CN103980149B - A kind of synthetic method of equal benzene four formyl four octylame - Google Patents
A kind of synthetic method of equal benzene four formyl four octylame Download PDFInfo
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- CN103980149B CN103980149B CN201410241178.5A CN201410241178A CN103980149B CN 103980149 B CN103980149 B CN 103980149B CN 201410241178 A CN201410241178 A CN 201410241178A CN 103980149 B CN103980149 B CN 103980149B
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 title claims abstract description 26
- 238000010189 synthetic method Methods 0.000 title claims abstract description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 117
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 54
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 40
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 22
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims abstract description 20
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 230000009471 action Effects 0.000 claims abstract description 16
- 229940059260 amidate Drugs 0.000 claims abstract description 16
- NPUKDXXFDDZOKR-LLVKDONJSA-N etomidate Chemical compound CCOC(=O)C1=CN=CN1[C@H](C)C1=CC=CC=C1 NPUKDXXFDDZOKR-LLVKDONJSA-N 0.000 claims abstract description 16
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 9
- IMJSEMKPJOTJHY-UHFFFAOYSA-N formyl chloride oxolane Chemical compound C(=O)Cl.O1CCCC1 IMJSEMKPJOTJHY-UHFFFAOYSA-N 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000004821 distillation Methods 0.000 claims description 12
- 239000006260 foam Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 4
- 239000000047 product Substances 0.000 abstract description 20
- 150000001263 acyl chlorides Chemical class 0.000 abstract description 4
- 239000012046 mixed solvent Substances 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000004042 decolorization Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 26
- 239000002994 raw material Substances 0.000 description 10
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CLWRFNUKIFTVHQ-UHFFFAOYSA-N [N].C1=CC=NC=C1 Chemical compound [N].C1=CC=NC=C1 CLWRFNUKIFTVHQ-UHFFFAOYSA-N 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of synthetic method of equal benzene four formyl four octylame: the first step: add pyromellitic dianhydride and phosphorus pentachloride in phosphorus oxychloride solvent, back flow reaction generates equal benzene four formyl chloride, and the equal benzene four formyl chloride tetrahydrofuran (THF) generated is dissolved, obtain intermediate solution; Second step: add pyridine and a n-octyl amine in tetrahydrofuran solvent, drip intermediate solution in tetrahydrofuran solvent, equal benzene four formyl chloride in intermediate solution and a n-octyl amine generation amidate action, generate equal benzene four formyl four octylame.This synthetic method only adopts two steps can obtain very high equal benzene four formyl four octylame of purity, and product purity is greater than 97%, and yield is 75%; And the single solvent used, the by product generated in the first step is phosphorus oxychloride, also recyclablely applies mechanically, and overcomes in prior art the difficulty using mixed solvent to be difficult to recovery; Reaction temperature and easily control, and the acyl chlorides color obtained is more shallow, avoids decolorization process extra in second step reaction.
Description
Technical field
The present invention relates to a kind of synthetic method of equal benzene four formyl four octylame, belong to technical field of organic synthesis.
Background technology
Equal benzene four formyl four octylame is a kind of flotation agent and properties-correcting agent, and it changes the characteristic of some solvent viscosity, and this heavy oil for field of petroleum exploitation is enriched with important effect.At present, equal benzene four formyl four octylame obtains Preliminary Applications in containing the improvement of ore deposit sewage, but its synthetic method or an industry difficult problem.The difficulty using mixed solvent to be difficult to recovery is there is in former technique.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of synthetic method of equal benzene four formyl four octylame, and method is simple and product purity that is synthesis is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A synthetic method for equal benzene four formyl four octylame, comprises the following steps:
The first step: add pyromellitic dianhydride and phosphorus pentachloride in phosphorus oxychloride solvent, back flow reaction generates equal benzene four formyl chloride, wherein, the mol ratio of phosphorus oxychloride, phosphorus pentachloride and pyromellitic dianhydride is (2 ~ 2.5): (2.8 ~ 3.1): 1; And the equal benzene four formyl chloride tetrahydrofuran (THF) generated is dissolved, obtain intermediate solution;
Second step: add pyridine and a n-octyl amine in tetrahydrofuran solvent, wherein, the mass ratio of tetrahydrofuran (THF) and pyromellitic dianhydride is (15 ~ 30): 1, and the mol ratio of pyridine, a n-octyl amine and pyromellitic dianhydride is (4 ~ 6): (6 ~ 9): 1; In tetrahydrofuran solvent, drip intermediate solution, equal benzene four formyl chloride in intermediate solution and a n-octyl amine generation amidate action, generate equal benzene four formyl four octylame.
As a preferred technical solution of the present invention, in the first step, back flow reaction temperature is 123 ~ 125 °; Back flow reaction total time is 4.8 ~ 5.5h.
As a preferred technical solution of the present invention, in the first step, after back flow reaction terminates, first steam remaining phosphorus oxychloride solvent, then add tetrahydrofuran (THF) dissolving.
As a preferred technical solution of the present invention, in the first step, after back flow reaction terminates, by first for system air distillation to liquid temperature 155 ~ 160 °, cool to 120 ~ 130 ° again and use underpressure distillation instead, vacuum tightness is 6 ~ 6.5KPa, steams to liquid temperature 145 ~ 160 °, system is cooled to 80 ~ 90 ° afterwards, adds tetrahydrofuran (THF) and dissolves.
As a preferred technical solution of the present invention, in the first step, the tetrahydrofuran (THF) volume added and the ratio of pyromellitic dianhydride weight are (6 ~ 7): 1.
As a preferred technical solution of the present invention, in second step, before intermediate solution drips, system temperature reduces to-13 ~-17 °; In intermediate solution dropping process, system temperature is no more than 10 °.
As a preferred technical solution of the present invention, in second step, after intermediate solution dropwises, system is warming up to 28 ~ 30 °, and the amidate action time is 20 ~ 24h.
As a preferred technical solution of the present invention, in second step, after amidate action terminates, tetrahydrofuran (THF) is steamed, and obtain equal benzene four formyl four octylame by after remaining reactant foam washing, filtration and oven dry.
As a preferred technical solution of the present invention, in second step, tetrahydrofuran (THF) steam process: system is steamed to liquid temperature 85 degree, stops distillation, then system is cooled to 40 °.
As a preferred technical solution of the present invention, in second step, after being steamed by tetrahydrofuran (THF), residual reactant is first by anhydrous methanol foam washing twice repeatedly, and the wet product of filtering gained, again by acetone foam washing twice repeatedly, is finally dried.
The beneficial effect adopting technique scheme to produce is:
Synthetic method of the present invention is simple and practical, is raw material in the first step with pyromellitic dianhydride, under the condition of phosphorus oxychloride as solvent, reacts generate equal benzene four formyl chloride with phosphorus pentachloride, is swift in response and fully; Under the existence having acid binding agent pyridine, sufficient amidate action is there is with a n-octyl amine in second step after being dissolved by the equal benzene four formyl chloride tetrahydrofuran (THF) generated.This synthetic method only adopts two steps can obtain very high equal benzene four formyl four octylame of purity, and product purity is greater than 97%, and yield is 75%; And the single solvent used, the by product generated in the first step is phosphorus oxychloride, also recyclablely applies mechanically, and overcomes in prior art the difficulty using mixed solvent to be difficult to recovery; Reaction temperature and easily control, and the acyl chlorides color obtained is more shallow, avoids decolorization process extra in second step reaction.
The selection of several key conditions in synthetic method of the present invention:
(1) in the synthetic method the first step of the present invention, phosphorus pentachloride instead of thionyl chloride are selected in the chloride of pyromellitic dianhydride, its reason is: first, the boiling point of thionyl chloride is lower, and back flow reaction temperature cannot reach very high, and the coloring matter that the easy generation of long-time reaction not easily removes; Secondly, thionyl chloride and pyromellitic dianhydride cannot react thorough, always have pyromellitic dianhydride remnants, and the intermediate generated also can be brought in the middle of second step reaction, and are difficult to removing (the solubleness extreme difference of product); In a word, if use thionyl chloride to carry out chloride, the purity of the finished product is up to 80%, and color is dark.And compared to thionyl chloride, the boiling point of phosphorus pentachloride is higher, the temperature of back flow reaction therefore can be made to reach higher, and phosphorus pentachloride is more thorough with the reaction of pyromellitic dianhydride, not easily generate the coloring matter being difficult to remove, the purity of the finished product is higher, and color is also fine.
(2) prepare in the reaction of equal benzene four formyl chloride, phosphorus pentachloride (B) is 2 ~ 2.5:1 with the mol ratio of raw material pyromellitic dianhydride (A); Optimum molar ratio is 2.2:1, and back flow reaction 5 hours acid anhydrides can complete reaction.If phosphorus pentachloride consumption is less, if mol ratio is 2:1, then reaction time consumption is longer, and pyromellitic dianhydride raw material has remaining; If phosphorus pentachloride consumption is more, if mol ratio is 2.5:1, although without acid anhydrides residue, phosphorus pentachloride residue is more, when steaming solvent, and excessive phosphorus pentachloride Severe blockage prolong.
(3) prepare in the reaction of equal benzene four formyl chloride, the mol ratio of phosphorus oxychloride and raw material pyromellitic dianhydride (A) is 2.8 ~ 3.1:1; Optimum molar ratio is 3:1.Phosphorus oxychloride exists as solvent and reaction product, and added amount is too much unsuitable, and also unsuitable very few, institute's dosage, pasty state thick for reactant can be advisable, so neither affects operation, can not waste reaction volume and solvent again.Can obtain through experiment, the mol ratio of phosphorus trichloride and raw material pyromellitic dianhydride is that 3:1 is comparatively suitable.
(4), in the amidate action of all benzene four formyl chloride and a n-octyl amine, the consumption of solvents tetrahydrofurane (C) and the mass ratio of raw material pyromellitic dianhydride (A) are 15 ~ 30:1, and 20:1 is wherein optimum.
(5), in amidate action, be 4 ~ 6:1 as the pyridine (D) of acid binding agent and the mol ratio of pyromellitic dianhydride, optimum is 4.8:1.The ratio that pyridine (D) adds needs the residue considering raw material pyromellitic dianhydride (A), the i.e. purity of product, also the impact on speed of response will be considered, if add too much will cause early stage speed of response be difficult to control, the optimum molar ratio finally chosen is 4.8:1, reacting balance, without starting material left, product purity 97%.
(6), in amidate action, a n-octyl amine (E) is 6 ~ 9:1 with the mol ratio of pyromellitic dianhydride, and optimum is 7:1.Here the metering of equal benzene four formyl chloride and raw material pyromellitic dianhydride (A) are considered as being equal to, the mole number dropping into a n-octyl amine (E) in theory should be four times of pyromellitic dianhydride (A), but prove through experiment, one n-octyl amine (E) of four times amount is not enough to make the equal benzene four formyl chloride complete reaction of generation to become equal benzene four formyl four octylame, the intermediate of its non-complete reaction cannot remove, and therefore must increase the charging capacity of a n-octyl amine.Prove through experiment, the most suitable when a n-octyl amine (E) is 7:1 with the mol ratio of raw material pyromellitic dianhydride.
| E/A (mol ratio) | Reacting phenomenon | Quality product |
| 4∶1 | Drip in acyl chlorides process, heat up slightly slow | Product purity 60% |
| 5∶1 | Normally | Product purity 73% |
| 6∶1 | Normally | Product purity 85% |
| 7∶1 | Normally | Product purity 97% |
| 9∶1 | Normally | Product purity 96.5% |
(7) drip in the process of acyl chlorides, temperature is unsuitable too high, generally more than 10 °, in order to reach this object, system temperature should should not dropped to less than-10 °.
| Charge temperature | Product purity |
| 5 degree | 97% (feed time is long) |
| 10 degree | 97％ |
| 15 degree | 96％ |
| 25 degree | 94％ |
(8) the choosing of amidate action temperature: mainly consider reaction times and quality product, temperature is too high, and amidation is too fast, easily forms double team, causes the reduction of product purity; Temperature is too low, and the reaction times is oversize.Therefore, consider that to choose 29 ° as amidate action temperature be a comparatively suitable temperature, and be more or less the same with room temperature, easily realize.
Embodiment
Following examples describe the present invention in detail.Various raw material used in the present invention and items of equipment are conventional commercial product, all can be bought by market and directly obtain.In the middle of synthetic method of the present invention use the specification of main agents as shown in the table:
| Reagent name | Specification |
| Pyromellitic dianhydride | Purity 99% |
| Phosphorus pentachloride | 99.9％ |
| Phosphorus oxychloride | 99.8％ |
| Tetrahydrofuran (THF) | Analytical pure |
| Nitrogen | High Purity Nitrogen |
| Pyridine | Chemical pure |
| N-octyl amine | 99％ |
| Methyl alcohol | Technical pure |
| Acetone | Technical pure |
The reaction equation of synthesizing equal benzene four formyl four octylame disclosed in the present invention is:
Embodiment 1
The first embodiment of the present invention, comprises the following steps:
The first step: add pyromellitic dianhydride and phosphorus pentachloride in phosphorus oxychloride solvent, back flow reaction generates equal benzene four formyl chloride, wherein, the mol ratio of phosphorus oxychloride, phosphorus pentachloride and pyromellitic dianhydride is (2 ~ 2.5): (2.8 ~ 3.1): 1; And the equal benzene four formyl chloride tetrahydrofuran (THF) generated is dissolved, obtain intermediate solution.
Back flow reaction temperature is 123 ~ 125 °; Back flow reaction total time is 4.8 ~ 5.5h.
After back flow reaction terminates, first steam remaining phosphorus oxychloride solvent, then add tetrahydrofuran (THF) dissolving; The mode steaming remaining phosphorus oxychloride solvent is: by first for system air distillation to liquid temperature 155 ~ 160 °, cool to 120 ~ 130 ° again and use underpressure distillation instead, vacuum tightness is 6 ~ 6.5KPa, steam to liquid temperature 145 ~ 160 °, system is cooled to 80 ~ 90 ° afterwards, is steamed completely by remaining phosphorus oxychloride solvent.The ratio for the tetrahydrofuran (THF) volume and pyromellitic dianhydride weight that dissolve equal benzene four formyl chloride added is (6 ~ 7): 1.
Second step: add pyridine and a n-octyl amine in tetrahydrofuran solvent, wherein, the mass ratio of tetrahydrofuran (THF) and pyromellitic dianhydride is (15 ~ 30): 1, and the mol ratio of pyridine, a n-octyl amine and pyromellitic dianhydride is (4 ~ 6): (6 ~ 9): 1; In tetrahydrofuran solvent, drip intermediate solution, equal benzene four formyl chloride in intermediate solution and a n-octyl amine generation amidate action, generate equal benzene four formyl four octylame.
Before intermediate solution drips, system temperature reduces to-13 ~-17 °; In intermediate solution dropping process, system temperature is no more than 10 °; After intermediate solution dropwises, system is warming up to 28 ~ 30 °, and the amidate action time is 20 ~ 24h; After amidate action terminates, tetrahydrofuran (THF) is steamed: system is steamed to liquid temperature 85 °, stops distillation, then system is cooled to 40 °; After tetrahydrofuran (THF) steams, by remaining reactant foam washing, filtration and obtain equal benzene four formyl four octylame after drying, method be residual reactant first by anhydrous methanol foam washing twice repeatedly, filter the wet product of gained again by acetone foam washing twice repeatedly, finally dry.
Embodiment 2
The step of the second embodiment of the present invention is:
The first step: select 3L four-hole bottle, logical nitrogen, solvent is the phosphorus oxychloride of 1310g, adds the pyromellitic dianhydride of 620g and the phosphorus pentachloride of 1300g, mix, stirring and refluxing, reflux temperature is 124 °, after for some time, system becomes transparent, and backflow total time is 5h; Normal pressure steams phosphorus oxychloride, steams and reaches 158 ° to liquid temperature, cool to 120 °, carry out underpressure distillation, steam to liquid temperature 155 °, vacuum tightness is 6.3KPa, stops distillation, system cools to 85 °, in four-hole bottle, drip tetrahydrofuran (THF) 1000ml, this solution is transferred in 5L single port bottle, then add the tetrahydrofuran (THF) dilution of 3000ml, obtain the tetrahydrofuran solution of equal benzene four formyl chloride, i.e. intermediate solution.
Second step: select 30L reactor, logical nitrogen, adds tetrahydrofuran (THF) 12400g, pyridine 1079g and a n-octyl amine 2570.6g, cools to-15 °; Drip the intermediate solution obtained in the first step, control rate of addition, reactor temperature is no more than 10 °; After dropwising, be warming up to 29 °, reaction 22h, steam tetrahydrofuran (THF), steam to liquid temperature 85 °, stop distillation, cool to 40 °, after adding the anhydrous methanol foam washing of 6000ml, filtration, again use the anhydrous methanol foam washing of 6000ml, filtration, and then use wet product acetone 6000ml foam washing twice, after filtration, oven dry, obtain equal benzene four formyl four octylame of white powdery solids and 1489g, its purity is 97%, and yield is 75%.
Foregoing description only proposes, not as the single restricted condition to its technical scheme itself as the enforceable technical scheme of the present invention.
Claims (6)
1. a synthetic method for equal benzene four formyl four octylame, is characterized in that: described synthetic method comprises the following steps:
The first step: add pyromellitic dianhydride and phosphorus pentachloride in phosphorus oxychloride solvent, back flow reaction generates equal benzene four formyl chloride, and wherein, the mol ratio of phosphorus oxychloride, phosphorus pentachloride and pyromellitic dianhydride is (2 ~ 2.5): (2.8 ~ 3.1): 1; And the equal benzene four formyl chloride tetrahydrofuran (THF) generated is dissolved, obtain intermediate solution;
Second step: add pyridine and a n-octyl amine in tetrahydrofuran solvent, wherein, the mass ratio of tetrahydrofuran (THF) and pyromellitic dianhydride is (15 ~ 30): 1, and the mol ratio of pyridine, a n-octyl amine and pyromellitic dianhydride is (4 ~ 6): (6 ~ 9): 1; In tetrahydrofuran solvent, drip intermediate solution, equal benzene four formyl chloride in intermediate solution and a n-octyl amine generation amidate action, generate equal benzene four formyl four octylame;
In the first step, back flow reaction temperature is 123 ~ 125 °; Back flow reaction total time is 4.8 ~ 5.5h;
After back flow reaction terminates, first steam remaining phosphorus oxychloride solvent, then add tetrahydrofuran (THF) dissolving;
In second step, before intermediate solution drips, system temperature reduces to-13 ~-17 °; In intermediate solution dropping process, system temperature is no more than 10 °;
In second step, after intermediate solution dropwises, system is warming up to 28 ~ 30 °, and the amidate action time is 20 ~ 24h.
2. the synthetic method of equal benzene four formyl four octylame according to claim 1, it is characterized in that: after back flow reaction terminates, by first for system air distillation to liquid temperature 155 ~ 160 °, cool to 120 ~ 130 ° again and use underpressure distillation instead, vacuum tightness is 6 ~ 6.5KPa, steam to liquid temperature 145 ~ 160 °, system is cooled to 80 ~ 90 ° afterwards, adds tetrahydrofuran (THF) and dissolves.
3. the synthetic method of equal benzene four formyl four octylame according to claim 2, is characterized in that: the tetrahydrofuran (THF) volume added and the ratio of pyromellitic dianhydride weight are (6 ~ 7): 1.
4. the synthetic method of equal benzene four formyl four octylame according to claim 1, is characterized in that: in second step, after amidate action terminates, is steamed by tetrahydrofuran (THF), and obtains equal benzene four formyl four octylame by after remaining reactant foam washing, filtration and oven dry.
5. the synthetic method of equal benzene four formyl four octylame according to claim 4, is characterized in that: tetrahydrofuran (THF) steam process: system is steamed to liquid temperature 85 °, stops distillation, then system is cooled to 40 degree.
6. the synthetic method of equal benzene four formyl four octylame according to claim 4, it is characterized in that: after tetrahydrofuran (THF) is steamed, residual reactant is first by anhydrous methanol foam washing twice repeatedly, and the wet product of filtering gained, again by acetone foam washing twice repeatedly, is finally dried.
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| CN110256271A (en) * | 2019-07-04 | 2019-09-20 | 新岸诺亚（北京）催化科技有限公司 | Four octylame of 3,3`, 4,4`- biphenyl tetracarboxylic acyl and preparation method thereof |
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| WO2013040718A1 (en) * | 2011-09-23 | 2013-03-28 | Synoil Fluids Holdings Inc. | Pyromellitamide gelling agents |
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