorbide-5-Nitrae, 7-trimesyl-Isosorbide-5-Nitrae, 7-7-triazacyclononane 159g.
In reaction flask, add the 400g vitriol oil and 120g1,4,7-trimesyl-Isosorbide-5-Nitrae, 7-7-triazacyclononane, is warmed up to 180 DEG C, and insulation reaction obtains vitriol oil mixed solution in 10 hours.Vitriol oil mixed solution adds 800mL30% aqueous sodium hydroxide solution, 450g37% formaldehyde and 450g88% formic acid after being down to room temperature.Be warmed up to 90 DEG C, insulation reaction cools to 0 degree in 14 hours again, and stir and add 1000g50% sodium hydroxide solution, add 300g ethyl acetate, stir 15 minutes, stratification, water layer is with adding 300g extraction into ethyl acetate.Merge organic layer, filter after adding 100g anhydrous sodium sulfate drying.Filtrate is concentrated into dry.Rectifying obtains Isosorbide-5-Nitrae again, 7-trimethylammonium-Isosorbide-5-Nitrae, 7-7-triazacyclononane 41g.
Embodiment 6:1,4,7-trimethylammonium-Isosorbide-5-Nitrae, the preparation of 7-7-triazacyclononane
160gN is added, two (2-methanesulfonamidoethyl) Toluidrin of N-, 16g benzyl triethyl ammonium bromide, 40g15-hat-5,42g sodium hydroxide, 1000g water and 1000g toluene at reaction flask.Slowly be warmed up to 90 DEG C, insulation reaction half an hour.Slowly 103g1 is added, 2-di-alcohol bis-mesylate under stirring.After adding, be incubated 90 DEG C of reactions after 10 hours, drop to room temperature, then stir 6 hours.Filter, solid product 500g water washing post-drying obtains product Isosorbide-5-Nitrae, 7-trimesyl-Isosorbide-5-Nitrae, 7-7-triazacyclononane 142g.
In reaction flask, add the 400g vitriol oil and 120g1,4,7-trimesyl-Isosorbide-5-Nitrae, 7-7-triazacyclononane, is warmed up to 180 DEG C, and insulation reaction obtains vitriol oil mixed solution in 10 hours.Vitriol oil mixed solution adds 800mL30% aqueous sodium hydroxide solution, 450g37% formaldehyde and 450g88% formic acid after being down to room temperature.Be warmed up to 90 DEG C, insulation reaction cools to 0 DEG C in 14 hours again, and stir and add 1000g50% sodium hydroxide solution, add 300g ethyl acetate, stir 15 minutes, stratification, water layer is with adding 300g extraction into ethyl acetate.Merge organic layer, filter after adding 100g anhydrous sodium sulfate drying.Filtrate is concentrated into dry.Rectifying obtains Isosorbide-5-Nitrae again, 7-trimethylammonium-Isosorbide-5-Nitrae, 7-7-triazacyclononane 39g.
Claims (5)
1. a preparation method for nitrogen heterocyclic, is characterized in that, comprises the steps:
(1) diethylenetriamine or triethylene tetramine and methylsulfonyl chloride react and generate Toluidrin;
(2) Toluidrin with there is the compound of structure as Suo Shi chemical formula (a) in two phase reaction, and under 90 DEG C to reflux conditions, through benzyl triethyl ammonium amine compound and 15 ?Guan ?5 composite catalyzing cyclizations obtain Toluidrin nitrogen heterocyclic, described benzyl triethyl ammonium amine compound is benzyltriethylammoinium chloride, benzyl triethyl ammonium bromide, benzyl triethyl ammonium ammonium iodide or benzyltriethylammonium hydroxide, " two-phase " in described two phase reaction is organic phase and aqueous phase
Wherein, X represents bromine, iodine or sulphonate;
(3) Toluidrin nitrogen heterocyclic is carried out piptonychia alkylsulfonyl, then remake the process that methylates.
2. the preparation method of nitrogen heterocyclic according to claim 1, it is characterized in that: as Suo Shi chemical formula (a), the compound of structure is 1,2-ethylene dibromide, 1,2-ethylidene periodide, 1,2-di-alcohol two p-toluenesulfonic esters, 1,2-di-alcohol bis-mesylate, 1,2-di-alcohol DAADBSA ester or 1,2-di-alcohol two triflate.
3. nitrogen heterocyclic preparation method according to claim 1 and 2, is characterized in that: the solvent of described organic phase is toluene or dimethylbenzene.
4. nitrogen heterocyclic preparation method according to claim 1 and 2, is characterized in that: in step (3), Toluidrin nitrogen heterocyclic is carried out piptonychia alkylsulfonyl and is in concentrated sulfuric acid, carries out under 180 DEG C of conditions.
5. nitrogen heterocyclic preparation method according to claim 3, is characterized in that: in step (3), Toluidrin nitrogen heterocyclic is carried out piptonychia alkylsulfonyl and is in concentrated sulfuric acid, carries out under 180 DEG C of conditions.
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| CN110922365A (en) * | 2019-12-13 | 2020-03-27 | 山东铂源药业有限公司 | Preparation method of high-purity cycleanine |
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