CN106632143A - Method for cyclically preparing N-methyl morpholine - Google Patents
Method for cyclically preparing N-methyl morpholine Download PDFInfo
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- CN106632143A CN106632143A CN201611073210.9A CN201611073210A CN106632143A CN 106632143 A CN106632143 A CN 106632143A CN 201611073210 A CN201611073210 A CN 201611073210A CN 106632143 A CN106632143 A CN 106632143A
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- ammonium salt
- salt transfer
- transfer agent
- reaction
- circulation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/023—Preparation; Separation; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
- C07D295/03—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to acyclic carbon atoms
Abstract
The invention discloses a method for cyclically preparing N-methyl morpholine. The method comprises the following steps: (1) synthesizing, namely reacting N-methyldiethanolamine and sulfuric acid, cooling to room temperature so as to obtain a synthetic reaction solution; (2) performing ammonium salt transfer, namely adding N-methyldiethanolamine into the synthetic reaction solution obtained in the step (1), adding ammonium salt transfer agent for carrying out an ammonium salt transfer exchange reaction; (3) distilling, namely performing reduced pressure distillation on the ammonium salt transfer reaction solution obtained in the step (2) so as to respectively obtain the fraction and residues, wherein the fraction is N-methyl morpholine; and (4) carrying out circular reaction, namely carrying out synthetic reaction on the residue obtained in the step (3), cooling to room temperature so as to obtain the residue for the circular reaction, replacing the synthetic reaction solution and the ammonium salt transfer agent in the step (2) by using the residue for the circular reaction, and sequentially performing the ammonium salt transfer in the step (2) and distillation in the step (3).
Description
Technical field
The present invention relates to the circulation preparation method of a kind of circulation preparation method of organic compound, i.e. N-methylmorpholine.
Background technology
N-methylmorpholine is a kind of heterocyclic tertiary amines, the property with ether and amine, is widely used in insecticide, bactericide, plant
The synthesis of the agricultural chemical compounds such as thing growth regulator, is also used for surfactant, lubrication oil coolant, metal antirusting agent, fiber
The synthesis of the fine chemical products such as inorganic agent, structural formula is as shown in S-1.
Comprehensive literature reports that the preparation of current N-methylmorpholine mainly adopts following methods：
1), morpholine method (DE2205597,1973)：Methylate manufacture by raw material Jing of morpholine.The reaction that process is stirred in band
Intermittently carry out in kettle, raw material proportioning is morpholine：Formaldehyde：Formic acid=1：1～2：1～2, reaction temperature 5O～110 DEG C, normal pressure is received
Rate nearly 90%.This law technology is more ripe, and condition is gentleer, and yield is higher, but raw material morpholine is expensive, production cost compared with
It is high.
2), dichloroether method (US3155656,1964)：Dichloroether reacts in the presence of 110 DEG C and alkali with methylamine,
N-methylmorpholine, yield 50%, while by-product dimethyl ether can be obtained.Dichloroether may be from the pair that chlorohydrination produces oxirane
Product, it is inexpensive, but resource-constrained.This method yield is relatively low, and raw and auxiliary material consumption is larger, and the waste that process is produced is more.
3), diglycol process (DE333337182,1986)：Diethylene glycol (DEG), methylamine, hydrogen are at 150～250 DEG C and 1 × 105～5 ×
105N-methylmorpholine is catalyzed and synthesized under the pressure of Pa.Its weak point is to react to carry out at high temperature under high pressure, and raw materials used first
Amine and hydrogen are inflammable and explosive, and the big toxicity of methylamine smell is big, and effect on environment is big so that the high cost of production and safety guarantee.
4), diethanolamine method (SU7939787,1981)：Diethanol amine and dimethyl suflfate react at 105～200 DEG C,
Active oxidation Calcium treatment, decomposition of methyl product and neutralisation of sulphuric acid radical ion are used, N-methylmorpholine, yield 81～95 is obtained.This
Method course of reaction should be alkylated reaction, while carrying out ring-closure reaction again.So technically have high demands, selecting response
Property is relatively low.
5), N methyldiethanol amine method (PL85092,1977)：With N methyldiethanol amine as raw material, hydrochloric acid is catalysis
Agent, needs to parse the N-methylmorpholine hydrochloride of generation with inorganic base, generates a large amount of sodium chloride, consumes big, and discharge is big, is not inconsistent
Close Green Chemistry principle.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of circulation of N-methylmorpholine of environmental protection and prepares method.
In order to solve above-mentioned technical problem, the present invention provides a kind of circulation of N-methylmorpholine and prepares method, including following step
Suddenly：
1), synthesize：
Add in container (for example, four-hole boiling flask) and add sulfuric acid, N- methyl diethyls under N methyldiethanol amine, stirring
Hydramine：The mol ratio of sulfuric acid is 1：1.1～1.5 (preferably 1:1.1～1.2), reaction temperature is 150～180 DEG C, so as to steam
The water that reaction is generated, the reaction time is 6～8 hours；Room temperature is subsequently cooled to, synthesis reaction solution is obtained；
Remarks explanation：In this step, sulfuric acid is added in the way of being added dropwise, and temperature is controlled during dropwise addition and is less than 60
℃；
2), ammonium salt transfer：
In step 1) obtained by synthesis reaction solution in add (dropwises addition) N methyldiethanol amine and addition ammonium salt transfer agent
Carry out ammonium salt transfer exchange reaction (purpose is to obtain free state N-methylmorpholine)；
The N methyldiethanol amine and step 1) in the mol ratio of N methyldiethanol amine be 1：1, ammonium salt transfer agent
With step 1) in N methyldiethanol amine mass ratio be 1%～2%；
Ammonium salt transfer exchange reaction temperature is 60～70 DEG C, and the time is 30 ± 5 minutes；
Remarks explanation：In this step, N methyldiethanol amine is added in the way of being added dropwise, and time for adding is controlled 25～30
Minute；
3), distill：
By step 2) obtained by ammonium salt transfer reaction liquid carry out vacuum distillation, respectively obtain cut and kettle liquid, cut is N-
Methyl morpholine；
4), circular response：
By step 3) obtained by kettle liquid react 6～8 hours at a temperature of 150～180 DEG C, steam reaction generate water；
Room temperature is subsequently cooled to, circular response kettle liquid is obtained；
With circular response kettle liquid alternative steps 2) in synthesis reaction solution and ammonium salt transfer agent, then carry out successively
Step 2) described in ammonium salt transfer and step 3) described in distillation.
Remarks explanation：Step 3) obtained by kettle liquid be the mixed liquor containing N methyldiethanol amine, sulfuric acid and ammonium salt transfer agent；
The operation of one cycle reaction is above are only, later each circular response is operated in this way.It is anti-in circulation
In " ammonium salt transfer " step that should be corresponding, the consumption and reaction temperature of N methyldiethanol amine and time are with original step
2)。
As the improvement of the circulation preparation method of the N-methylmorpholine of the present invention：
The step 4) circular response in, with circular response kettle liquid alternative steps 2) in synthesis reaction solution and
Ammonium salt transfer agent, and addition ammonium salt transfer agent is supplemented, the ammonium salt transfer agent for supplementing addition accounts for the ammonium salt transfer agent for adding first
The 0.6%～3% of weight.
Described in remarks：Because of the loss of front primary first-order equation, it is therefore desirable to add ammonium salt transfer agent in right amount.
As the further improvement of the circulation preparation method of the N-methylmorpholine of the present invention：
The ammonium salt transfer agent is polyether substance, and polyether substance is polyethers or polyamine ether；Polyethers is polyethylene glycol
(PEG), for example, polyethylene glycol is PEG-8000, PEG-6000；Polyamine ether is, for example, T-5000, D-4000, M-2070.
As the further improvement of the circulation preparation method of the N-methylmorpholine of the present invention：
Step 1) in sulfuric acid for mass concentration >=98% the concentrated sulfuric acid.
In the present invention, step 1) it is to make N methyldiethanol amine that generation N- methyl is reacted under the catalytic action of sulfuric acid
Quinoline sulfate.
T-5000, D-4000, M-2070 are purchased from JEFFAMINE companies of the U.S..Its structural formula is as follows：
With N methyldiethanol amine as raw material, the reaction under the catalytic action of the concentrated sulfuric acid generates N-methylmorpholine to the present invention
Sulfate, the polyether substance by adding raw material N methyldiethanol amine in reactant liquor and as ammonium salt transfer agent carries out ammonium
Transfer exchange reaction obtains free state N-methylmorpholine, vacuum distillation, so as to steam all N-methylmorpholines；Kettle liquid continues anti-
Should；That is, after distillation terminates, ammonium salt transfer agent need not be processed, reusable edible.Then heating up carries out next secondary response, is formed
One recycles the technique that sulphuric acid catalysis synthesize N-methylmorpholine.In the present invention, the number of times of circulation can be example many times
Such as it is at least 5 times.
The course of reaction of the present invention is made up of following catalyst etherifying and ammonium salt transfer process：
The present invention has following technical advantage：
Using raw material with ammonium salt transfer agent by N-methylmorpholine sulfate conversion into free state N-methylmorpholine and N- methyl
Diethanol amine sulfate, compared with existing conventional method, it is not necessary to the inorganic base division thing sulfate such as NaOH, and can follow
Ring utilizes the concentrated sulfuric acid.Present invention process has saves sour material, does not use inorganic base material, does not produce sodium sulphate, and accessory substance is
The advantages of water.Therefore there is Important Economic meaning and the value of environmental protection.
Specific embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This.
Embodiment 1, a kind of circulation of N-methylmorpholine prepare method, with N methyldiethanol amine as raw material, the concentrated sulfuric acid (concentration
98%) it is catalyst, follows the steps below successively：
1), synthesize：
In the four-hole boiling flask of 500ml, by the 110g concentrated sulfuric acids, (98%) 1.1mol is slowly added dropwise and (controls temperature to be less than
60 DEG C, completion of dropwise addition in about 30 minutes) into the N methyldiethanol amine (1mol) of 119.16g, it is warming up to 160～170 DEG C and returns
Stream reaction 7 hours, has water to steam in course of reaction.After reaction terminates, room temperature is cooled to, obtains synthesis reaction solution.
2), ammonium salt transfer：
Under the conditions of being stirred at room temperature, by 119.16gN- methyl diethanolamines (1mol) instillation, (time for adding is about 30 points
Clock) in synthesis reaction solution, the PEG-8000 (about the 1% of N methyldiethanol amine quality) of 1.19g is then added, then rise
Temperature to 60～70 DEG C are stirred 30 minutes.
3), distill：
By step 2) obtained by ammonium salt transfer reaction liquid carry out vacuum distillation, under -0.95MPa pressure collect 55～60 DEG C
Under cut, obtain N-methylmorpholine 98.72g.Product purity is 99.9%；On the basis of the N methyldiethanol amine for consuming,
Yield is 97.5%.
Embodiment 1-1, first time circular response：
By the step 3 of embodiment 1) (that is, kettle liquid, the kettle liquid contains N methyldiethanol amine, sulfuric acid to distill the reactant liquor after terminating
With the polyether substance as ammonium salt transfer agent) be warming up to 160～170 DEG C react 7 hours, be subsequently cooled to room temperature, must circulate
Reaction kettle liquid；
With this circular response step 2 of kettle liquid alternate embodiment 1) in synthesis reaction solution and polyether substance (PEG-
8000), and the appropriate PEG-8000 for supplementing addition 0.015g, i.e. supplement PEG-8000 and account for the PEG-8000 for adding first
The 1.26% of weight.60～70 DEG C are then heated to, is stirred 30 minutes；The consumption and feed postition of N methyldiethanol amine is with real
The step of applying example 1 2).
The step of finally repeating above-described embodiment 1 3).
Remarks explanation：It is contemplated that every time ammonium salt transfer agent has moderate loss in experiment, it is therefore desirable to carry out appropriate
Addition.
Embodiment 1-2, second circular response：
Kettle liquid after the distillation of embodiment 1-1 is terminated carries out second circular response according to embodiment 1-1 methods described, mends
Fill the Change Weight To 0.02g of the PEG-8000 of addition.
By that analogy ,～the five circulation is circulated so as to obtain the third time corresponding to embodiment 1-3～embodiment 1-5,
Acquired results are described in table 1 below.
Table 1
Embodiment 2, a kind of circulation of N-methylmorpholine prepare method, with N methyldiethanol amine as raw material, the concentrated sulfuric acid (concentration
98%) it is catalyst, follows the steps below successively：
1), synthesize：
In 500ml four-hole boiling flasks, by the 120g concentrated sulfuric acids, (98%) 1.2mol is slowly added dropwise and (controls temperature and be less than 60
DEG C, completion of dropwise addition in about 30 minutes) into 119.16gN- methyl diethanolamines (1mol), it is warming up to 160～170 DEG C of backflows anti-
Answer 7 hours, have water to steam in course of reaction.After reaction terminates, room temperature is cooled to, obtains synthesis reaction solution.
2), ammonium salt transfer：
Under the conditions of being stirred at room temperature, by 119.16gN- methyl diethanolamines (1mol) instillation, (time for adding is about 30 points
Clock) in synthesis reaction solution, the T-5000 (about the 2% of N methyldiethanol amine quality) of 2.38g is then added, then heat up
Stir 30 minutes to 60～70 DEG C.
3), distill：
By step 2) obtained by ammonium salt transfer reaction liquid carry out vacuum distillation, under -0.95MPa pressure collect 55～60 DEG C
Under cut, obtain N-methylmorpholine 99.63g.Product purity is 99.9%；On the basis of the N methyldiethanol amine for consuming,
Yield is 98.4%.
Embodiment 2-1, first time circular response：
By the step 3 of embodiment 2) distillation terminate after reactant liquor (that is, kettle liquid) be warming up to 160～170 DEG C react 7 hours,
Room temperature is subsequently cooled to, circular response kettle liquid is obtained；
With this circular response step 2 of kettle liquid alternate embodiment 2) in synthesis reaction solution and polyether substance (T-
5000), and the appropriate T-5000 for supplementing addition 0.015g, i.e. supplement T-5000 and account for the T-5000 weight that adds first
0.63%.60～70 DEG C are then heated to, is stirred 30 minutes；The consumption and feed postition of N methyldiethanol amine is with embodiment 2
The step of 2).
The step of finally repeating above-described embodiment 2 3).
Embodiment 2-2, second circular response：
Kettle liquid after the distillation of embodiment 2-1 is terminated carries out second circular response according to embodiment 2-1 methods described, mends
Fill the Change Weight To 0.03g of the T-5000 of addition.
By that analogy ,～the five circulation is circulated so as to obtain the third time corresponding to embodiment 2-3～embodiment 2-5,
Acquired results are described in table 2 below.
Table 2
Embodiment 3～6, change embodiment 1 in reaction condition, that is, change step 1) in reaction temperature and reaction when
Between, remaining is equal to embodiment 1, and so as to obtain embodiment 3～6, gained total recovery is shown in Table 3.
Table 3
| Embodiment | 3 | 4 | 5 | 6 |
| Reaction temperature/DEG C | 150～159 | 171～180 | 160～170 | 160～170 |
| Reaction time/h | 7 | 7 | 6 | 8 |
| Yield/% | 96.8 | 97.1 | 96.9 | 97.1 |
| Product purity/% | 99.9 | 99.8 | 99.9 | 99.8 |
Embodiment 7～10, the species of the ammonium salt transfer agent changed in embodiment 1 and consumption, remaining process conditions are equal to
Embodiment 1, so as to obtain embodiment 7～10, gained total recovery is shown in Table 4.
Table 4
| Embodiment | 7 | 8 | 9 | 10 |
| Ammonium salt transfer agent model | PEG-6000 | T-5000 | D-4000 | M-2070 |
| Molecular weight | 5500～7000 | 5000 | 4000 | 2000 |
| Consumption/g | 1.19 | 1.19 | 2.38 | 2.38 |
| Mass fraction % | 1% | 1% | 2% | 2% |
| Yield/% | 97.2 | 97.1 | 97.5 | 97.5 |
| Product purity/% | 99.9 | 99.8 | 99.8 | 99.9 |
Comparative example 1, the use for cancelling ammonium salt transfer agent in embodiment 1, the i.e. consumption of PEG-8000 makes 0g into by 1.19g.
Remaining condition is equal to embodiment 1.Experiment acquired results：Product purity is 99.0%, and yield is 85.7%.
Comparative example 2～3, change embodiment 1 in reaction condition, that is, change step 1) in reaction temperature, reaction time,
Remaining is equal to embodiment 1, and so as to obtain comparative example 2～3, acquired results are shown in Table 5.
Table 5
| Comparative example | 2 | 3 |
| Reaction temperature/DEG C | 130～140 | 190～200 |
| Reaction time | 7 | 7 |
| Product purity/% | 99.3 | 99.1 |
| Yield/% | 84.9 | 85.1 |
Comparative example 4, the catalyst type (mole is constant, is still 1.1mol) changed in embodiment 1, will step 1) in
The concentrated sulfuric acid make concentrated hydrochloric acid into, remaining process is equal to embodiment 1, so as to obtain corresponding comparative example 4.
Comparative example 4-1, by comparative example 4 distillation terminate after kettle liquid followed according to recycling mode of the present invention
Ring reacts, so as to obtain comparative example 4-1.
Comparative example 5, the catalyst type (mole is constant, is still 1.1mol) changed in embodiment 1, will step 1) in
The concentrated sulfuric acid make SPA into, remaining process is equal to embodiment 1, so as to obtain corresponding comparative example 5.
Comparative example 5-1, by comparative example 5 distillation terminate after kettle liquid followed according to recycling mode of the present invention
Ring reacts, so as to obtain comparative example 5-1.
Acquired results are shown in Table 6.
Table 6
| Comparative example | 6 | 6-1 | 7 | 7-1 |
| Catalyst type | Concentrated hydrochloric acid | Concentrated hydrochloric acid | SPA | SPA |
| Catalyst recycles number of times | 0 | 1 | 0 | 1 |
| Ammonium salt transfer agent addition/g | 1.19 | 0.015 | 1.19 | 0.015 |
| Product purity/% | 99.2 | 99.0 | 99.2 | 99.0 |
| Yield/% | 87.5 | 83.1 | 86.4 | 81.9 |
Remarks explanation：The hydrochloric acid is the concentrated hydrochloric acid of mass concentration >=37%；The phosphoric acid is mass concentration >=85%
SPA.
Finally, it should also be noted that exemplified as above is only some specific embodiments of the invention.Obviously, the present invention not
It is limited to above example, also very many deformations.One of ordinary skill in the art can directly lead from present disclosure
The all deformations for going out or associating, are considered as protection scope of the present invention.
Claims (7)
- The circulation of 1.N- methyl morpholines prepares method, it is characterized in that comprising the following steps：1), synthesize：The lower addition sulfuric acid of N methyldiethanol amine, stirring, N methyldiethanol amine are added in a reservoir：The mol ratio of sulfuric acid is 1： 1.1～1.5, reaction temperature is 150～180 DEG C, and so as to steam the water that reaction is generated, the reaction time is 6～8 hours；Then it is cold But to room temperature, synthesis reaction solution is obtained；2), ammonium salt transfer：In step 1) obtained by synthesis reaction solution in add N methyldiethanol amine and add ammonium salt transfer agent carry out ammonium salt turn Move exchange reaction；The N methyldiethanol amine and step 1) in the mol ratio of N methyldiethanol amine be 1：1, ammonium salt transfer agent with step It is rapid 1) in N methyldiethanol amine mass ratio be 1%～2%；Ammonium salt transfer exchange reaction temperature is 60～70 DEG C, and the time is 30 ± 5 minutes；3), distill：By step 2) obtained by ammonium salt transfer reaction liquid carry out vacuum distillation, respectively obtain cut and kettle liquid, cut is N- methyl Morpholine；4), circular response：By step 3) obtained by kettle liquid react 6～8 hours at a temperature of 150～180 DEG C, steam reaction generate water；Then Room temperature is cooled to, circular response kettle liquid is obtained；With circular response kettle liquid alternative steps 2) in synthesis reaction solution and ammonium salt transfer agent, step is then carried out successively 2) described in ammonium salt transfer and step 3) described in distillation.
- 2. the circulation of N-methylmorpholine according to claim 1 prepares method, it is characterized in that：The step 4) circular response in, with circular response kettle liquid alternative steps 2) in synthesis reaction solution and ammonium salt Transfer agent, and addition ammonium salt transfer agent is supplemented, the ammonium salt transfer agent for supplementing addition accounts for the ammonium salt transfer agent weight for adding first 0.6%～3%.
- 3. the circulation of N-methylmorpholine according to claim 1 and 2 prepares method, it is characterized in that：The ammonium salt transfer agent is polyether substance.
- 4. the circulation of N-methylmorpholine according to claim 3 prepares method, it is characterized in that：The polyether substance is polyethers or polyamine ether.
- 5. the circulation of N-methylmorpholine according to claim 4 prepares method, it is characterized in that：The polyethers is polyethylene glycol；The polyamine ether is T-5000, D-4000, M-2070.
- 6. the circulation of N-methylmorpholine according to claim 5 prepares method, it is characterized in that：Polyethylene glycol is PEG-8000, PEG-6000.
- 7. the circulation of N-methylmorpholine according to claim 1 and 2 prepares method, it is characterized in that：Step 1) in sulfuric acid for mass concentration >=98% the concentrated sulfuric acid.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3155656A (en) * | 1960-04-14 | 1964-11-03 | Pennsalt Chemicals Corp | Novel process for nu-alkylmorpholines |
| CN101012208A (en) * | 2007-02-07 | 2007-08-08 | 浙江理工大学 | Process for preparing N-methyl morpholine |
| CN101638397A (en) * | 2009-06-22 | 2010-02-03 | 曲阜市圣泉催化应用科技有限公司 | Method for synthesizing N-methylmorpholine with granular solid superacid as catalyst |
-
2016
- 2016-11-29 CN CN201611073210.9A patent/CN106632143B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3155656A (en) * | 1960-04-14 | 1964-11-03 | Pennsalt Chemicals Corp | Novel process for nu-alkylmorpholines |
| CN101012208A (en) * | 2007-02-07 | 2007-08-08 | 浙江理工大学 | Process for preparing N-methyl morpholine |
| CN101638397A (en) * | 2009-06-22 | 2010-02-03 | 曲阜市圣泉催化应用科技有限公司 | Method for synthesizing N-methylmorpholine with granular solid superacid as catalyst |
Non-Patent Citations (1)
| Title |
|---|
| EMILE CHERBULIEZ等: "Recherches sup la formation et la transformation des esters XI11 ’).Sur la rCaction des aminoalcools avec l’acide polyphosphorique : phosphorylation et/ou cyclisation", 《VOLUMEN XLI, FASCICULUS IV》 * |
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