CN101735067A - Synthesis method of 1,4-butanediamine - Google Patents
Synthesis method of 1,4-butanediamine Download PDFInfo
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- CN101735067A CN101735067A CN 200910155160 CN200910155160A CN101735067A CN 101735067 A CN101735067 A CN 101735067A CN 200910155160 CN200910155160 CN 200910155160 CN 200910155160 A CN200910155160 A CN 200910155160A CN 101735067 A CN101735067 A CN 101735067A
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- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000001308 synthesis method Methods 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 147
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000001273 butane Substances 0.000 claims abstract description 66
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000007787 solid Substances 0.000 claims abstract description 53
- 238000003756 stirring Methods 0.000 claims abstract description 52
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000706 filtrate Substances 0.000 claims abstract description 28
- 238000010992 reflux Methods 0.000 claims abstract description 28
- 239000012153 distilled water Substances 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 17
- -1 1,4-dibromobutyl Chemical group 0.000 claims abstract description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 134
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 78
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 71
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 58
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 54
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 54
- 238000000605 extraction Methods 0.000 claims description 51
- 239000003795 chemical substances by application Substances 0.000 claims description 44
- FYRHIOVKTDQVFC-UHFFFAOYSA-M potassium phthalimide Chemical compound [K+].C1=CC=C2C(=O)[N-]C(=O)C2=C1 FYRHIOVKTDQVFC-UHFFFAOYSA-M 0.000 claims description 32
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 29
- 238000004821 distillation Methods 0.000 claims description 28
- 238000001514 detection method Methods 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 26
- SSMHQPSHEZKUOM-UHFFFAOYSA-N 1,4-dibromobutan-1-amine Chemical compound BrC(CCCBr)N SSMHQPSHEZKUOM-UHFFFAOYSA-N 0.000 claims description 25
- 239000000284 extract Substances 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000010189 synthetic method Methods 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- BQFCCCIRTOLPEF-UHFFFAOYSA-N chembl1976978 Chemical compound CC1=CC=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 BQFCCCIRTOLPEF-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 229960001701 chloroform Drugs 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 2
- PVIQRYGPUWWMBZ-UHFFFAOYSA-N [Br].C(CCC)N Chemical compound [Br].C(CCC)N PVIQRYGPUWWMBZ-UHFFFAOYSA-N 0.000 claims description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- BYXYCUABYHCYLY-UHFFFAOYSA-N isoindole-1,3-dione;potassium Chemical compound [K].C1=CC=C2C(=O)NC(=O)C2=C1 BYXYCUABYHCYLY-UHFFFAOYSA-N 0.000 abstract 1
- LFETXMWECUPHJA-UHFFFAOYSA-N methanamine;hydrate Chemical compound O.NC LFETXMWECUPHJA-UHFFFAOYSA-N 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 description 44
- 239000012230 colorless oil Substances 0.000 description 23
- 238000005160 1H NMR spectroscopy Methods 0.000 description 22
- 238000011084 recovery Methods 0.000 description 22
- 238000000967 suction filtration Methods 0.000 description 22
- 238000007039 two-step reaction Methods 0.000 description 22
- 238000005303 weighing Methods 0.000 description 22
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005700 Putrescine Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- PTAYFGHRDOMJGC-UHFFFAOYSA-N 4-aminobutyl(diaminomethylidene)azanium;hydrogen sulfate Chemical compound OS(O)(=O)=O.NCCCCN=C(N)N PTAYFGHRDOMJGC-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007098 aminolysis reaction Methods 0.000 description 1
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyrrole Compounds (AREA)
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 1, the synthetic method of 4-butanediamine.
(2) background technology
1, the 4-butanediamine has another name called 1,4-diaminobutane, tetramethylene-diamine, saprine, English name 1,4-Diaminobutane.
1, the 4-butanediamine is a kind of important chemical intermediate, for example, has the drug rehabilitation class medicine agmatine sulfate of DEVELOPMENT PROSPECT, is exactly with 1, and the 4-butanediamine comes synthetic (Chinese publication CN1834085A and CN101121677) as main raw material.Again for example, some main engineering plastics (polymeric amide-4,6, homopolymer or multipolymer form) also are with 1, and the 4-butanediamine is that important raw and processed materials is come synthetic.Therefore, 1, the 4-butanediamine has vast market prospect.
About 1,4-butanediamine synthetic, many countries all research and develop its synthetic method, and the chemical synthesis that integrates mainly contains following a few class: (1) with 1, the 4-diisocyanate butane is a raw material, hydrolysis under acidic conditions (Naegeli, C.; Lendorff, P.HelveticaChimica Acta (1932), 15,49-59.), make 1, the 4-butanediamine; (2) with 1,4-two phthalic imidine butane are 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 1, the 4-butanediamine; (3) make 1 with corresponding triazo-compound through azido reaction, 4-butanediamine (Khoukhi, Mostafa; Vaultier, Michel; Benalil, Aziza; Carboni, Bertrand.Synthesis (1996), (4), 483-7).; (4) 1,4-succinonitrile methods, this method is a catalyzer by Co or Ni, is solvent with water, makes 1,4-butanediamine (Jouichi, Akiko; Ito, Kazuhisa.Jpn.Kokai Tokkyo Koho (2001), 5pp.).Yet still there are some problems in process of production in appeal technology, and for example, the hydrolysis temperature high pressure is big; 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 environment are polluted, and are unfavorable for labour protection, more do not meet industry policy of energy-saving and emission-reduction or the like
(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, do not have the synthetic 1 of " three wastes " discharging, the method for 4-butanediamine substantially.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, reaction finishes, and reaction solution filters, filter cake washs 1～3 time with aquae destillata, obtain 1 shown in the formula (3), 4-two phthalic imidine butane, described 1, the amount of substance 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 molten entirely to be heated to solid, the backflow 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 product 1, the 4-butanediamine changes into hydrochloride, and the accelerated reaction forward carries out, and improves productive rate.Described 1,4-two phthalic imidine butane (3) and methylamine in 40% aqueous methylamine solution amount of substance ratio that feeds intake is 1: 4.0～8.0, add the hydrogenchloride and 1 in the concentrated hydrochloric acid, the amount of substance ratio that feeds intake of 4-two phthalic imidine butane (3) is 1: 2.0～4.0; (c) reaction product is filtered, get filtrate being concentrated into and begin to be thick back with transferring pH to 7 among the solid NaOH, extract with extraction agent again, can extract repeatedly, the extraction back merges the extraction agent layer with the siccative dried overnight, multiple siccative can use, as anhydrous sodium sulphate, anhydrous magnesium sulfate, Vanadium Pentoxide in FLAKES etc., it is siccative that the present invention recommends with the anhydrous sodium sulphate, boils off extraction agent after removing siccative, the present invention recommends to adopt Rotary Evaporators to boil 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, between collecting 158～160 ℃ cut promptly get described 1, the 4-butanediamine; Described 1, the 4-butanediamine is the liquid that colorless oil has decomposed odour.
Reaction equation of the present invention is as follows:
Of the present invention 1, the synthetic method of 4-butanediamine (4), the described solvent orange 2 A of described step (a) is one of following or their arbitrary combination: water, methyl alcohol, ethanol, acetone.Preferred solvent A is an acetone.The consumption of described solvent orange 2 A is 1,20～30 times of 4-dibromo butylamine volume, and the consumption of preferred solvent A is 1,15～20 times of 4-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 an 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 is about reactant and concentrates 3 times of back volume, uses 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 a methylene dichloride.
Step of the present invention (a) is described 1, and the molar ratio of 4-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 was generally 1～24 hour, was preferably 12～15 hours.
The molar ratio of methylamine is 1: 4.0～1: 8.0 in 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 was generally 4～10 hours total time, was preferably 5～8 hours.
Concrete, the preferred synthetic method of the present invention be (a) 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, and reaction finishes, and reaction solution filters, obtain 1 shown in the formula (3), 4-two phthalic imidine butane, described 1,4-dibromo butylamine is 1: 2.0～3.0 with the amount of substance ratio that feeds intake of potassium phthalimide, the consumption of acetone is 1,15～20 times of 4-fourth bromine butylamine volume; (b) step (a) is obtained 1,4-two phthalic imidine butane add ethanol and 40% aqueous methylamine solution, it is molten entirely to be heated to solid, stir, after back flow reaction 0.5-4 hour, solution is yellow transparent, add a certain amount of concentrated hydrochloric acid, continue backflow and finish reaction after 3-9 hour, get reaction product; Described 1,4-two phthalic imidine butane (3) and methylamine in 40% aqueous methylamine solution amount of substance 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) the amount of substance 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, be the extraction agent extraction again with the methylene dichloride, the consumption of described extraction agent is 3 times that reactant concentrates the back volume, same dose extraction 3 times, get dichloromethane layer with the dry liquid of crossing of siccative, boil off extraction agent after removing siccative, carry out air distillation again, collect 158～160 ℃ between cut promptly 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.
Step (a) obtain 1,4-two phthalic imidine butane, only pipe is not highly purified, but purity can reach more than 96% usually.Step (b) is described 1, the amount of substance of 4-two phthalic imidine butane be exactly be used as pure product count with 40% aqueous methylamine solution in methylamine amount of substance ratio be 1: 4.0～8.0,
The present invention is with existing 1, and the preparation method of 4-butanediamine compares, and 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 reaction conditions gentleness, easily control.Therefore, the present invention has safety simple to operate, and reaction yield is higher, and the advantage that production cost is low has bigger 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 1,4-dibromo butylamine 10.90g (0.05mol) adds 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 2 after drying of 20ml distilled water wash, 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 suddenly, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, the back adds 18.90g 40% aqueous methylamine solution (the mole number 0.24mol that contains methylamine), it is molten entirely 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 back and is neutralized to pH=7 with solid NaOH, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying standing over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collects 158～160 ℃ between cut, the liquid 2.61g of decomposed odour must colorless oil be arranged, 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 1,4-dibromo butylamine 10.90g (0.05mol) adds 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 2 after drying of 20ml distilled water wash, 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 suddenly, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, the back adds 40% aqueous methylamine solution (the molar weight 0.21mol that contains methylamine) of 16.81g, it is molten entirely 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 back and is neutralized to pH=7 with solid NaOH, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying standing over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collects 158～160 ℃ between cut, the liquid 1.91g of decomposed odour must colorless oil be arranged, two-step reaction total recovery 43.4%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 3
Take by weighing 1,4-dibromo butylamine 10.90g (0.05mol) adds 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 2 after drying of 20ml distilled water wash, 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 suddenly, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, the back adds 14.99g 40% aqueous methylamine solution (the molar weight 0.19mol that contains methylamine), it is molten entirely 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 back and is neutralized to pH=7 with solid NaOH, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying standing over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collects 158～160 ℃ between cut, the liquid 1.69g of decomposed odour must colorless oil be arranged, two-step reaction total recovery 38.7%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 4
Take by weighing 1,4-dibromo butylamine 10.90g (0.05mol) adds 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 2 after drying of 20ml distilled water wash, 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 suddenly, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, the back adds 18.9g (the molar weight 0.24mol that contains methylamine) 40% aqueous methylamine solution, it is molten entirely 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 back and is neutralized to pH=7 with solid NaOH, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying standing over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collects 158～160 ℃ between cut, the liquid 2.33g of decomposed odour must colorless oil be arranged, two-step reaction total recovery 52.8%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 5
Take by weighing 1,4-dibromo butylamine 10.90g (0.05mol) adds 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 2 after drying of 20ml distilled water wash, 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 suddenly, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, the back adds 19.76g (the molar weight 0.26mol that contains methylamine) 40% aqueous methylamine solution, it is molten entirely 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 back and is neutralized to pH=7 with solid NaOH, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying standing over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collects 158～160 ℃ between cut, the liquid 2.40g of decomposed odour must colorless oil be arranged, two-step reaction total recovery 54.7%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 6
Take by weighing 1,4-dibromo butylamine 10.90g (0.05mol) adds 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 2 after drying of 20ml distilled water wash, 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 suddenly, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, the back adds 21.39g (the molar weight 0.28mol that contains methylamine) 40% aqueous methylamine solution, it is molten entirely 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 back and is neutralized to pH=7 with solid NaOH, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying standing over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collects 158～160 ℃ between cut, the liquid 2.57g of decomposed odour must colorless oil be arranged, two-step reaction total recovery 58.3%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 7
Take by weighing 1,4-dibromo butylamine 10.90g (0.05mol) adds 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 2 after drying of 20ml distilled water wash, 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 suddenly, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, the back adds 20.06g (the molar weight 0.26mol that contains methylamine) 40% aqueous methylamine solution, it is molten entirely 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 back and is neutralized to pH=7 with solid NaOH, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying standing over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collects 158～160 ℃ between cut, the liquid 2.35g of decomposed odour must colorless oil be arranged, two-step reaction total recovery 53.5%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 8
Take by weighing 1,4-dibromo butylamine 10.90g (0.05mol) adds 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 2 after drying of 20ml distilled water wash, 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 suddenly, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, the back adds 21.39g (the molar weight 0.28mol that contains methylamine) 40% aqueous methylamine solution, it is molten entirely 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 back and is neutralized to pH=7 with solid NaOH, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying standing over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collects 158～160 ℃ between cut, the liquid 2.63g of decomposed odour must colorless oil be arranged, two-step reaction total recovery 59.7%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 9
Take by weighing 1,4-dibromo butylamine 10.90g (0.05mol) adds 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 2 after drying of 20ml distilled water wash, 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 suddenly, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, the back adds 21.39g (the molar weight 0.28mol that contains methylamine) 40% aqueous methylamine solution, it is molten entirely 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 back and is neutralized to pH=7 with solid NaOH, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying standing over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collects 158～160 ℃ between cut, the liquid 2.36g of decomposed odour must colorless oil be arranged, two-step reaction total recovery 53.6%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 10
Take by weighing 1,4-dibromo butylamine 10.90g (0.05mol) adds 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 2 after drying of 20ml distilled water wash, 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 suddenly, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, the back adds 14.00g (the molar weight 0.18mol that contains methylamine) 40% aqueous methylamine solution, it is molten entirely 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 back and is neutralized to pH=7 with solid NaOH, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying standing over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collects 158～160 ℃ between cut, the liquid 1.66g of decomposed odour must colorless oil be arranged, two-step reaction total recovery 37.9%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 11
Take by weighing 1,4-dibromo butylamine 10.90g (0.05mol) adds 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 2 after drying of 20ml distilled water wash, 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 suddenly, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, the back adds 21.18g (the molar weight 0.27mol that contains methylamine) 40% aqueous methylamine solution, it is molten entirely 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 back and is neutralized to pH=7 with solid NaOH, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying standing over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collects 158～160 ℃ between cut, the liquid 2.69g of decomposed odour must colorless oil be arranged, two-step reaction total recovery 61.0%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 12
Take by weighing 1,4-dibromo butylamine 10.90g (0.05mol) adds 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 2 after drying of 20ml distilled water wash, 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 suddenly, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, the back adds 28.83g (the molar weight 0.37mol that contains methylamine) 40% aqueous methylamine solution, it is molten entirely 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 back and is neutralized to pH=7 with solid NaOH, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying standing over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collects 158～160 ℃ between cut, the liquid 2.25g of decomposed odour must colorless oil be arranged, two-step reaction total recovery 51.1%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 13
Take by weighing 1,4-dibromo butylamine 10.90g (0.05mol) adds 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 2 after drying of 20ml distilled water wash, 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 suddenly, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, the back adds 18.83g (the molar weight 0.24mol that contains methylamine) 40% aqueous methylamine solution, it is molten entirely 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 back and is neutralized to pH=7 with solid NaOH, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying standing over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collects 158～160 ℃ between cut, the liquid 2.37g of decomposed odour must colorless oil be arranged, two-step reaction total recovery 53.8%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 14
Take by weighing 1,4-dibromo butylamine 10.90g (0.05mol) adds 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 2 after drying of 20ml distilled water wash, 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 suddenly, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, the back adds 21.02g (the molar weight 0.27mol that contains methylamine) 40% aqueous methylamine solution, it is molten entirely 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 back and is neutralized to pH=7 with solid NaOH, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying standing over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collects 158～160 ℃ between cut, the liquid 2.53g of decomposed odour must colorless oil be arranged, two-step reaction total recovery 57.3%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 15
Take by weighing 1,4-dibromo butylamine 10.90g (0.05mol) adds 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 2 after drying of 20ml distilled water wash, 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 suddenly, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, the back adds 15.76g (the molar weight 0.20mol that contains methylamine) 40% aqueous methylamine solution, it is molten entirely 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 back and is neutralized to pH=7 with solid NaOH, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying standing over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collects 158～160 ℃ between cut, the liquid 2.01g of decomposed odour must colorless oil be arranged, two-step reaction total recovery 45.7%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 16
Take by weighing 1,4-dibromo butylamine 10.90g (0.05mol) adds 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 2 after drying of 20ml distilled water wash, 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 suddenly, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, the back adds 20.69g (the molar weight 0.27mol that contains methylamine) 40% aqueous methylamine solution, it is molten entirely 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 back and is neutralized to pH=7 with solid NaOH, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying standing over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collects 158～160 ℃ between cut, the liquid 2.60g of decomposed odour must colorless oil be arranged, two-step reaction total recovery 59.2%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 17
Take by weighing 1,4-dibromo butylamine 10.90g (0.05mol) adds 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 2 after drying of 20ml distilled water wash, 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 suddenly, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, the back adds 21.02g (the molar weight 0.27mol that contains methylamine) 40% aqueous methylamine solution, it is molten entirely 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 back and is neutralized to pH=7 with solid NaOH, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying standing over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collects 158～160 ℃ between cut, the liquid 2.68g of decomposed odour must colorless oil be arranged, two-step reaction total recovery 60.9%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 18
Take by weighing 1,4-dibromo butylamine 10.90g (0.05mol) adds 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 2 after drying of 20ml distilled water wash, 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 suddenly, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, the back adds 21.34g (the molar weight 0.28mol that contains methylamine) 40% aqueous methylamine solution, it is molten entirely 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 back and is neutralized to pH=7 with solid NaOH, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying standing over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collects 158～160 ℃ between cut, the liquid 2.68g of decomposed odour must colorless oil be arranged, two-step reaction total recovery 61.0%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 19
Take by weighing 1,4-dibromo butylamine 10.90g (0.05mol) adds 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 2 after drying of 20ml distilled water wash, 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 suddenly, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 70mL ethanol, the back adds 21.20g (the molar weight 0.27mol that contains methylamine) 40% aqueous methylamine solution, it is molten entirely 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 back and is neutralized to pH=7 with solid NaOH, then extracts 3 times with methylene dichloride 50mL, adds the anhydrous sodium sulfate drying standing over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collects 158～160 ℃ between cut, the liquid 2.43g of decomposed odour must colorless oil be arranged, two-step reaction total recovery 55.2%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 20
Take by weighing 1,4-dibromo butylamine 10.90g (0.05mol) adds 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 2 after drying of 20ml distilled water wash, 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 suddenly, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL ethanol, the back adds 21.48g (the molar weight 0.27mol that contains methylamine) 40% aqueous methylamine solution, it is molten entirely 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 back and is neutralized to pH=7 with solid NaOH, then extracts 3 times with ether 50mL, adds the anhydrous sodium sulfate drying standing over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collects 158～160 ℃ between cut, the liquid 2.66g of decomposed odour must colorless oil be arranged, two-step reaction total recovery 60.4%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 21
Take by weighing 1,4-dibromo butylamine 10.90g (0.05mol) adds 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 2 after drying of 20ml distilled water wash, 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 suddenly, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 100mL methyl alcohol, the back adds 21.04g (the molar weight 0.27mol that contains methylamine) 40% aqueous methylamine solution, it is molten entirely 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 back and is neutralized to pH=7 with solid NaOH, then extracts 3 times with chloroform 50mL, adds the anhydrous sodium sulfate drying standing over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collects 158～160 ℃ between cut, the liquid 2.86g of decomposed odour must colorless oil be arranged, two-step reaction total recovery 57.4%, 1HNMR (400MHz, D2O) δ: 1.69 (m, 1H), 2.98 (m, 1H).
Embodiment 22
Take by weighing 1,4-dibromo butylamine 10.90g (0.05mol) adds 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 2 after drying of 20ml distilled water wash, 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 suddenly, 4-two phthalic imidine butane add in the 250mL there-necked flask, add 150mL ethanol, the back adds 21.39g (the molar weight 0.28mol that contains methylamine) 40% aqueous methylamine solution, it is molten entirely 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 back and is neutralized to pH=7 with solid NaOH, then extracts 3 times with ether 50mL, adds the anhydrous sodium sulfate drying standing over night; Revolve steam remove extraction agent after, remaining raffinate air distillation, collects 158～160 ℃ between cut, the liquid 2.44g of decomposed odour must colorless oil be arranged, 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), 4-dibromo butylamine is dissolved in the solvent orange 2 A, potassium phthalimide shown in the adding formula (2), reflux temperature stirs reaction down down, reaction finishes, reaction solution filters, with obtaining 1 shown in the formula (3) behind the distilled water wash, 4-two phthalic imidine butane, described 1,4-dibromo butylamine is 1: 2.0～4.0 with the amount of substance ratio that feeds intake of potassium phthalimide, 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 molten entirely 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 1,4-two phthalic imidine butane (3) are 1: 4.0～8.0 with methylamine amount of substance ratio in 40% aqueous methylamine solution, add the hydrogenchloride and 1 in the concentrated hydrochloric acid, and 4-two phthalic imidine butane (3) the amount of substance ratio that feeds intake is 1: 2.0～4.0; (c) reaction product is filtered, filtrate being concentrated into begins to be thick back and uses among the solid NaOH and accent pH to 7, extract with extraction agent again, get the extraction agent layer with the dry liquid of crossing of siccative, extraction agent is removed in underpressure distillation after removing siccative, remaining raffinate carries out air distillation again, collect 158～160 ℃ between cut promptly get described 1, the 4-butanediamine;
2. as claimed in claim 11, the synthetic method of 4-butanediamine (4) is characterized in that described solvent orange 2 A is one of following: water, methyl alcohol, ethanol, acetone.
3. as claimed in claim 11, the synthetic method of 4-butanediamine (4) is characterized in that described solvent B is one of following: water, methyl alcohol, ethanol.
4. as claimed in claim 11, the synthetic method of 4-butanediamine (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. as claimed in claim 11, the synthetic method of 4-butanediamine (4) is characterized in that the consumption of the described solvent orange 2 A of step (a) is 1,20～30 times of 4-dibromo butylamine volume.
6. as claimed in claim 11, the synthetic method of 4-butanediamine (4) is characterized in that the described reaction times of step (a) is 1～24 hour.
7. as claimed in claim 11, the synthetic method of 4-butanediamine (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. as claimed in claim 41, the synthetic method of 4-butanediamine (4), the consumption that it is characterized in that described extraction agent is 3 times that reactant concentrates the back volume, extraction agent same dose extraction 2～3 times merges each extraction agent layer.
9. as claimed in claim 11, the synthetic method of 4-butanediamine (4) is characterized in that the described reaction of step (a) follows the tracks of the detection reaction terminal point with TLC.
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), 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, reaction finishes, reaction solution filters, and obtains 1 shown in the formula (3), 4-two phthalic imidine butane, described 1,4-dibromo butylamine is 1: 2.0～3.0 with the amount of substance ratio that feeds intake of potassium phthalimide, and the consumption of acetone is 1,15～20 times of 4-fourth 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 ℃ molten entirely 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 1,4-two phthalic imidine butane (3) and methylamine in 40% aqueous methylamine solution amount of substance ratio that feeds intake is 1: 4.0～6.0, hydrogenchloride and 1 in the concentrated hydrochloric acid that adds, the amount of substance ratio of 4-two phthalic imidine butane (3) is 1: 2.0～4.0; Described solvent B consumption is 10～30 times of 40% aqueous methylamine solution volume; (c) reaction product is filtered, getting filtrate and be concentrated into and slightly be behind the thickness state with transferring pH to 7 among the solid NaOH, is the extraction agent extraction again with the methylene dichloride, and the consumption of described extraction agent is 3 times that reactant concentrates the back volume, same dose extraction 3 times merges each extraction agent layer; Get dichloromethane layer with the dry liquid of crossing of siccative, remove pressure reducing and steaming extraction agent behind the siccative, carry out air distillation again, collect 158～160 ℃ between cut promptly get describedly 1,4-butanediamine, described siccative are anhydrous sodium sulphate.
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| CN117025117A (en) * | 2023-08-11 | 2023-11-10 | 青岛德聚胶接技术有限公司 | High-temperature-resistant and deformation-resistant chip epoxy adhesive film and preparation method thereof |
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| KR100407428B1 (en) * | 1999-03-19 | 2003-11-28 | 미쯔이카가쿠 가부시기가이샤 | Novel process for the preparation of n,n'-dialkylalkanediamines |
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| CN117025117A (en) * | 2023-08-11 | 2023-11-10 | 青岛德聚胶接技术有限公司 | High-temperature-resistant and deformation-resistant chip epoxy adhesive film and preparation method thereof |
| CN117025117B (en) * | 2023-08-11 | 2024-09-24 | 青岛德聚胶接技术有限公司 | High-temperature-resistant and deformation-resistant chip epoxy adhesive film and preparation method thereof |
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