CN110256280A - A kind of 2,2 '-azos (2- methyl-N-(2- hydroxyethyl) propionamide) preparation method - Google Patents
A kind of 2,2 '-azos (2- methyl-N-(2- hydroxyethyl) propionamide) preparation method Download PDFInfo
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- CN110256280A CN110256280A CN201811386202.9A CN201811386202A CN110256280A CN 110256280 A CN110256280 A CN 110256280A CN 201811386202 A CN201811386202 A CN 201811386202A CN 110256280 A CN110256280 A CN 110256280A
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- hydroxyethyl
- propionamide
- azos
- methyl
- methanol
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- WTNTZFRNCHEDOS-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-methylpropanamide Chemical compound CC(C)C(=O)NCCO WTNTZFRNCHEDOS-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 138
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims abstract description 56
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000000463 material Substances 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 239000007789 gas Substances 0.000 claims abstract description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012074 organic phase Substances 0.000 claims abstract description 24
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 23
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 230000007062 hydrolysis Effects 0.000 claims abstract description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 15
- 238000004321 preservation Methods 0.000 claims abstract description 12
- 238000004821 distillation Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000004128 high performance liquid chromatography Methods 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- 238000009413 insulation Methods 0.000 claims abstract description 6
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000021050 feed intake Nutrition 0.000 claims 1
- 238000005119 centrifugation Methods 0.000 abstract description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 8
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000007098 aminolysis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- JUINSXZKUKVTMD-UHFFFAOYSA-N hydrogen azide Chemical compound N=[N+]=[N-] JUINSXZKUKVTMD-UHFFFAOYSA-N 0.000 description 2
- -1 isobutyryl Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- NIQCNGHVCWTJSM-UHFFFAOYSA-N dimethyl benzenedicarboxylate Natural products COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- DNMZJIGSDQVGSA-UHFFFAOYSA-N methoxymethane;hydrochloride Chemical compound Cl.COC DNMZJIGSDQVGSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/04—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses one kind 2,2 '-azos (2- methyl-N-(2- hydroxyethyl) propionamide) preparation method, it is in the reactor with stirring and reflux unit, first put into 2,2 '-azodiisobutyronitriles, methanol and toluene, stirring is opened, is passed through hydrogen chloride gas at leisure under cooling, then control material temperature and carries out insulation reaction；Reaction solution is instilled in water after reaction, reaction is hydrolyzed, hydrolysis terminates layering, organic vacuum distillation a period of time after being added to a small amount of methanol；After distillation, organic phase is slowly dropped into sodium methoxide and the mixed solution of monoethanolamine and is kept the temperature；It after heat preservation, will be separated by solid-liquid separation with centrifuge, solid continues to use clear water wash crystallization, and centrifugation is dry to expecting, then material is placed in drier and is dried；It is cooled to room temperature after drying to material, just obtains 2,2 '-azos (2- methyl-N- (2- hydroxyethyl) propionamide) product, the product content (HPLC) 98% or more.Yield 55~75%.
Description
Technical field
The present invention relates to chemical industry synthesis fields, and in particular to a kind of 2,2 '-azos (2- methyl-N- (2- hydroxyethyl) third
Amide) preparation method.
Background technique
2,2 '-azos (2- methyl-N- (2- hydroxyethyl) propionamide) are a kind of safe and efficient initiators, due to its tool
There is a stabilization, low toxicity and the features such as be not easily decomposed.
The data for being related to 2,2 '-azos (2- methyl-N- (2- hydroxyethyl) propionamide) synthetic method has: Changzhou University
Journal (natural science edition) the 4th phase " synthesis of two isobutyryl of azo (N- ethyl alcohol) amine " of volume 23 in December, 2011.
This method reacts to obtain azoimide methyl ether using azodiisobutyronitrile and methanol as raw material by the way that thionyl chloride is added dropwise
Hydrochloride, azoimide methyl ether hydrochloride obtains intermediate azo-bis-iso-dimethyl after hydrolysis, layering, drying, even
With monoethanolamine aminolysis reaction occurs for two isobutyl dimethyl phthalate of nitrogen under sodium methoxide catalyzed effect, obtains 2,2 '-azo (2- first
Base-N- (2- hydroxyethyl) propionamide).
Party's law limitation is mainly:
(1) methanol is seriously excessive in reaction, 2,2 '-azodiisobutyronitrile of molar ratio: methanol=1:10, and excessive methanol inhibits
Reaction；
(2) after hydrolyzing, in order to obtain intermediate azo-bis-iso-dimethyl, static layering is needed, body when layering
There are a large amount of floccules, hierarchical operations are extremely difficult for system, not can guarantee efficiently separating for water phase and organic phase；
(3) a large amount of sulfur dioxide pernicious gases are generated in reaction process, environmental pollution is serious；
(4) it needs using a large amount of natrium carbonicum calcinatum desiccant；
(5) there is certain loss of material during individually obtaining intermediate azo-bis-iso-dimethyl.
Summary of the invention
In order to overcome drawbacks described above of the existing technology, the purpose of the present invention is to provide a kind of easy to operate, stable
Efficiently, easy to industrialized production 2,2 '-azo (2- methyl-N- (2- hydroxyethyl) propionamide) preparation method.
One of in order to achieve the object of the present invention, used technical solution is:
A kind of preparation method of 2,2 '-azos (2- methyl-N- (2- hydroxyethyl) propionamide), be with stirring and
In the reactor of reflux unit, 2,2 '-azodiisobutyronitriles, methanol and toluene are first put into, stirring is opened, leads at leisure under cooling
Enter hydrogen chloride gas, then control material temperature and carries out insulation reaction；Reaction solution is instilled in water after reaction and is hydrolyzed instead
It answers, hydrolysis terminates layering, organic vacuum distillation a period of time after being added to a small amount of methanol；It is after distillation, organic phase is slow
It instills in sodium methoxide and the mixed solution of monoethanolamine and is kept the temperature；After heat preservation, it will be separated by solid-liquid separation with centrifuge, solid
Continue to be centrifuged to material and done, then material is placed in drier and is dried with clear water wash crystallization；It is cooled to after drying to material
Room temperature just obtains 2,2 '-azos (2- methyl-N- (2- hydroxyethyl) propionamide) product, the product content (HPLC) 98%
More than.Yield 55~75%, wherein the chemical equation of preparation method is as follows:
In a preferred embodiment of the invention, 2, the 2 '-azodiisobutyronitrile mass percentages are 98%
More than；The methanol quality percentage composition is 99% or more；99% or more the hydrogen chloride gas purity；The sodium methoxide
Solution quality percentage composition is between 25%~30%；The monoethanolamine mass percentage is 95% or more.
In a preferred embodiment of the invention, 2, the 2 '-azodiisobutyronitriles are configured to solution using toluene
It feeds intake.
In a preferred embodiment of the invention, every 1 parts by weight, 2,2 '-azodiisobutyronitrile adds 5~6 parts by weight first
Benzene.
In a preferred embodiment of the invention, the methanol is added using dropwise addition mode.
In a preferred embodiment of the invention, in order to promote fully reacting and improve yield, described 2,2 '-azos two
Isobutyronitrile, hydrogen chloride gas, methanol, monoethanolamine, the molar ratio between sodium methoxide are 1:2~2.3:2~2.3:2~2.15:
0.3~0.75；This methanol content does not include organic methanol content when being added to a small amount of methanol.Preferred molar ratio is 1:2.2:
2.2:2.1:0.68。
In a preferred embodiment of the invention, hydrogen chloride gas is passed through under the cooling at leisure to refer to 15~18
Hydrogen chloride gas is passed through at DEG C, the rate that is passed through of hydrogen chloride gas is 38~45 Grams Per Hours.
In a preferred embodiment of the invention, the control material temperature and carry out insulation reaction refer to control material temperature 18
~22 DEG C and heat preservation 36~42 hours.Preferably control material temperature at 20 DEG C and keeps the temperature 40 hours.
In a preferred embodiment of the invention, the hydrolysis time is 0.5~1.5 hour.
In a preferred embodiment of the invention, it is described it is organic be added to after a small amount of methanol to be evaporated under reduced pressure be for a period of time
It is evaporated under reduced pressure 2~4 hours after referring to the methanol of organic 5~10% weight percent for being added to organic phase weight, vacuum distillation
Pressure is -0.097~-0.1MPa.
In a preferred embodiment of the invention, organic phase is slowly dropped into the mixed solution of sodium methoxide and monoethanolamine
In and carry out heat preservation and refer to instill organic phase in the mixed solution of sodium methoxide and monoethanolamine with 95~105 Grams Per Hour speed
And kept the temperature, wherein holding temperature is 38~42 DEG C, and the time is 5~15 hours.To preferably have with 100 Grams Per Hour speed
Machine is mutually instilled in sodium methoxide and the mixed solution of monoethanolamine and is kept the temperature, and wherein holding temperature is 40 DEG C, and the time is 6 small
When.
Due to using following technical solution, main innovation point of the invention is the following:
1. the molar ratio of reasonably optimizing 2,2 '-azodiisobutyronitrile and methanol；
2. substituting thionyl chloride and 2 using hydrogen chloride gas, 2 '-azodiisobutyronitriles, methanol reaction avoid generating dioxy
Change sulphur gas；
3. introducing toluene makees solvent, keep layering interfaces clear, operates and be easy to carry out；
4. direct layering after hydrolysis takes away residual moisture by distilling a small amount of methanol, it is dry to avoid solid
The use of agent；
5. eliminating the step of individually obtaining intermediate azo-bis-iso-dimethyl, the intermediate obtained after hydrolysis is not necessarily to
It is separated from toluene, aminolysis reaction is directly carried out under toluene environment, avoids material loss.
Specific embodiment
The present invention further illustrates its technical process in combination with following example, and the following example, which is only used as, to be illustrated to use, and
Unrestricted protection scope of the present invention.
Embodiment 1
In 500 milliliters of three-necked flasks with stirring and reflux unit, 41.8 gram 98%2 is first put into, 2 '-azos two are different
Butyronitrile (0.25mol) and 200 grams of toluene put into 18.4 gram of 99.9% methanol (0.575mol), open stirring, open at 15 DEG C cooling
Beginning be passed through 19.4 gram of 99% hydrogen chloride gas (0.525mol) at leisure, wherein hydrogen chloride gas be passed through rate be with 38 grams/it is small
When rate.
Then control material temperature keeps the temperature 38 hours at 18 DEG C.Reaction solution is instilled with 110 Grams Per Hour rates after reaction
Reaction 0.5 hour is hydrolyzed in water, is layered after hydrolysis, 12 grams of methanol are added in organic phase, is evaporated under reduced pressure 2 hours, subtracts
Pressure distillation pressure is -0.097MPa.
After distillation, organic phase is instilled into 31.5 gram of 30% sodium methoxide solution (sodium methoxide with 105 Grams Per Hour rates
0.175mol) and in 33.5 gram of 98% monoethanolamine (0.5375mol) mixed solution, 6 hours, 42 DEG C of holding temperature are kept the temperature.
After heat preservation, it will be separated by solid-liquid separation with centrifuge, solid continues to use clear water wash crystallization, and centrifugation is dry to expecting, then by
Material is placed in drier and is dried.It is cooled to room temperature after drying to material, just obtains 2,2 '-azos (2- methyl-N- (2-
Hydroxyethyl) propionamide) product, yield (with 2,2 '-azodiisobutyronitrile meters) is 56.9%.Product content (HPLC)
99.5%.
Embodiment 2
In 500 milliliters of three-necked flasks with stirring and reflux unit, 41.8 gram 98%2 is first put into, 2 '-azos two are different
Butyronitrile (0.25mol) and 200 grams of toluene put into 16.4 gram of 99.9% methanol (0.5125mol), stirring are opened, at 15 DEG C cooling
Begin slowly to be passed through 20.3 gram of 99% hydrogen chloride gas (0.55mol), wherein hydrogen chloride gas be passed through rate be 45 grams/it is small
When.
Then 22 DEG C of material temperature are controlled, keeps the temperature 38 hours.After reaction by reaction solution with 110 Grams Per Hour rates) instill water
In be hydrolyzed reaction 1.5 hours, be layered after hydrolysis, in organic phase be added 18 grams of methanol, be evaporated under reduced pressure 2.5 hours, subtract
Pressure distillation pressure is -0.099MPa.
After distillation, organic phase is instilled into 27.0 gram of 30% sodium methoxide solution (sodium methoxide with 95 Grams Per Hour rates
0.15mol) and in 32.7 gram of 98% monoethanolamine (0.525mol) mixed solution, 6 hours, 38 DEG C of holding temperature are kept the temperature.
After heat preservation, it will be separated by solid-liquid separation with centrifuge, solid continues to use clear water wash crystallization, and centrifugation is dry to expecting, then by
Material is placed in drier and is dried.It is cooled to room temperature after drying to material, just obtains 2,2 '-azos (2- methyl-N- (2-
Hydroxyethyl) propionamide) product, yield (with 2,2 '-azodiisobutyronitrile meters) is 73.6%.Product content (HPLC)
99.8%.
Embodiment 3
In 500 milliliters of three-necked flasks with stirring and reflux unit, 41.8 gram 98%2 is first put into, 2 '-azos two are different
Butyronitrile (0.25mol) and 200 grams of toluene put into 17.6 gram of 99.9% methanol (0.55mol), open stirring, open at 15 DEG C cooling
Beginning is passed through 19.4 gram of 99% hydrogen chloride gas (0.525mol) at leisure, and it is 42 Grams Per Hours that wherein hydrogen chloride gas, which is passed through rate,.
Then 20 DEG C of material temperature are controlled, keeps the temperature 38 hours.Reaction solution is instilled into water with 110 Grams Per Hour rates after reaction
In be hydrolyzed reaction 1.5 hours, be layered after hydrolysis, in organic phase be added 20 grams of methanol, be evaporated under reduced pressure 2.5 hours, subtract
Pressure distillation pressure is -0.01MPa.
After distillation, organic phase is instilled into 15.3 gram of 30% sodium methoxide solution (sodium methoxide with 100 Grams Per Hours
0.085mol) and in 32.7 gram of 98% monoethanolamine (0.525mol) mixed solution, 6 hours, 41 DEG C of holding temperature are kept the temperature.
After heat preservation, it will be separated by solid-liquid separation with centrifuge, solid continues to use clear water wash crystallization, and centrifugation is dry to expecting, then by
Material is placed in drier and is dried.It is cooled to room temperature after drying to material, just obtains 2,2 '-azos (2- methyl-N- (2-
Hydroxyethyl) propionamide) product, yield (with 2,2 '-azodiisobutyronitrile meters) is 71.6%.Product content (HPLC)
99.2%.
Embodiment 4
In 500 milliliters of three-necked flasks with stirring and reflux unit, 41.8 gram 98%2 is first put into, 2 '-azos two are different
Butyronitrile (0.25mol) and 200 grams of toluene put into 17.6 gram of 99.9% methanol (0.55mol), open stirring, open at 15 DEG C cooling
Beginning is passed through 19.4 gram of 99% hydrogen chloride gas (0.525mol) at leisure, and it is 43 Grams Per Hours that wherein hydrogen chloride gas, which is passed through rate,.
Then 20 DEG C of material temperature are controlled, keeps the temperature 38 hours.Reaction solution is instilled into water with 100 Grams Per Hour rates after reaction
In be hydrolyzed reaction 1 hour, be layered after hydrolysis, in organic phase be added 22 grams of methanol, be evaporated under reduced pressure 3 hours, decompression steam
Evaporating pressure is -0.01MPa.
After distillation, organic phase is instilled into 30.6 gram of 30% sodium methoxide solution (sodium methoxide with 100 Grams Per Hour rates
0.17mol) and in 32.7 gram of 98% monoethanolamine (0.525mol) mixed solution, 6 hours, 39 DEG C of holding temperature are kept the temperature.
After heat preservation, it will be separated by solid-liquid separation with centrifuge, solid continues to use clear water wash crystallization, and centrifugation is dry to expecting, then by
Material is placed in drier and is dried.It is cooled to room temperature after drying to material, just obtains 2,2 '-azos (2- methyl-N- (2-
Hydroxyethyl) propionamide) product, yield (with 2,2 '-azodiisobutyronitrile meters) is 74.2%.Product content (HPLC)
99.5%.
Embodiment 5
In 500 milliliters of three-necked flasks with stirring and reflux unit, 41.8 gram 98%2 is first put into, 2 '-azos two are different
Butyronitrile (0.25mol) and 200 grams of toluene put into 17.6 gram of 99.9% methanol (0.55mol), open stirring, open at 15 DEG C cooling
Beginning is passed through 20.3 gram of 99% hydrogen chloride gas (0.55mol) at leisure, and it is 40 Grams Per Hours that wherein hydrogen chloride gas, which is passed through rate,.
Then 20 DEG C of material temperature are controlled, keeps the temperature 38 hours.Reaction solution is instilled into water with 100 Grams Per Hour rates after reaction
In be hydrolyzed reaction 1 hour, be layered after hydrolysis, in organic phase be added 22 grams of methanol, be evaporated under reduced pressure 4 hours, decompression steam
Evaporating pressure is -0.01MPa.
After distillation, 100 Grams Per Hour of organic phase is instilled into 30.6 gram of 30% sodium methoxide solution (sodium methoxide 0.17mol)
In 32.7 gram of 98% monoethanolamine (0.525mol) mixed solution, 3 hours, 40 DEG C of holding temperature are kept the temperature.
After heat preservation, it will be separated by solid-liquid separation with centrifuge, solid continues to use clear water wash crystallization, and centrifugation is dry to expecting, then by
Material is placed in drier and is dried.It is cooled to room temperature after drying to material, just obtains 2,2 '-azos (2- methyl-N- (2-
Hydroxyethyl) propionamide) product, yield (with 2,2 '-azodiisobutyronitrile meters) is 74.9%.Product content (HPLC)
99.5%.
Comparative example
In 500 milliliters of three-necked flasks with stirring and reflux unit, 41.8 gram 98%2 is first put into, 2 '-azos two are different
Butyronitrile (0.25mol) and 200 grams of dichloroethanes put into 80.0 gram of 99.9% methanol (2.5mol), open stirring, are cooled to 25 DEG C
After start that 63.1 gram of 99% thionyl chloride (0.525mol) is slowly added dropwise.
Then material temperature is controlled, keeps the temperature 6 hours.Material is instilled in 100 grams of 0 DEG C of ice water after reaction and is hydrolyzed instead
It answers, reaction is layered after 0.5 hour.By organic phase with appropriate water washing 3 times, layering, organic phase is dry with 6 grams of natrium carbonicum calcinatums,
Obtain liquid azo-bis-iso-dimethyl (intermediate).
Liquid azo-bis-iso-dimethyl instills 30.6 gram of 30% sodium methoxide solution (sodium methoxide 0.17mol) and 32.7 grams
In 98% monoethanolamine (0.525mol) mixed solution, 12 hours are kept the temperature at 55 DEG C.After reaction, it is cooled to room temperature, is added
100 grams 10 DEG C of cold water stirs 1 hour at 20 DEG C, and vacuum filtration will be separated by solid-liquid separation, and solid continues plus water recrystallization, filters, will
Solid material is placed in drier and is dried.It is cooled to room temperature after drying to material, just obtains 2,2 '-azos (2- methyl-N-
(2- hydroxyethyl) propionamide) product, yield (with 2,2 '-azodiisobutyronitrile meters) is 48.1%.Product content (HPLC)
99.4%.
Embodiment and comparative example is felt it is found that the embodiment for using the present processes effectively increases the receipts of product
Rate, and ensure that the quality of product, it is more in line with the existing production requirement for avoiding waste from improving efficiency.
Due to using following technical solution, main innovation point of the invention is:
1. the molar ratio of reasonably optimizing 2,2 '-azodiisobutyronitrile and methanol；
2. substituting thionyl chloride and 2 using hydrogen chloride gas, 2 '-azodiisobutyronitriles, methanol reaction avoid generating dioxy
Change sulphur gas；
3. introducing toluene makees solvent, keep layering interfaces clear, operates and be easy to carry out；
4. direct layering after hydrolysis takes away residual moisture by distilling a small amount of methanol, it is dry to avoid solid
The use of agent；
5. eliminating the step of individually obtaining intermediate azo-bis-iso-dimethyl, the intermediate obtained after hydrolysis is not necessarily to
It is separated from toluene, aminolysis reaction is directly carried out under toluene environment, avoids material loss.
Claims (13)
1. the preparation method of 2,2 '-azo of one kind (2- methyl-N- (2- hydroxyethyl) propionamide), it is characterized in that: being stirred having
It mixes and stirs in the reactor of reflux unit, first puts into 2,2 '-azodiisobutyronitriles, methanol and toluene, open stirring, under cooling slowly
Ground is passed through hydrogen chloride gas, then controls material temperature and carries out insulation reaction；Reaction solution is instilled in water after reaction and carries out water
Reaction is solved, hydrolysis terminates layering, organic vacuum distillation a period of time after being added to a small amount of methanol；After distillation, by organic phase
It is slowly dropped into sodium methoxide and the mixed solution of monoethanolamine and is kept the temperature；After heat preservation, it will be separated by solid-liquid separation with centrifuge,
Solid continues to be centrifuged to material and done, then material is placed in drier and is dried with clear water wash crystallization；It is cold to material after drying
But to room temperature, 2,2 '-azos (2- methyl-N- (2- hydroxyethyl) propionamide) product, the product content (HPLC) are just obtained
98% or more.Yield 55~75%, wherein the chemical equation of preparation method is as follows:
2. the preparation method of 2,2 '-azos of one kind as described in claim 1 (2- methyl-N- (2- hydroxyethyl) propionamide),
It is characterized in that, described 2,2 '-azodiisobutyronitrile mass percentages are 98% or more；The methanol quality percentage contains
Amount is 99% or more；99% or more the hydrogen chloride gas purity；The sodium methoxide solution mass percentage be 25%~
Between 30%；The monoethanolamine mass percentage is 95% or more.
3. the preparation method of 2,2 '-azos of one kind as described in claim 1 (2- methyl-N- (2- hydroxyethyl) propionamide),
It is characterized in that, described 2,2 '-azodiisobutyronitriles are configured to solution using toluene and feed intake.
4. the preparation method of 2,2 '-azos of one kind as claimed in claim 3 (2- methyl-N- (2- hydroxyethyl) propionamide),
It is characterized in that, every 1 parts by weight, 2,2 '-azodiisobutyronitrile adds 5~6 parts by weight of toluene.
5. the preparation method of 2,2 '-azos of one kind as described in claim 1 (2- methyl-N- (2- hydroxyethyl) propionamide),
It is characterized in that, the methanol is added using dropwise addition mode.
6. the preparation method of 2,2 '-azos of one kind as described in claim 1 (2- methyl-N- (2- hydroxyethyl) propionamide),
It is characterized in that, described 2,2 '-azodiisobutyronitriles, hydrogen chloride gas, methanol, monoethanolamine, the molar ratio between sodium methoxide
For 1:2~2.3:2~2.3:2~2.15:0.3~0.75；This methanol content does not include organic first when being added to a small amount of methanol
Alcohol content.
7. the preparation method of 2,2 '-azos of one kind as described in claim 1 (2- methyl-N- (2- hydroxyethyl) propionamide),
It is characterized in that, described 2,2 '-azodiisobutyronitriles, hydrogen chloride gas, methanol, monoethanolamine, the molar ratio between sodium methoxide
For 1:2.2:2.2:2.1:0.68, this methanol content does not include organic methanol content when being added to a small amount of methanol.
8. the preparation method of 2,2 '-azos of one kind as described in claim 1 (2- methyl-N- (2- hydroxyethyl) propionamide),
It is characterized in that, the control material temperature and carry out insulation reaction refer to control material temperature at 18~22 DEG C and keep the temperature 36~42 hours.
9. the preparation method of 2,2 '-azos of one kind as described in claim 1 (2- methyl-N- (2- hydroxyethyl) propionamide),
It is characterized in that, the control material temperature and carry out insulation reaction refer to control material temperature at 20 DEG C and keep the temperature 40 hours.
10. the preparation method of 2,2 '-azos of one kind as described in claim 1 (2- methyl-N- (2- hydroxyethyl) propionamide),
It is characterized in that, the hydrolysis time is 0.5~1.5 hour.
11. the preparation method of 2,2 '-azos of one kind as described in claim 1 (2- methyl-N- (2- hydroxyethyl) propionamide),
It organic be added to vacuum distillation a period of time after a small amount of methanol it is characterized in that, described and refer to organic organic phase weight that is added to
It is evaporated under reduced pressure 2~4 hours after the methanol of 5~10% weight percent, the pressure of vacuum distillation is -0.097~-0.1MPa.
12. the preparation method of 2,2 '-azos of one kind as described in claim 1 (2- methyl-N- (2- hydroxyethyl) propionamide),
It is characterized in that, organic phase is slowly dropped into sodium methoxide and the mixed solution of monoethanolamine and carry out heat preservation refer to 95~
Organic phase is instilled in sodium methoxide and the mixed solution of monoethanolamine and is kept the temperature by 105 Grams Per Hour speed, wherein holding temperature
It is 38~42 DEG C, the time is 5~15 hours.
13. the preparation method of 2,2 '-azos of one kind as described in claim 1 (2- methyl-N- (2- hydroxyethyl) propionamide),
It is characterized in that, organic phase is slowly dropped into sodium methoxide and the mixed solution of monoethanolamine and carry out heat preservation refer to 100 grams/
Organic phase is instilled in sodium methoxide and the mixed solution of monoethanolamine and is kept the temperature by hour speed, and wherein holding temperature is 40
DEG C, the time is 6 hours.
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