CN101735067B - Synthesis method of 1,4-butanediamine - Google Patents
Synthesis method of 1,4-butanediamine Download PDFInfo
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Abstract
The invention provides a synthesis method of 1,4-butanediamine, which comprises the steps of: (a) dissolving the 1,4-dibromobutyl amine represented by formula (1) in a solvent A, adding the phthalimide potassium represented by formula (2), reacting while stirring at a reflux temperature, filtering reaction liquid, washing by using distilled water to obtain the 1,4-diphthalimide butane represented by formula (3); (b) adding the 1,4-diphthalimide butane obtained in the step (1) and 40% methylamine water solution to a solvent B, heating until solids are dissolved completely, stirring and reacting for 0.5-4 hours at the reflux temperature to obtain reaction products; and (c) filtering the reaction products, post-treating filtrate, distilling the filtrate under normal pressure, and collecting the fractions between 158 DEG C and 160 DEG C to obtain the 1,4-butanediamine. The invention has simple and convenient technological conditions, cheap raw materials, mild reaction conditions, easy control and convenient industrial production.
Description
(1) technical field
The present invention relates to a kind of synthetic method of Putriscine.
(2) background technology
Putriscine has another name called 1,4-Diaminobutane, tetramethylene-diamine, saprine, English name Isosorbide-5-Nitrae-Diaminobutane.
Putriscine is a kind of important chemical intermediate, for example, has the drug rehabilitation class medicine agmatine sulfate of DEVELOPMENT PROSPECT, (Chinese publication CN1834085A and the CN101121677) that synthesizes as main raw material with Putriscine exactly.Again for example, some main engineering plastics (polymeric amide-4,6, homopolymer or multipolymer form) also synthesize take Putriscine as important raw and processed materials.Therefore, Putriscine has wide market outlook.
About synthesizing of Putriscine, many countries all are studied and develop its synthetic method, the chemical synthesis that integrates mainly contains following a few class: (1) is with 1, the 4-diisocyanate butane is raw material, hydrolysis (Naegeli, C. under acidic conditions; Lendorff, P.HelveticaChimica Acta (1932), 15,49-59.), make Putriscine; (2) take Isosorbide-5-Nitrae-two phthalic imidine butane as raw material, under high-temperature and high-pressure conditions through basic hydrolysis (Chambret, Fernand; Joly, Daniel.Bulletin de la Societe Chimique de France (1947), 1023-6) or acid hydrolysis (Langenbeck, Wolfgang; Waltersdorf, Werner; Blachnitzky, Hermann. (I.G.Farbenindustrie AG). (1940), DE69903319401024.) produce Putriscine; (3) make Putriscine (Khoukhi, Mostafa with corresponding triazo-compound through azido reaction; Vaultier, Michel; Benalil, Aziza; Carboni, Bertrand.Synthesis (1996), (4), 483-7).; (4) Isosorbide-5-Nitrae-succinonitrile method, this method is catalyzer by Co or Ni, take water as solvent, makes Putriscine (Jouichi, Akiko; Ito, Kazuhisa.Jpn.Kokai Tokkyo Koho (2001), 5pp.).Yet still there are some problems in process of production in appeal technique, and for example, the hydrolysis temperature high pressure is large; Diazonium salt adds heat release a large amount of nitrogen, sets off an explosion easily, and suitability for industrialized production is absolutely unsafe, and technological operation is had relatively high expectations; Expensive raw material price, reaction easily produce " three wastes ", easily to environment, are unfavorable for labour protection, more do not meet industry policy of energy-saving and emission-reduction etc.
(3) summary of the invention
The object of the invention be to provide a kind of easy and simple to handle, production cost is low, reaction yield is higher, substantially without the method for the synthetic Putriscine of " three wastes " discharging.For realizing the object of the invention, technical scheme of the present invention is as follows:
Shown in a kind of formula (4) 1, the synthetic method of 4-butanediamine (4), described method is that (a) is with 1 shown in the formula (1), 4-dibromo butylamine is dissolved in the solvent orange 2 A, potassium phthalimide reacting by heating shown in the adding formula (2), constantly stir in the reaction process, with TLC detection reaction terminal point, react complete, reaction solution filters, filter cake washs 1～3 time with aquae destillata, obtain the Isosorbide-5-Nitrae-two phthalic imidine butane shown in the formula (3), described 1, the molar ratio that feeds intake of 4-dibromo butylamine and potassium phthalimide be 1: 2.0～4.0 (b) with step (a) obtain 1,4-two phthalic imidine butane add solvent B and 40% aqueous methylamine solution, and it is entirely molten to be heated to solid, the return stirring reaction, usually in 30～100 ℃ of temperature ranges, reacted 0.5-4 hour, and when reaction solution is the yellow transparent shape, added a certain amount of concentrated hydrochloric acid, continue backflow and finish reaction after 3-9 hour, get reaction product; Here add concentrated hydrochloric acid and can make the product Putriscine change into hydrochloride, the accelerated reaction forward carries out, and improves productive rate.Described 1, methylamine in 4-two phthalic imidine butane (3) and 40% aqueous methylamine solution molar ratio that feeds intake is 1: 4.0～8.0, hydrogenchloride in the adding concentrated hydrochloric acid and the molar ratio that feeds intake of Isosorbide-5-Nitrae-two phthalic imidine butane (3) are 1: 2.0～4.0; (c) reaction product is filtered, get filtrate being concentrated into and begin to be thick rear with transferring pH to 7 among the solid NaOH, extract with extraction agent again, can extract repeatedly, merging the extraction agent layer after the extraction spends the night with desiccant dryness, multiple siccative can use, such as anhydrous sodium sulphate, anhydrous magnesium sulfate, Vanadium Pentoxide in FLAKES etc., the present invention recommends take anhydrous sodium sulphate as siccative, boils off extraction agent after removing siccative, recommend adoption Rotary Evaporators of the present invention boils off extraction solvent, the velocity ratio of underpressure distillation is very fast, and waiting not steam solvent can stop, and remaining raffinate carries out air distillation again, cut namely gets described Putriscine between collecting 158～160 ℃; Described Putriscine is the liquid that colorless oil has decomposed odour.
Reaction equation of the present invention is as follows:
The synthetic method of Putriscine of the present invention (4), the described solvent orange 2 A of described step (a) are one of following or their arbitrary combination: water, methyl alcohol, ethanol, acetone.Preferred solvent A is acetone.The consumption of described solvent orange 2 A is 20～30 times of Isosorbide-5-Nitrae-dibromo butylamine volume, and the consumption of preferred solvent A is 15～20 times of Isosorbide-5-Nitrae-dibromo butylamine volume.
The solvent B of step of the present invention (b) is one of following or their arbitrary combination: water, methyl alcohol, ethanol.Preferred described solvent B is ethanol.The consumption of described solvent B is 10～30 times of 40% aqueous methylamine solution volume., the consumption of preferred solvent B is 15～20 times of 40% aqueous methylamine solution volume.
The described extraction agent of step of the present invention (c) be following under: methylene dichloride, trichloromethane, tetracol phenixin, ether, propyl ether, isopropyl ether, butyl ether.The consumption of described extraction agent be about reactant concentrated after 3 times of volume, use the extraction agent extraction 2～3 times with the same dose first time at every turn.The preferred extraction agent of the present invention is methylene dichloride.
The molar ratio of the described Isosorbide-5-Nitrae of step of the present invention (a)-dibromo butylamine and potassium phthalimide is 1: 2.0～1: 4.0, is preferably 1: 2.0～1: 3.0; Described temperature of reaction is generally 30～100 ℃, and temperature more commonly used is at 40～80 ℃; Reaction times is generally 1～24 hour, is preferably 12～15 hours.
The molar ratio of methylamine is 1: 4.0～1: 8.0 in the described potassium phthalimide of step of the present invention (b) and 40% aqueous methylamine solution, is preferably 1: 4.0～1: 6.0; Described temperature of reaction is 30～100 ℃, and the most common is 50～80 ℃; Reaction is generally 4～10 hours total time, is preferably 5～8 hours.
Concrete, the preferred synthetic method of the present invention is that (a) is with 1 shown in the formula (1), 4-dibromo butylamine is dissolved in the acetone, potassium phthalimide back flow reaction shown in the adding formula (2), TLC follows the tracks of the detection reaction terminal point, react complete, reaction solution filters, obtain 1 shown in the formula (3), 4-two phthalic imidine butane, the molar ratio that feeds intake of described Isosorbide-5-Nitrae-dibromo butylamine and potassium phthalimide is 1: 2.0～3.0, the consumption of acetone is 15～20 times of Isosorbide-5-Nitrae-Ding bromine butylamine volume; (b) step (a) is obtained 1,4-two phthalic imidine butane add ethanol and 40% aqueous methylamine solution, it is entirely molten to be heated to solid, stir, after back flow reaction 0.5-4 hour, solution is yellow transparent, adds a certain amount of concentrated hydrochloric acid, continue backflow and finish reaction after 3-9 hour, get reaction product; Described 1, methylamine in 4-two phthalic imidine butane (3) and 40% aqueous methylamine solution molar ratio that feeds intake is 1: 4.0～6.0, add the hydrogenchloride and 1 in the concentrated hydrochloric acid, 4-two phthalic imidine butane (3) molar ratio that feeds intake is 1: 2.0～4.0, and solvent B consumption is 10～30 times of 40% aqueous methylamine solution volume; (c) reaction product is filtered, get and use accent pH to 7 among the solid NaOH after filtrate is concentrated into the beginning thickness, the again extraction take methylene dichloride as extraction agent, the consumption of described extraction agent are 3 times of the concentrated rear volume of reactant, same dose extraction 3 times, get dichloromethane layer and cross liquid with desiccant dryness, boil off extraction agent after removing siccative, carry out again air distillation, collect 158～160 ℃ between cut namely get described 1,4-butanediamine, described siccative are anhydrous sodium sulphate.Concentrated hydrochloric acid of the present invention is that mass concentration is 36.5% aqueous hydrochloric acid.
Isosorbide-5-Nitrae-two phthalic imidine the butane that step (a) obtains, only pipe is not highly purified, but purity can reach more than 96% usually.The amount of substance of step (b) described Isosorbide-5-Nitrae-two phthalic imidine butane is exactly that to be used as the sterling meter be 1: 4.0～8.0 with methylamine molar ratio in 40% aqueous methylamine solution,
The present invention compares with the preparation method of existing Putriscine, has the following advantages: (1) processing condition are easy, reasonable; (2) prices of raw and semifnished materials are cheap; (3) adopt 40% aqueous methylamine solution as aminolysis reagent, suitability for industrialized production is convenient in gentle, the easily control of reaction conditions.Therefore, the present invention has safety simple to operate, and reaction yield is higher, and the advantage that production cost is low has larger implementary value and economic results in society.
(4) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Used 40% aqueous methylamine solution of present embodiment is the commercial goods.
Embodiment 1
Take by weighing Isosorbide-5-Nitrae-dibromo butylamine 10.90g (0.05mol), add in the 500ml there-necked flask, add 200mL acetone, 70 ℃ of stirrings add 22.20g (0.12mol) potassium phthalimide, the TLC detection reaction is to terminal after 14 hours for back flow reaction, with the reaction solution suction filtration, obtain the insolubles of white, with dry behind the 20ml distilled water wash 2 times, obtain 1,4-two phthalic imidine butane 15.66g, yield 90%, mp.227～229 ℃.The 15.66g (0.045mol) 1 that previous step is made, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, rear adding 18.90g 40% aqueous methylamine solution (the mole number 0.24mol that contains methylamine), it is entirely molten to be heated to solid, continue stirring until and add concentrated hydrochloric acid 8mL after reaction solution is yellow transparent, end reaction after continuing to reflux 4 hours.Reaction product is filtered, and filtrate is concentrated into and slightly is thick and is neutralized to pH=7 with solid NaOH afterwards, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying hold over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collect 158～160 ℃ between cut, get the liquid 2.61g that colorless oil has decomposed odour, two-step reaction total recovery 59.4%,
1HNMR (400MHz, D
2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 2
Take by weighing Isosorbide-5-Nitrae-dibromo butylamine 10.90g (0.05mol), add in the 500ml there-necked flask, add 200mL ethanol, 70 ℃ of stirrings add 22.20g (0.12mol) potassium phthalimide, the TLC detection reaction is to terminal after 15 hours for back flow reaction, with the reaction solution suction filtration, obtain the insolubles of white, with dry behind the 20ml distilled water wash 2 times, obtain 1,4-two phthalic imidine butane 11.23g, yield 72.3%, mp.227～229 ℃.The 12.58g (0.036mol) 1 that previous step is made, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, 40% aqueous methylamine solution (the molar weight 0.21mol that contains methylamine) of rear adding 16.81g, it is entirely molten to be heated to solid, continue stirring until and add concentrated hydrochloric acid 8ml after reaction solution is yellow transparent, end reaction after continuing to reflux 4 hours.Reaction product is filtered, and filtrate is concentrated into and slightly is thick and is neutralized to pH=7 with solid NaOH afterwards, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying hold over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collect 158～160 ℃ between cut, get the liquid 1.91g that colorless oil has decomposed odour, two-step reaction total recovery 43.4%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 3
Take by weighing Isosorbide-5-Nitrae-dibromo butylamine 10.90g (0.05mol), add in the 500ml there-necked flask, add 200mL methyl alcohol, 70 ℃ of stirrings add 22.20g (0.12mol) potassium phthalimide, the TLC detection reaction is to terminal after 12 hours for back flow reaction, with the reaction solution suction filtration, obtain the insolubles of white, with dry behind the 20ml distilled water wash 2 times, obtain 1,4-two phthalic imidine butane 11.23g, yield 64.5%, mp.227～229 ℃.The 11.23g (0.032mol) 1 that previous step is made, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, rear adding 14.99g 40% aqueous methylamine solution (the molar weight 0.19mol that contains methylamine), it is entirely molten to be heated to solid, continue stirring until and add concentrated hydrochloric acid 8ml after reaction solution is yellow transparent, end reaction after continuing to reflux 4 hours.Reaction product is filtered, and filtrate is concentrated into and slightly is thick and is neutralized to pH=7 with solid NaOH afterwards, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying hold over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collect 158～160 ℃ between cut, get the liquid 1.69g that colorless oil has decomposed odour, two-step reaction total recovery 38.7%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 4
Take by weighing Isosorbide-5-Nitrae-dibromo butylamine 10.90g (0.05mol), add in the 500ml there-necked flask, add 200mL acetone, 70 ℃ of stirrings add 22.20g (0.12mol) potassium phthalimide, the TLC detection reaction is to terminal after 14 hours for back flow reaction, with the reaction solution suction filtration, obtain the insolubles of white, with dry behind the 20ml distilled water wash 2 times, obtain 1,4-two phthalic imidine butane 14.15g, yield 81.3%, mp.227～229 ℃.The 14.15g (0.041mol) 1 that previous step is made, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, rear adding 18.9g (the molar weight 0.24mol that contains methylamine) 40% aqueous methylamine solution, it is entirely molten to be heated to solid, continue stirring until and add concentrated hydrochloric acid 8ml after reaction solution is yellow transparent, end reaction after continuing to reflux 4 hours.Reaction product is filtered, and filtrate is concentrated into and slightly is thick and is neutralized to pH=7 with solid NaOH afterwards, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying hold over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collect 158～160 ℃ between cut, get the liquid 2.33g that colorless oil has decomposed odour, two-step reaction total recovery 52.8%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 5
Take by weighing Isosorbide-5-Nitrae-dibromo butylamine 10.90g (0.05mol), add in the 500ml there-necked flask, add 300mL acetone, 70 ℃ of stirrings add 22.20g (0.12mol) potassium phthalimide, the TLC detection reaction is to terminal after 14 hours for back flow reaction, with the reaction solution suction filtration, obtain the insolubles of white, with dry behind the 20ml distilled water wash 2 times, obtain 1,4-two phthalic imidine butane 14.79g, yield 85.0%, mp.227～229 ℃.The 14.79g (0.043mol) 1 that previous step is made, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, rear adding 19.76g (the molar weight 0.26mol that contains methylamine) 40% aqueous methylamine solution, it is entirely molten to be heated to solid, continue stirring until and add concentrated hydrochloric acid 8ml after reaction solution is yellow transparent, end reaction after continuing to reflux 4 hours.Reaction product is filtered, and filtrate is concentrated into and slightly is thick and is neutralized to pH=7 with solid NaOH afterwards, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying hold over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collect 158～160 ℃ between cut, get the liquid 2.40g that colorless oil has decomposed odour, two-step reaction total recovery 54.7%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 6
Take by weighing Isosorbide-5-Nitrae-dibromo butylamine 10.90g (0.05mol), add in the 500ml there-necked flask, add 250mL acetone, 70 ℃ of stirrings add 22.20g (0.12mol) potassium phthalimide, the TLC detection reaction is to terminal after 14 hours for back flow reaction, with the reaction solution suction filtration, obtain the insolubles of white, with dry behind the 20ml distilled water wash 2 times, obtain 1,4-two phthalic imidine butane 14.79g, yield 92.0%, mp.227～229 ℃.The 14.79g (0.046mol) 1 that previous step is made, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, rear adding 21.39g (the molar weight 0.28mol that contains methylamine) 40% aqueous methylamine solution, it is entirely molten to be heated to solid, continue stirring until and add concentrated hydrochloric acid 8ml after reaction solution is yellow transparent, end reaction after continuing to reflux 4 hours.Reaction product is filtered, and filtrate is concentrated into and slightly is thick and is neutralized to pH=7 with solid NaOH afterwards, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying hold over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collect 158～160 ℃ between cut, get the liquid 2.57g that colorless oil has decomposed odour, two-step reaction total recovery 58.3%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 7
Take by weighing Isosorbide-5-Nitrae-dibromo butylamine 10.90g (0.05mol), add in the 500ml there-necked flask, add 250mL acetone, 70 ℃ of stirrings add 18.50g (0.10mol) potassium phthalimide, the TLC detection reaction is to terminal after 15 hours for back flow reaction, with the reaction solution suction filtration, obtain the insolubles of white, with dry behind the 20ml distilled water wash 2 times, obtain 1,4-two phthalic imidine butane 15.02g, yield 86.3%, mp.227～229 ℃.The 15.02g (0.043mol) 1 that previous step is made, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, rear adding 20.06g (the molar weight 0.26mol that contains methylamine) 40% aqueous methylamine solution, it is entirely molten to be heated to solid, continue stirring until and add concentrated hydrochloric acid 8ml after reaction solution is yellow transparent, end reaction after continuing to reflux 4 hours.Reaction product is filtered, and filtrate is concentrated into and slightly is thick and is neutralized to pH=7 with solid NaOH afterwards, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying hold over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collect 158～160 ℃ between cut, get the liquid 2.35g that colorless oil has decomposed odour, two-step reaction total recovery 53.5%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 8
Take by weighing Isosorbide-5-Nitrae-dibromo butylamine 10.90g (0.05mol), add in the 500ml there-necked flask, add 250mL acetone, 70 ℃ of stirrings add 24.05g (0.13mol) potassium phthalimide, the TLC detection reaction is to terminal after 13 hours for back flow reaction, with the reaction solution suction filtration, obtain the insolubles of white, with dry behind the 20ml distilled water wash 2 times, obtain 1,4-two phthalic imidine butane 15.50g, yield 89.1%, mp.227～229 ℃.The 15.50g (0.045mol) 1 that previous step is made, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, rear adding 21.39g (the molar weight 0.28mol that contains methylamine) 40% aqueous methylamine solution, it is entirely molten to be heated to solid, continue stirring until and add concentrated hydrochloric acid 8ml after reaction solution is yellow transparent, end reaction after continuing to reflux 4 hours.Reaction product is filtered, and filtrate is concentrated into and slightly is thick and is neutralized to pH=7 with solid NaOH afterwards, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying hold over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collect 158～160 ℃ between cut, get the liquid 2.63g that colorless oil has decomposed odour, two-step reaction total recovery 59.7%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 9
Take by weighing Isosorbide-5-Nitrae-dibromo butylamine 10.90g (0.05mol), add in the 500ml there-necked flask, add 250mL acetone, 70 ℃ of stirrings add 27.75g (0.15mol) potassium phthalimide, the TLC detection reaction is to terminal after 12 hours for back flow reaction, with the reaction solution suction filtration, obtain the insolubles of white, with dry behind the 20ml distilled water wash 2 times, obtain 1,4-two phthalic imidine butane 14.79g, yield 92.0%, mp.227～229 ℃.The 14.79g (0.046mol) 1 that previous step is made, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, rear adding 21.39g (the molar weight 0.28mol that contains methylamine) 40% aqueous methylamine solution, it is entirely molten to be heated to solid, continue stirring until and add concentrated hydrochloric acid 8ml after reaction solution is yellow transparent, end reaction after continuing to reflux 4 hours.Reaction product is filtered, and filtrate is concentrated into and slightly is thick and is neutralized to pH=7 with solid NaOH afterwards, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying hold over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collect 158～160 ℃ between cut, get the liquid 2.36g that colorless oil has decomposed odour, two-step reaction total recovery 53.6%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 10
Take by weighing Isosorbide-5-Nitrae-dibromo butylamine 10.90g (0.05mol), add in the 500ml there-necked flask, add 250mL acetone, 70 ℃ of stirrings add 24.05g (0.13mol) potassium phthalimide, the TLC detection reaction is to terminal after 13 hours for back flow reaction, with the reaction solution suction filtration, obtain the insolubles of white, with dry behind the 20ml distilled water wash 2 times, obtain 1,4-two phthalic imidine butane 15.71g, yield 90.3%, mp.227～229 ℃.The 15.71g (0.045mol) 1 that previous step is made, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, rear adding 14.00g (the molar weight 0.18mol that contains methylamine) 40% aqueous methylamine solution, it is entirely molten to be heated to solid, continue stirring until and add concentrated hydrochloric acid 8ml after reaction solution is yellow transparent, end reaction after continuing to reflux 4 hours.Reaction product is filtered, and filtrate is concentrated into and slightly is thick and is neutralized to pH=7 with solid NaOH afterwards, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying hold over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collect 158～160 ℃ between cut, get the liquid 1.66g that colorless oil has decomposed odour, two-step reaction total recovery 37.9%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 11
Take by weighing Isosorbide-5-Nitrae-dibromo butylamine 10.90g (0.05mol), add in the 500ml there-necked flask, add 250mL acetone, 70 ℃ of stirrings add 24.05g (0.13mol) potassium phthalimide, the TLC detection reaction is to terminal after 13 hours for back flow reaction, with the reaction solution suction filtration, obtain the insolubles of white, with dry behind the 20ml distilled water wash 2 times, obtain 1,4-two phthalic imidine butane 15.85g, yield 91.1%, mp.227～229 ℃.The 15.85g (0.046mol) 1 that previous step is made, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, rear adding 21.18g (the molar weight 0.27mol that contains methylamine) 40% aqueous methylamine solution, it is entirely molten to be heated to solid, continue stirring until and add concentrated hydrochloric acid 8ml after reaction solution is yellow transparent, end reaction after continuing to reflux 4 hours.Reaction product is filtered, and filtrate is concentrated into and slightly is thick and is neutralized to pH=7 with solid NaOH afterwards, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying hold over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collect 158～160 ℃ between cut, get the liquid 2.69g that colorless oil has decomposed odour, two-step reaction total recovery 61.0%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 12
Take by weighing Isosorbide-5-Nitrae-dibromo butylamine 10.90g (0.05mol), add in the 500ml there-necked flask, add 250mL acetone, 70 ℃ of stirrings add 24.05g (0.13mol) potassium phthalimide, the TLC detection reaction is to terminal after 13 hours for back flow reaction, with the reaction solution suction filtration, obtain the insolubles of white, with dry behind the 20ml distilled water wash 2 times, obtain 1,4-two phthalic imidine butane 16.18g, yield 93.0%, mp.227～229 ℃.The 16.18g (0.047mol) 1 that previous step is made, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, rear adding 28.83g (the molar weight 0.37mol that contains methylamine) 40% aqueous methylamine solution, it is entirely molten to be heated to solid, continue stirring until and add concentrated hydrochloric acid 8ml after reaction solution is yellow, end reaction after continuing to reflux 4 hours.Reaction product is filtered, and filtrate is concentrated into and slightly is thick and is neutralized to pH=7 with solid NaOH afterwards, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying hold over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collect 158～160 ℃ between cut, get the liquid 2.25g that colorless oil has decomposed odour, two-step reaction total recovery 51.1%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 13
Take by weighing Isosorbide-5-Nitrae-dibromo butylamine 10.90g (0.05mol), add in the 500ml there-necked flask, add 250mL acetone, 100 ℃ of stirrings add 24.05g (0.13mol) potassium phthalimide, the TLC detection reaction is to terminal after 12 hours for back flow reaction, with the reaction solution suction filtration, obtain the insolubles of white, with dry behind the 20ml distilled water wash 2 times, obtain 1,4-two phthalic imidine butane 14.09g, yield 810%, mp.227～229 ℃.The 14.09g (0.041mol) 1 that previous step is made, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, rear adding 18.83g (the molar weight 0.24mol that contains methylamine) 40% aqueous methylamine solution, it is entirely molten to be heated to solid, continue stirring until and add concentrated hydrochloric acid 5ml after reaction solution is yellow transparent, end reaction after continuing to reflux 4 hours.Reaction product is filtered, and filtrate is concentrated into and slightly is thick and is neutralized to pH=7 with solid NaOH afterwards, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying hold over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collect 158～160 ℃ between cut, get the liquid 2.37g that colorless oil has decomposed odour, two-step reaction total recovery 53.8%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 14
Take by weighing Isosorbide-5-Nitrae-dibromo butylamine 10.90g (0.05mol), add in the 500ml there-necked flask, add 250mL acetone, 70 ℃ of stirrings add 24.05g (0.13mol) potassium phthalimide, the TLC detection reaction is to terminal after 24 hours for back flow reaction, with the reaction solution suction filtration, obtain the insolubles of white, with dry behind the 20ml distilled water wash 2 times, obtain 1,4-two phthalic imidine butane 15.73g, yield 90.4%, mp.227～229 ℃.The 15.73g (0.045mol) 1 that previous step is made, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, rear adding 21.02g (the molar weight 0.27mol that contains methylamine) 40% aqueous methylamine solution, it is entirely molten to be heated to solid, continue stirring until and add concentrated hydrochloric acid 8ml after reaction solution is yellow transparent, end reaction after continuing to reflux 4 hours.Reaction product is filtered, and filtrate is concentrated into and slightly is thick and is neutralized to pH=7 with solid NaOH afterwards, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying hold over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collect 158～160 ℃ between cut, get the liquid 2.53g that colorless oil has decomposed odour, two-step reaction total recovery 57.3%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 15
Take by weighing Isosorbide-5-Nitrae-dibromo butylamine 10.90g (0.05mol), add in the 500ml there-necked flask, adding refluxes is reacted into 250mL acetone, and 30 ℃ of stirrings add 24.05g (0.13mol) potassium phthalimide, the TLC detection reaction to terminal after 13 hours, with the reaction solution suction filtration, obtain the insolubles of white, with dry behind the 20ml distilled water wash 2 times, obtain 1,4-two phthalic imidine butane 11.80g, yield 67.8%, mp.227～229 ℃.The 11.80g (0.034mol) 1 that previous step is made, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, rear adding 15.76g (the molar weight 0.20mol that contains methylamine) 40% aqueous methylamine solution, it is entirely molten to be heated to solid, continue stirring until and add concentrated hydrochloric acid 12ml after reaction solution is yellow transparent, end reaction after continuing to reflux 4 hours.Reaction product is filtered, and filtrate is concentrated into and slightly is thick and is neutralized to pH=7 with solid NaOH afterwards, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying hold over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collect 158～160 ℃ between cut, get the liquid 2.01g that colorless oil has decomposed odour, two-step reaction total recovery 45.7%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 16
Take by weighing Isosorbide-5-Nitrae-dibromo butylamine 10.90g (0.05mol), add in the 500ml there-necked flask, add 250mL acetone, 70 ℃ of stirrings add 24.05g (0.13mol) potassium phthalimide, the TLC detection reaction is to terminal after 24 hours for back flow reaction, with the reaction solution suction filtration, obtain the insolubles of white, with dry behind the 20ml distilled water wash 2 times, obtain 1,4-two phthalic imidine butane 15.49g, yield 89.0%, mp.227～229 ℃.The 15.49g (0.045mol) 1 that previous step is made, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, rear adding 20.69g (the molar weight 0.27mol that contains methylamine) 40% aqueous methylamine solution, it is entirely molten to be heated to solid, continue stirring until and add concentrated hydrochloric acid 8ml after reaction solution is yellow transparent, end reaction after continuing to reflux 3 hours.Reaction product is filtered, and filtrate is concentrated into and slightly is thick and is neutralized to pH=7 with solid NaOH afterwards, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying hold over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collect 158～160 ℃ between cut, get the liquid 2.60g that colorless oil has decomposed odour, two-step reaction total recovery 59.2%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 17
Take by weighing Isosorbide-5-Nitrae-dibromo butylamine 10.90g (0.05mol), add in the 500ml there-necked flask, add 250mL acetone, 70 ℃ of stirrings add 24.05g (0.13mol) potassium phthalimide, the TLC detection reaction is to terminal after 24 hours for back flow reaction, with the reaction solution suction filtration, obtain the insolubles of white, with dry behind the 20ml distilled water wash 2 times, obtain 1,4-two phthalic imidine butane 15.73g, yield 90.4%, mp.227～229 ℃.The 15.73g (0.045mol) 1 that previous step is made, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, rear adding 21.02g (the molar weight 0.27mol that contains methylamine) 40% aqueous methylamine solution, it is entirely molten to be heated to solid, continue stirring until and add concentrated hydrochloric acid 8ml after reaction solution is yellow transparent, end reaction after continuing to reflux 4 hours.Reaction product is filtered, and filtrate is concentrated into and slightly is thick and is neutralized to pH=7 with solid NaOH afterwards, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying hold over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collect 158～160 ℃ between cut, get the liquid 2.68g that colorless oil has decomposed odour, two-step reaction total recovery 60.9%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 18
Take by weighing Isosorbide-5-Nitrae-dibromo butylamine 10.90g (0.05mol), add in the 500ml there-necked flask, add 250mL acetone, 70 ℃ of stirrings add 24.05g (0.13mol) potassium phthalimide, the TLC detection reaction is to terminal after 24 hours for back flow reaction, with the reaction solution suction filtration, obtain the insolubles of white, with dry behind the 20ml distilled water wash 2 times, obtain 1,4-two phthalic imidine butane 15.97g, yield 91.8%, mp.227～229 ℃.The 15.97g (0.046mol) 1 that previous step is made, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, rear adding 21.34g (the molar weight 0.28mol that contains methylamine) 40% aqueous methylamine solution, it is entirely molten to be heated to solid, continue stirring until reaction solution and be yellow transparent, add concentrated hydrochloric acid 8ml, finish reaction after continuing to reflux 6 hours.Reaction product is filtered, and filtrate is concentrated into and slightly is thick and is neutralized to pH=7 with solid NaOH afterwards, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying hold over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collect 158～160 ℃ between cut, get the liquid 2.68g that colorless oil has decomposed odour, two-step reaction total recovery 61.0%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 19
Take by weighing Isosorbide-5-Nitrae-dibromo butylamine 10.90g (0.05mol), add in the 500ml there-necked flask, add 250mL acetone, 70 ℃ of stirrings add 24.05g (0.13mol) potassium phthalimide, the TLC detection reaction is to terminal after 24 hours for back flow reaction, with the reaction solution suction filtration, obtain the insolubles of white, with dry behind the 20ml distilled water wash 2 times, obtain 1,4-two phthalic imidine butane 15.87g, yield 91.2%, mp.227～229 ℃.The 15.87g (0.046mol) 1 that previous step is made, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 70mL ethanol, rear adding 21.20g (the molar weight 0.27mol that contains methylamine) 40% aqueous methylamine solution, it is entirely molten to be heated to solid, continue stirring until reaction solution and be yellow transparent, add concentrated hydrochloric acid 8ml, finish reaction after continuing to reflux 6 hours.Reaction product is filtered, and filtrate is concentrated into and slightly is thick and is neutralized to pH=7 with solid NaOH afterwards, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying hold over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collect 158～160 ℃ between cut, get the liquid 2.43g that colorless oil has decomposed odour, two-step reaction total recovery 55.2%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 20
Take by weighing Isosorbide-5-Nitrae-dibromo butylamine 10.90g (0.05mol), add in the 500ml there-necked flask, add 250mL acetone, 70 ℃ of stirrings add 24.05g (0.13mol) potassium phthalimide, the TLC detection reaction is to terminal after 24 hours for back flow reaction, with the reaction solution suction filtration, obtain the insolubles of white, with dry behind the 20ml distilled water wash 2 times, obtain 1,4-two phthalic imidine butane 16.08g, yield 92.4%, mp.227～229 ℃.The 16.08g (0.046mol) 1 that previous step is made, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, rear adding 21.48g (the molar weight 0.27mol that contains methylamine) 40% aqueous methylamine solution, it is entirely molten to be heated to solid, continue stirring until reaction solution and be yellow, add concentrated hydrochloric acid 8ml, finish reaction after continuing to reflux 6 hours.Reaction product is filtered, and filtrate is concentrated into and slightly is thick and is neutralized to pH=7 with solid NaOH afterwards, then extracts 3 times with ether 50mL, adds the anhydrous sodium sulfate drying hold over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collect 158～160 ℃ between cut, get the liquid 2.66g that colorless oil has decomposed odour, two-step reaction total recovery 60.4%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 21
Take by weighing Isosorbide-5-Nitrae-dibromo butylamine 10.90g (0.05mol), add in the 500ml there-necked flask, add 250mL acetone, 70 ℃ of stirrings add 24.05g (0.13mol) potassium phthalimide, the TLC detection reaction is to terminal after 24 hours for back flow reaction, with the reaction solution suction filtration, obtain the insolubles of white, with dry behind the 20ml distilled water wash 2 times, obtain 1,4-two phthalic imidine butane 15.74g, yield 90.5%, mp.227～229 ℃.The 15.74g (0.045mol) 1 that previous step is made, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL methyl alcohol, rear adding 21.04g (the molar weight 0.27mol that contains methylamine) 40% aqueous methylamine solution, it is entirely molten to be heated to solid, continue stirring until reaction solution and be yellow transparent, add concentrated hydrochloric acid 8ml, finish reaction after continuing to reflux 6 hours.Reaction product is filtered, and filtrate is concentrated into and slightly is thick and is neutralized to pH=7 with solid NaOH afterwards, then extracts 3 times with chloroform 50mL, adds the anhydrous sodium sulfate drying hold over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collect 158～160 ℃ between cut, get the liquid 2.86g that colorless oil has decomposed odour, two-step reaction total recovery 57.4%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 22
Take by weighing Isosorbide-5-Nitrae-dibromo butylamine 10.90g (0.05mol), add in the 500ml there-necked flask, add 250mL acetone, 70 ℃ of stirrings add 24.05g (0.13mol) potassium phthalimide, the TLC detection reaction is to terminal after 24 hours for back flow reaction, with the reaction solution suction filtration, obtain the insolubles of white, with dry behind the 20ml distilled water wash 2 times, obtain 1,4-two phthalic imidine butane 16.00g, yield 92.0%, mp.227～229 ℃.The 16.00g (0.046mol) 1 that previous step is made, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 150mL ethanol, rear adding 21.39g (the molar weight 0.28mol that contains methylamine) 40% aqueous methylamine solution, it is entirely molten to be heated to solid, continue stirring until reaction solution and be yellow transparent, add concentrated hydrochloric acid 8ml, finish reaction after continuing to reflux 6 hours.Reaction product is filtered, and filtrate is concentrated into and slightly is thick and is neutralized to pH=7 with solid NaOH afterwards, then extracts 3 times with ether 50mL, adds the anhydrous sodium sulfate drying hold over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collect 158～160 ℃ between cut, get the liquid 2.44g that colorless oil has decomposed odour, two-step reaction total recovery 55.6%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Claims (10)
1. 1 shown in the formula (4), the synthetic method of 4-butanediamine (4), it is characterized in that described method is that (a) is with 1 shown in the formula (1), the 4-dibromobutane is dissolved in the solvent orange 2 A, potassium phthalimide shown in the adding formula (2), stir lower reaction under the reflux temperature, react complete, reaction solution filters, with obtaining the Isosorbide-5-Nitrae-two phthalic imidine butane shown in the formula (3), described 1 behind the distilled water wash, the molar ratio that feeds intake of 4-dibromobutane and potassium phthalimide is 1: 2.0～4.0, and the reaction times is 1～24 hour; (b) step (a) is obtained 1,4-two phthalic imidine butane and 40% aqueous methylamine solution join among the solvent B, it is entirely molten to be heated to solid, under the reflux temperature stirring reaction 0.5-4 hour, after being yellow transparent to reaction system, add concentrated hydrochloric acid, finish reaction after continuing to reflux 3～9 hours, get reaction product; Described 1, methylamine molar ratio in 4-two phthalic imidine butane (3) and 40% aqueous methylamine solution is 1: 4.0～8.0, adding hydrogenchloride in the concentrated hydrochloric acid and Isosorbide-5-Nitrae-two phthalic imidine butane (3) molar ratio that feeds intake is 1: 2.0～4.0; (c) reaction product is filtered, filtrate being concentrated into begins to be among the thick rear usefulness solid NaOH and transfers pH to 7, extract with extraction agent again, getting the extraction agent layer spends the night with desiccant dryness, extraction agent is removed in underpressure distillation after removing siccative, remaining raffinate carries out air distillation again, collect 158～160 ℃ between cut namely get described Putriscine;
2. the synthetic method of Putriscine as claimed in claim 1 (4) is characterized in that described solvent orange 2 A is one of following: water, methyl alcohol, ethanol, acetone.
3. the synthetic method of Putriscine as claimed in claim 1 (4) is characterized in that described solvent B is one of following: water, methyl alcohol, ethanol.
4. the synthetic method of Putriscine as claimed in claim 1 (4) is characterized in that described extraction agent is one of following: methylene dichloride, trichloromethane, tetracol phenixin, ether, propyl ether, isopropyl ether, butyl ether.
5. the synthetic method of Putriscine as claimed in claim 1 (4), the consumption that it is characterized in that the described solvent orange 2 A of step (a) is 20～30 times of Isosorbide-5-Nitrae-dibromobutane volume.
6. the synthetic method of Putriscine as claimed in claim 1 (4) is characterized in that the described reaction times of step (a) is 1～24 hour.
7. the synthetic method of Putriscine as claimed in claim 1 (4), the consumption that it is characterized in that the described solvent B of step (b) is 10～30 times of 40% aqueous methylamine solution volume.
8. the synthetic method of Putriscine as claimed in claim 4 (4), the consumption that it is characterized in that described extraction agent be reactant concentrated after 3 times of volume, extraction agent same dose extraction 2～3 times merges each extraction agent layer.
9. the synthetic method of Putriscine as claimed in claim 1 (4) is characterized in that the described reaction of step (a) is with TLC tracking detection reaction terminal point.
10. as claimed in claim 11, the synthetic method of 4-butanediamine (4), it is characterized in that described synthetic method is that (a) is with 1 shown in the formula (1), the 4-dibromobutane is dissolved in the acetone, potassium phthalimide back flow reaction shown in the adding formula (2), TLC follows the tracks of the detection reaction terminal point, react complete, reaction solution filters, and obtains the Isosorbide-5-Nitrae-two phthalic imidine butane shown in the formula (3), described 1, the molar ratio that feeds intake of 4-dibromobutane and potassium phthalimide is 1: 2.0～3.0, and the consumption of acetone is 15～20 times of Isosorbide-5-Nitrae-Ding bromine butylamine volume; (b) step (a) is obtained 1,4-two phthalic imidine butane add ethanol and 40% aqueous methylamine solution, be heated to 30～100 ℃ entirely molten to solid, stir, after back flow reaction 0.5-4 hour, solution is yellow transparent, adds concentrated hydrochloric acid, continue backflow and finish reaction after 3-9 hour, get reaction product; Described 1, methylamine in 4-two phthalic imidine butane (3) and 40% aqueous methylamine solution molar ratio that feeds intake is 1: 4.0～6.0, hydrogenchloride in the concentrated hydrochloric acid that adds and the molar ratio of Isosorbide-5-Nitrae-two phthalic imidine butane (3) are 1: 2.0～4.0; Described ethanol consumption is 10～30 times of 40% aqueous methylamine solution volume; (c) reaction product is filtered, get filtrate be concentrated into slightly be behind the thickness state with among the solid NaOH and transfer pH to 7, the again extraction take methylene dichloride as extraction agent, the consumption of described extraction agent be reactant concentrated after 3 times of volume, same dose extraction 3 times merges each extraction agent layer; Get dichloromethane layer and spend the night with desiccant dryness, remove pressure reducing and steaming extraction agent behind the siccative, carry out again air distillation, collect 158～160 ℃ between cut namely get described Putriscine, described siccative is anhydrous sodium sulphate.
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| Title |
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| Ennio Ciuffarin et al..Catalysis in aprotic solvents. Inter- and intramolecular hydrogen bonding complexation.《J. Org. Chem.》.1981,第46卷(第15期),3064–3070. * |
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