CN108484529B - A kind of synthetic method of N, N '-di-2-ethylhexylphosphine oxide morpholine - Google Patents
A kind of synthetic method of N, N '-di-2-ethylhexylphosphine oxide morpholine Download PDFInfo
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- CN108484529B CN108484529B CN201810572759.5A CN201810572759A CN108484529B CN 108484529 B CN108484529 B CN 108484529B CN 201810572759 A CN201810572759 A CN 201810572759A CN 108484529 B CN108484529 B CN 108484529B
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- morpholine
- ethylhexylphosphine oxide
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- quaternary ammonium
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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
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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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of N, the synthetic method of N '-di-2-ethylhexylphosphine oxide morpholine, under certain temperature and solvent, by quaternary ammonium base catalysis, the paraformaldehyde of morpholine and formalin or solid forms is obtained by the condensation reaction of amine aldehyde.Using quaternary ammonium aqueous alkali as catalyst, concentration of aqueous solution is 1 ~ 30%, and dosage is the 0.01 ~ 0.1% of morpholine quality；Wherein the quaternary ammonium base is with general formula R1R2R3R4N+OH‑Shown in quaternary ammonium base, the molar ratio of morpholine and formaldehyde is 1:0.4 ~ 1:0.8, and reaction temperature is 70 ~ 90 DEG C.The present invention has by-product few, and target product yield is high, the advantages such as technological operation is simple, and preparation cost is low.
Description
Technical field
The present invention relates to formaldehyde release-type fungicide fields, and in particular to the synthesis side of a kind of N, N'- di-2-ethylhexylphosphine oxide morpholine
Method.
Background technique
Formaldehyde release-type fungicide is a kind of organic matter using formalin or paraformaldehyde as raw material Jing Guo polycondensation, can
Trace formaldehyde is slowly released within a certain period of time, to play formaldehyde very efficient effect in terms of killing microorganism.First
Aldehyde release type fungicide is that a kind of important bactericide is widely used in because of its low toxicity and unique sterilization feature
The industries such as industry, coating, water process, oil field.Formaldehyde sustained release class preservative as the microbiocidal agent being widely used earliest it
One, there is the usage history of decades, anti-corrosion, bactericidal effect have been obtained for widely accepting.
N, N'- di-2-ethylhexylphosphine oxide morpholine are called MBM, methylene dimorpholine, are a kind of with wide spectrum, fast and efficiently formaldehyde
Release type fungicide prevents corruption and foul odour suitable for inhibiting the growth and breeding of microorganism under various wet environments
It generates.N, N'- di-2-ethylhexylphosphine oxide morpholine are widely used in metal working fluid, detergent, leather, coating, paper pulp and adhesive etc.
Water-based system has many advantages, such as that the continuous action time is long, smell is mild, small to skin irritatin.With the global level of consumption and ring
Protect consciousness step up, each application field also increasingly focus on sterilization, corrosion-resistant importance, N, N'- di-2-ethylhexylphosphine oxide morpholine because
Its excellent sterilization feature also concern increasingly by each application field.
Existing to be reactant synthesis N with morpholine and formaldehyde, in the method for N'- di-2-ethylhexylphosphine oxide morpholine, most of is nothing
Directly reaction is made under catalysts conditions, and by-product is more in the product that this method obtains, and product yield is low.
2010 " Green Chemistry " periodical volume 12 the 6th it is interim describe under no catalysts conditions, pass through
Microwave radiation, 100 DEG C of reaction temperature, the reaction time 10 minutes, efficiency of pcr product can reach 98%.Although this method is in microwave radiation
Under the conditions of, the reaction time greatly shortens, and efficiency of pcr product is also higher, but this method realizes that facing production equipment in industrialized production wants
Ask high, the problem of consersion unit is expensive, high production cost.
Interim a kind of homemade support type oxidation is described at " Green Chemistry " periodical volume 18 the 3rd within 2016
Al catalysts are done under catalyst reaction with the support type aluminium oxide, and efficiency of pcr product reaches 96%, but catalyst preparation in this method
Complex process, reaction condition is more harsh, equally faces the higher problem of industrial production cost.
Therefore, the present invention provides using quaternary ammonium alkaloid compound as the N of catalyst, the synthesis of N'- di-2-ethylhexylphosphine oxide morpholine is new
Method has by-product few, and target product yield is high, the advantages such as technological operation is simple, and preparation cost is low, can generate well
Economic benefit and social benefit.
Summary of the invention
The purpose of the present invention is to overcome the above shortcomings, provides that a kind of by-product is few, target product yield is high, technique
The synthetic method of N easy to operate, preparation cost is low, N '-di-2-ethylhexylphosphine oxide morpholine.
The purpose of the present invention is achieved through the following technical solutions: the synthetic method of a kind of N, N '-di-2-ethylhexylphosphine oxide morpholine, In
Under certain temperature and solvent, under the catalysis that quaternary ammonium base makees catalyst, pass through morpholine and formalin or the poly of solid forms
Formaldehyde carries out the condensation reaction of amine aldehyde and obtains；Reaction equation is as follows:
；
Reaction temperature is 70 ~ 90 DEG C；Solvent is chlorine benzene,toluene,xylene or paraxylene.
A further improvement of the present invention is that: the molar ratio of morpholine and the formaldehyde is 1:0.4 ~ 1:0.8.
A further improvement of the present invention is that: with general formula R1R2R3R4N+OH-Shown in quaternary ammonium base be catalyst, aqueous solution
Concentration is 1 ~ 30%, and dosage is the 0.01 ~ 0.1% of morpholine quality, in which: R1、R2、R3、R4It may be the same or different, represent C1-C20
Alkyl, benzyl or aryl alkane.
Compared with the prior art, the present invention has the following advantages: the present invention has by-product few, and target product yield is high, work
The advantages such as skill is easy to operate, and preparation cost is low.
Specific embodiment:
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described, it is clear that described embodiments are some of the embodiments of the present invention, rather than
Whole embodiments.The elements and features described in one embodiment of the invention can be with one or more other realities
Elements and features shown in mode are applied to combine.It should be noted that being omitted for purposes of clarity, in explanation and nothing of the present invention
Expression and description close, component known to persons of ordinary skill in the art and processing.Based on the embodiments of the present invention, ability
Domain those of ordinary skill every other embodiment obtained under the premise of not making the creative labor, belongs to the present invention
The range of protection.
A kind of synthetic method of N, N '-di-2-ethylhexylphosphine oxide morpholine, reaction temperature be 70 ~ 90 DEG C and solvent be chlorobenzene, toluene,
Under conditions of dimethylbenzene or paraxylene, under the catalysis that quaternary ammonium base makees catalyst, pass through morpholine and formalin or solid shape
The paraformaldehyde of state carries out the condensation reaction of amine aldehyde and obtains, and the molar ratio of morpholine and formaldehyde is 1:0.4 ~ 1:0.8；Reaction equation is as follows:
；
With general formula R1R2R3R4N+OH-Shown in quaternary ammonium base be catalyst, concentration of aqueous solution be 1 ~ 30%, dosage be
The 0.01 ~ 0.1% of quinoline quality, in which: R1、R2、R3、R4It may be the same or different, represent C1-C20Alkyl, benzyl or aryl alkane.
Embodiment 1:
Solvent chlorobenzene, 174g(2 mol are sequentially added in the 500 mL four-hole boiling flasks equipped with electric mixer, condenser pipe)
Morpholine and 0.348g5% dodecyl dimethyl benzyl ammonium hydroxide aqueous solution, slowly by 81.08g(1mol) under ice-water bath
37% formalin is put into four-hole boiling flask, and temperature is no more than 70 DEG C during feeding intake, and heat preservation 3 is small at 70 DEG C after feeding intake
When, it is then cooled to room temperature, vacuum distillation removal solvent chlorobenzene and water, obtains target product N, N '-di-2-ethylhexylphosphine oxide morpholine
189.23g yield 98.01%.
Embodiment 2:
Solvent chlorobenzene, 174g(2 mol are sequentially added in the 500 mL four-hole boiling flasks equipped with electric mixer, condenser pipe)
10% myristyl benzyl dimethyl ammonium hydroxide aqueous solution of morpholine and 0.174g, slowly by 81.08g under ice-water bath
(1mol) 37% formalin is put into four-hole boiling flask, and temperature is no more than 70 DEG C during feeding intake, and is protected at 70 DEG C after feeding intake
Temperature 3 hours is then cooled to room temperature, vacuum distillation removal solvent chlorobenzene and water, finally obtains target product N, N '-di-2-ethylhexylphosphine oxide
Morpholine 188.79g, yield 98.23%.
Embodiment 3:
Solvent toluene, 174g(2 mol are sequentially added in the 500 mL four-hole boiling flasks equipped with electric mixer, condenser pipe)
10% trimethyl ammonium hydroxide aqueous solution of morpholine and 0.80g, slowly by 37.5g(1.2 mol) under ice-water bath
96% solid polyformaldehyde is put into four-hole boiling flask, and temperature is no more than 70 DEG C during feeding intake, and is kept the temperature at 70 DEG C after feeding intake
3 hours, it is then cooled to room temperature, vacuum distillation removal solvent chlorobenzene and water, obtains target product N, N '-di-2-ethylhexylphosphine oxide morpholine
188.42g yield 98.75%.
Embodiment 4:
Solvent xylene, 174g(2 are sequentially added in the 500 mL four-hole boiling flasks equipped with electric mixer, condenser pipe
Mol) 10% benzyltriethylammonium hydroxide aqueous solution of morpholine and 0.50g, slowly by 37.5g(1.2 mol) under ice-water bath
96% solid polyformaldehyde is put into four-hole boiling flask, and temperature is no more than 80 DEG C during feeding intake, and is kept the temperature at 80 DEG C after feeding intake
3 hours, it is then cooled to room temperature, vacuum distillation removal solvent chlorobenzene and water, obtains target product N, N '-di-2-ethylhexylphosphine oxide morpholine
189.17g yield 98.86%.
Embodiment 5:
Solvent xylene, 174g(2 are sequentially added in the 500 mL four-hole boiling flasks equipped with electric mixer, condenser pipe
Mol) 10 % tricaprylmethyl ammonium hydroxide aqueous solution of morpholine and 0.87g, slowly by 25g(0.8 mol) under ice-water bath
96% solid polyformaldehyde is put into four-hole boiling flask, and temperature is no more than 80 DEG C during feeding intake, and is kept the temperature at 80 DEG C after feeding intake
3 hours, it is then cooled to room temperature, vacuum distillation removal solvent chlorobenzene and water, obtains target product N, N '-di-2-ethylhexylphosphine oxide morpholine
151.56g yield 97.68%.
The present invention has by-product few, and target product yield is high, the advantages such as technological operation is simple, and preparation cost is low.
Finally, it should be noted that although the present invention and its advantage have been described in detail above it should be appreciated that not
Can be carried out in the case where beyond the spirit and scope of the present invention being defined by the claims appended hereto various changes, substitution and
Transformation.Moreover, the scope of the present invention is not limited only to the specific reality of process, equipment described in specification, means, method and steps
Apply example.One of ordinary skilled in the art holds from the disclosure it will be readily understood that can be used according to the present invention
The row function essentially identical to corresponding embodiment described herein obtains the result essentially identical with it, existing and future
Process, equipment, means, method or step to be developed.Therefore, the attached claims are intended to wrap in the range of them
Include such process, equipment, means, method or step.
Claims (3)
1. the synthetic method of a kind of N, N '-di-2-ethylhexylphosphine oxide morpholine, it is characterised in that: under certain temperature and solvent, in catalyst
Catalysis under, the condensation reaction of amine aldehyde is carried out by morpholine and formalin and is obtained, wherein with general formula R1R2R3R4N+OH-Shown in season
Ammonium alkali is catalyst, and concentration of aqueous solution is 1 ~ 30%, and dosage is the 0.01 ~ 0.1% of morpholine quality, in which: R1、R2、R3、R4
It may be the same or different, represent C1-C20Alkyl, benzyl；Reaction equation is as follows:
；
The reaction temperature is 70 ~ 90 DEG C；The solvent is chlorine benzene,toluene,xylene or paraxylene.
2. the synthetic method of a kind of N according to claim 1, N '-di-2-ethylhexylphosphine oxide morpholine, it is characterised in that: the morpholine
Molar ratio with the formaldehyde is 1:0.4 ~ 1:0.8.
3. the synthetic method of a kind of N according to claim 1, N '-di-2-ethylhexylphosphine oxide morpholine, it is characterised in that: the catalysis
Agent is dodecyl dimethyl benzyl ammonium hydroxide, myristyl benzyl dimethyl ammonium hydroxide, trimethyl hydrogen-oxygen
Change ammonium, benzyltriethylammonium hydroxide or tricaprylmethyl ammonium hydroxide.
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