CN109053459A - A kind of preparation method of four N-propyl bromides - Google Patents
A kind of preparation method of four N-propyl bromides Download PDFInfo
- Publication number
- CN109053459A CN109053459A CN201811097054.9A CN201811097054A CN109053459A CN 109053459 A CN109053459 A CN 109053459A CN 201811097054 A CN201811097054 A CN 201811097054A CN 109053459 A CN109053459 A CN 109053459A
- Authority
- CN
- China
- Prior art keywords
- propyl
- ethyl alcohol
- reaction
- tpabr
- method described
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/12—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of quaternary ammonium compounds
Abstract
The invention discloses a kind of preparation methods of four N-propyl bromides.Using 1- N-Propyl Bromide and Tri-n-Propylamine as raw material, ethyl alcohol is solvent, synthesizes four N-propyl bromides in a kettle, is that 2.8:1.1:1 feeds according to ethyl alcohol, 1- N-Propyl Bromide, Tri-n-Propylamine molar ratio, reaction yield is up to 92%.The present invention accelerates reaction rate using the ethyl alcohol of small toxicity as solvent, and four N-propyl bromide crystal sizes of preparation are uniform, and purity is high, high income, operating procedure is simple, and production cost is low, has good prospects for commercial application.
Description
Technical field
The present invention relates to four N-propyl bromide preparation fields, are related to a kind of preparation method of four N-propyl bromides.
Background technique
Four n-propyl ammonium hydroxide (TPAOH), are synthesizing new catalysis materials --- the unique alkali of titanium-silicon molecular sieve TS-1
Source and template, currently, TS-1 molecular sieve realizes industrialization during oxidation of phenol prepares hydroquinone, in cyclohexanone
Ammoxidation prepare also show that during the important petrochemical process such as cyclohexanone oxime, preparing epoxypropane by epoxidation of propene it is good
Good prospects for commercial application, but existing major issue first is that at high cost, the price of TPAOH and consumption be influence molecular sieve at
This principal element.
The current country TPAOH there is no commodity, and foreign countries are used as specialty chemicals, expensive, even if tonne batch import is every
Ton price also up to million yuan, make in novel titanosilicate TS-1 cost only template one exceed per ton million yuan, serious resistance
Hinder the extensive use of novel titanosilicate.Therefore, template production new technique is developed, the cost for reducing TPAOH is to reduce newly
Type Titanium Sieve Molecular Sieve cost, realizes one of key factor of industrial application.The preparation method of TPAOH has silver oxide method, electricity at present
Solution and ion-exchange.Silver oxide method is expensive, and contains more bromine in solution；It is more that electrolysis method consumes the energy；With
It is excellent that four n-propyl brominations by TPAOH made from ion-exchange that (TPABr) is raw material have that synthesis cost is low, quality is controllable
Point, committed step are synthesis TPABr first, then carry out ion exchange through anion exchange resin and prepare TPAOH.
In the prior art, it discloses 1- N-Propyl Bromide liquid and Tri-n-Propylamine liquid reactions synthesizes four N-propyl bromide solids
Method, any solvent is not used in the method.With the progress of reaction, TPABr is precipitated in solid form, with reaction
Gradually increasing for amount of solid is generated, TPABr can be attached on the internal components such as agitating paddle, reaction kettle wall and thermocouple sheath, and
It finally is combined into lump in reaction kettle wall and reaction kettle bottom, products obtained therefrom particle is thick, viscous and uneven, this can seriously affect reaction
Heat transfer conditions in device, not only make reactor temperature can not stability contorting, side reaction can also occur because of hot-spot, influence
The quality of reaction yield (usually less than 40%) and reaction product TPABr.
For other existing about TPABr using in the preparation method of solvent, solvent for use is mostly ethyl acetate, acetone, fourth
Ketone, acetonitrile, n,N-Dimethylformamide etc., product TPABr be easily condensed into blocks to influence reaction rate, product yield and
TPABr quality, and there is a problem of that TPABr yield is low.
Summary of the invention
Low for the TPABr yield in the presence of the prior art, TPABr is condensed into blocks influence reaction speed in reaction kettle
The problem of rate, reaction yield, reaction product TPABr quality, the present invention propose a kind of preparation method of four N-propyl bromides, this
The preparation method of invention TPABr high income (92%) obtained, overcomes the condensation problem of reaction product TPABr, improves
The quality of reaction product TPABr, accelerates reaction rate.
The technical solution adopted by the invention is as follows:
A kind of preparation method of four N-propyl bromides includes the following steps: to make 1- N-Propyl Bromide, Tri-n-Propylamine in ethyl alcohol
It is reacted in the case where for solvent, to generate four N-propyl bromides.
The ethyl alcohol, 1- N-Propyl Bromide, Tri-n-Propylamine molar ratio be (1.5~5): (0.5~1.5): 1, optimum mole ratio
For 2.8:1.1:1.
The reaction is completed under the conditions of the spontaneous pressure of reaction kettle.
8~16h is reacted in the reaction at a temperature of 80~250 DEG C.
It is described after the reaction was completed, carry out vacuum distillation recycling ethyl alcohol and 1- N-Propyl Bromide；It is obtained after the completion of vacuum distillation
Isolate four N-propyl bromides in solution, the separation include be added into the solution detergent carry out washing suction filtration and
It is dry；The detergent includes acetone, butanone, ethyl acetate, acetonitrile, hexamethylene, petroleum ether；Temperature when dry is less than or equal to
80℃。
The present invention compared with the existing technology, has the advantage that
(1) present invention is accelerated reaction rate, is significantly improved four N-propyl bromides using ethyl alcohol as solvent
(TPABr) yield；
(2) condensation problem for overcoming reaction product TPABr improves the quality of reaction product TPABr, products therefrom TPABr
Crystal size is uniform；
(3) reaction is carried out in spontaneous pressure, is conducive to accelerate reaction rate, is easy to engineering construction, is convenient for commercial introduction (reaction pressure
Too low, then yield is not high；Hypertonia, then factory safety grade is excessively high, is unfavorable for engineering construction).
Specific embodiment
Below the technical scheme of the invention is illustrated by a specific example, but the scope of the present invention is not limited thereto:
Solubilizer does not prepare TPABr to embodiment 1
CH3CH2CH2Br+(C3H7)3N=(CH3CH2CH2)4NBr
According to molar ratio n (1- N-Propyl Bromide): n (Tri-n-Propylamine)=1.1:1, to polytetrafluoroethyllining lining stainless steel cauldron
Middle addition 1- N-Propyl Bromide 13.53g (0.11mol), Tri-n-Propylamine 14.33g (0.1mol), stir evenly, and seal reaction kettle, pressure
Condition be it is spontaneous pressure (etc. appearances container in, if temperature changes, will result in the variation of pressure, this variation is exactly
Spontaneous pressure), reaction kettle is placed in baking oven, is warming up to 100 DEG C, when temperature it is constant at 100 DEG C when start timing, stoichiometric number is small
When (16,18,20,22, for 24 hours) take out reaction kettle afterwards, washing suction filtration is carried out to reaction product using ethyl acetate, by what is filtered
Solid sample, which is put into vacuum oven, to be dried to constant mass, and simultaneously calculated yield is weighed, using a mole matter for method measurement product
Measure score.The yield and purity of the TPABr obtained under the differential responses time is listed in Table 1 below.
Table 1
| Reaction time (h) | TPABr yield (%) | TPABr purity (%) |
| 16 | 14.71 | 95.21 |
| 18 | 16.64 | 96.25 |
| 20 | 17.92 | 95.31 |
| 22 | 18.92 | 96.41 |
| 24 | 20.30 | 95.87 |
From result above as it can be seen that under conditions of not solubilizer, directly reacted by 1- N-Propyl Bromide, Tri-n-Propylamine, TPABr's
Yield becomes larger with the increase in reaction time, but the yield of TPABr is still very low, below 20.30%；When reaction
Between influence to TPABr purity it is unobvious, purity is between 95%~96%；In general, solubilizer does not prepare the effect of TPABr
Fruit is undesirable.
Embodiment 2 is added different solvents and prepares TPABr
According to molar ratio n (solvent): solvent (is once added one by n (1- N-Propyl Bromide): n (Tri-n-Propylamine)=5:1.1:1
Kind of solvent, solvent is respectively water, acetone, methanol, ethyl alcohol, ethyl acetate, dimethylbenzene), 1- N-Propyl Bromide, Tri-n-Propylamine be added to it is poly-
In tetrafluoroethene inner liner stainless steel reaction kettle, the Tri-n-Propylamine quality of addition is 14.33g (0.1mol), and 1- N-Propyl Bromide quality is
13.53g (0.11mol), stirs evenly, and seals reaction kettle, and pressure condition is spontaneous pressure, and reaction kettle is placed in baking oven, rises
Temperature to 100 DEG C, when temperature it is constant at 100 DEG C when start timing, react 14h.It is after reaction that reaction solution is cooling, reuse second
Acetoacetic ester carries out washing suction filtration to it, and (when solvent is water, methanol, ethyl alcohol, washing first carries out vacuum distillation recovered solvent before filtering
With 1- N-Propyl Bromide), filtered solid sample is put into vacuum oven and is dried to constant mass, simultaneously calculated yield is weighed,
Using a mole mass fraction for method measurement product.Change solvent type in experimentation successively to be tested, under different solvents
To TPABr yield and purity be listed in Table 2 below.
Table 2
| Solvent | TPABr yield (%) | TPABr purity (%) |
| Water | 17.23 | 98.79 |
| Acetone | 34.50 | 99.12 |
| Methanol | 43.98 | 98.59 |
| Ethyl alcohol | 79.21 | 99.73 |
| Ethyl acetate | 27.19 | 98.85 |
| Dimethylbenzene | 1.15 | 95.12 |
From result above as it can be seen that different solvents to TPABr to prepare influential effect obvious, preparation TPABr effect is optimal
Solvent is ethyl alcohol, and ethyl alcohol is n (ethyl alcohol): n (1- N-Propyl Bromide): under n (Tri-n-Propylamine)=5:1.1:1 in molar ratio as solvent
It feeds intake, in spontaneous pressure, reacts 14h at 100 DEG C, the yield of TPABr is up to the purity of 79.21%, TPABr up to 99.73%.
The alcohol solvent that different amounts are added in embodiment 3 prepares TPABr
According to molar ratio n (ethyl alcohol): n (1- N-Propyl Bromide): n (Tri-n-Propylamine)=(1~5): 1.1:1, by 4.61~
23.04g (0.1~0.5mol) ethyl alcohol, 13.53g (0.11mol) 1- N-Propyl Bromide, 14.33g (0.1mol) Tri-n-Propylamine are added poly-
It in tetrafluoroethene inner liner stainless steel reaction kettle, stirs evenly, seals reaction kettle, reaction kettle is placed in baking oven, is warming up to 100
DEG C, when temperature it is constant at 100 DEG C when start timing, spontaneous pressure react 14h.Decompression steaming is carried out to reaction solution after reaction
It evaporates, recycles ethyl alcohol and excessive 1- N-Propyl Bromide, then, ethyl acetate is added and carries out washing suction filtration, the solid sample that will have been filtered
It is put into vacuum oven and dries to constant mass, weigh simultaneously calculated yield, using a mole mass fraction for method measurement product.It is real
The additional amount for changing etoh solvent during testing successively is tested, the yield of the TPABr obtained under different ethanol consumptions and pure
Degree is listed in Table 3 below.
Table 3
| N (ethyl alcohol): n (1- N-Propyl Bromide): n (Tri-n-Propylamine) | TPABr yield (%) | TPABr purity (%) |
| 1:1.1:1 | 46.75 | 99.55 |
| 2:1.1:1 | 83.22 | 99.63 |
| 3:1.1:1 | 87.39 | 99.47 |
| 4:1.1:1 | 76.80 | 99.64 |
| 5:1.1:1 | 43.92 | 99.48 |
It can be seen from the above result that the molar ratio of ethyl alcohol, 1- N-Propyl Bromide, Tri-n-Propylamine is in (2~4): when 1.1:1 range,
The yield of TPABr significantly improves, and refines the additional amount of etoh solvent, yield and the purity column of obtained TPABr within this range
In table 4.
Table 4
| N (ethyl alcohol): n (1- N-Propyl Bromide): n (Tri-n-Propylamine) | TPABr yield (%) | TPABr purity (%) |
| 2.5:1.1:1 | 88.46 | 99.49 |
| 2.8:1.1:1 | 92.17 | 99.59 |
| 3.5:1.1:1 | 81.63 | 99.53 |
From the above results, it can be seen that the yield of TPABr first increases to be subtracted afterwards with the increase of etoh solvent dosage, purity is maintained
At higher level (99.5%), when n (ethyl alcohol): n (1- N-Propyl Bromide): when n (Tri-n-Propylamine)=2.8:1.1:1, the yield of TPABr
Highest, up to 92.17%, the purity of TPABr is 99.59% at this time.
Claims (9)
1. a kind of preparation method of four N-propyl bromides, includes the following steps:
React 1- N-Propyl Bromide, Tri-n-Propylamine in the case where ethyl alcohol is as solvent, to generate four N-propyl bromides.
2. according to the method described in claim 1, it is characterized by: the molar ratio of ethyl alcohol, 1- N-Propyl Bromide, Tri-n-Propylamine is (1.5
~5): (0.5~1.5): 1.
3. according to the method described in claim 2, it is characterized by: the molar ratio of ethyl alcohol, 1- N-Propyl Bromide, Tri-n-Propylamine is 2.8:
1.1:1。
4. according to the method described in claim 1, it is characterized by: the reaction is completed under the conditions of the spontaneous pressure of reaction kettle.
5. according to the method described in claim 1, it is characterized by: 8~16h is reacted in the reaction at a temperature of 80~250 DEG C.
6. according to the method described in claim 1, it is characterized by: it is described after the reaction was completed, carry out vacuum distillation recycling ethyl alcohol
With 1- N-Propyl Bromide.
7. according to the method described in claim 6, characterized by further comprising: from after the completion of vacuum distillation in the solution that obtains point
Four N-propyl bromides are separated out, the separation includes that detergent is added into the solution to carry out washing suction filtration and drying.
8. according to the method described in claim 7, it is characterized by: the detergent includes acetone, butanone, ethyl acetate, second
Nitrile, hexamethylene, petroleum ether.
9. according to the method described in claim 7, it is characterized by: temperature when dry is less than or equal to 80 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811097054.9A CN109053459A (en) | 2018-09-20 | 2018-09-20 | A kind of preparation method of four N-propyl bromides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811097054.9A CN109053459A (en) | 2018-09-20 | 2018-09-20 | A kind of preparation method of four N-propyl bromides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109053459A true CN109053459A (en) | 2018-12-21 |
Family
ID=64762239
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811097054.9A Pending CN109053459A (en) | 2018-09-20 | 2018-09-20 | A kind of preparation method of four N-propyl bromides |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109053459A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114318376A (en) * | 2022-01-26 | 2022-04-12 | 肯特催化材料股份有限公司 | Preparation method of tetrapropylammonium hydroxide and quaternary ammonium alkaline water solution prepared by same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4931593A (en) * | 1988-03-31 | 1990-06-05 | Degussa Aktiengesellschaft | Method for producing tetrapropylammonium bromide |
| JP2004010570A (en) * | 2002-06-10 | 2004-01-15 | Tosoh Corp | Method for producing quaternary halogenated ammonium salt |
| CN101148411A (en) * | 2007-11-06 | 2008-03-26 | 华东理工大学 | Method for preparing tetrapropylammonium bromide and horizontal autoclave |
| CN101870659A (en) * | 2010-07-20 | 2010-10-27 | 江苏扬农化工集团有限公司 | Preparation method for tetra-alkyl ammonium hydroxide and application |
| CN102408343A (en) * | 2010-09-20 | 2012-04-11 | 东北大学 | Method for synthetizing tetra(n-propyl)ammonium bromide |
| CN104098443A (en) * | 2014-07-24 | 2014-10-15 | 江苏索普（集团）有限公司 | Synthetic method of dichlorohydrin |
-
2018
- 2018-09-20 CN CN201811097054.9A patent/CN109053459A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4931593A (en) * | 1988-03-31 | 1990-06-05 | Degussa Aktiengesellschaft | Method for producing tetrapropylammonium bromide |
| JP2004010570A (en) * | 2002-06-10 | 2004-01-15 | Tosoh Corp | Method for producing quaternary halogenated ammonium salt |
| CN101148411A (en) * | 2007-11-06 | 2008-03-26 | 华东理工大学 | Method for preparing tetrapropylammonium bromide and horizontal autoclave |
| CN101870659A (en) * | 2010-07-20 | 2010-10-27 | 江苏扬农化工集团有限公司 | Preparation method for tetra-alkyl ammonium hydroxide and application |
| CN102408343A (en) * | 2010-09-20 | 2012-04-11 | 东北大学 | Method for synthetizing tetra(n-propyl)ammonium bromide |
| CN104098443A (en) * | 2014-07-24 | 2014-10-15 | 江苏索普（集团）有限公司 | Synthetic method of dichlorohydrin |
Non-Patent Citations (2)
| Title |
|---|
| 沈雨生等: "离子对的聚集作用及几种对称溴化烷基铵盐的合成(Ⅳ) ", 《吉林大学学报(理学版)》 * |
| 秦瑞霞等: "四正丙基溴化铵的合成研究 ", 《化工科技》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114318376A (en) * | 2022-01-26 | 2022-04-12 | 肯特催化材料股份有限公司 | Preparation method of tetrapropylammonium hydroxide and quaternary ammonium alkaline water solution prepared by same |
| CN114318376B (en) * | 2022-01-26 | 2022-08-05 | 肯特催化材料股份有限公司 | Preparation method of tetrapropylammonium hydroxide and quaternary ammonium alkaline water solution prepared by same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106496264B (en) | A kind of bisphenol-A is double（Diphenyl phosphoester）Continuous preparation method | |
| CN105924623B (en) | A kind of eugenol epoxy resin and the preparation method and application thereof | |
| CN1911890B (en) | Method of producing high-purity hydroxypivalaldehyde and/or dimer thereof | |
| CN105085392A (en) | Method for producing ethoxyquin | |
| CN109053459A (en) | A kind of preparation method of four N-propyl bromides | |
| CN111205200A (en) | Method and device for preparing heptafluoroisobutyronitrile | |
| CN105503582A (en) | Continuous production method for trifluoro monochloro chrysanthemic acid | |
| CN109678699A (en) | A kind of milk lactone spice is continuously synthesizing to method | |
| CN106748630A (en) | A kind of synthetic method of antalgesic intermediate Bromomethylcyclobutane | |
| CN109942373A (en) | The preparation method of monopentaerythritol and dipentaerythritol | |
| CN109485564B (en) | Novel method for preparing bifenthrin | |
| CN111892572B (en) | Synthesis process of watermelon ketone precursor | |
| CN108484484B (en) | Preparation method of 2-oxo-3-ethyl piperidinecarboxylate | |
| CN106478422A (en) | A kind of preparation method of paranitrophenylacetic acid | |
| CN217265508U (en) | Cis-4- (6-methyl-4-oxopyrimidinyl) -1-methoxycyclohexanecarboxylate production device | |
| CN106117039B (en) | A method of preparing sodium acetate using humin | |
| CN108276258A (en) | A kind of synthetic method of terephthaldehyde's ether | |
| CN110981831B (en) | Preparation method of 3-morpholine propanesulfonic acid | |
| CN107417533B (en) | Dimethyl isophthalate and process for producing the same | |
| CN115093317B (en) | Continuous process for preparing butenone by acid resin catalysis | |
| CN105837440B (en) | A kind of preparation process of the chloro- 2- acetyl group methoxy propane of 1,3- bis- | |
| CN109810012B (en) | Preparation method of anhydrous solvent blue 122 | |
| CN114835577B (en) | Aldehyde synthesis method | |
| CN114349765B (en) | Efficient green synthesis method of 2-phenylamino-3-methyl-6-dibutylamino fluorane | |
| CN111777524B (en) | Post-treatment method for preparing naphthol AS-PH |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20181221 |