CN105085161A - Preparation method of p-tetrafluorobenzyl - Google Patents
Preparation method of p-tetrafluorobenzyl Download PDFInfo
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- CN105085161A CN105085161A CN201510589111.5A CN201510589111A CN105085161A CN 105085161 A CN105085161 A CN 105085161A CN 201510589111 A CN201510589111 A CN 201510589111A CN 105085161 A CN105085161 A CN 105085161A
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Abstract
The invention discloses a method for preparing p-tetrafluorobenzyl, which mainly comprises the following steps: dissolving p-tetrachlorobenzyl and KF subjected to microwave treatment in a mole ratio of 1:(4-16) in an organic solvent, adding a phase-transfer catalyst (the mass ratio of the phase-transfer catalyst to the p-tetrachlorobenzyl is (1-20):100), thoroughly mixing, and reacting at 90-150 DEG C under the action of microwaves for 5-200 minutes; adding potassium carbonate, and reacting at 130-200 DEG C for 0.1-50 hours; and carrying out central control analysis to obtain the p-tetrafluorobenzyl product, wherein the KF microwave treatment power is 200-1000W, the organic solvent is one or mixture of sulfolane, N,N-dimethylformamide, N,N-dimethylacetamide and dimethyl sulfoxide, the mass ratio of the organic solvent to the p-tetrachlorobenzyl is (2-10):1, the phase-transfer catalyst is one or mixture of crown ethers, tetraphenyl phosphonium halides and quaternary ammonium salts, and the mole ratio of the acid-binding agent potassium carbonate to the p-tetrachlorobenzyl is (0.005-0.1):1.
Description
Technical field
The present invention relates to the preparation method of organic compound, be specifically related to a kind of preparation method to tetrafluoro benzyl.
Background technology
ParyleneHT film (1) is commercialization member up-to-date in Parylene series thin film, is a state-of-the-art type coating material in the world today.Except there is the advantage such as chemical stability, biocompatibility, thermostability that other Parylene films have, ParyleneHT film also has lower specific inductivity, better heat-resisting ability, the advantages such as stronger anti-uv-ray, are suitable as the protective material of high frequency microwave device.Usually, this polymkeric substance is synthesized by chemical vacuum gas phase deposition technology by ring disome 1,1,2,2,9,9,10,10-octafluoro [2,2] dimeric p-xylene (AF4,2), has the advantages that by product is few.
And compound is the important organic intermediate of synthesis AF4 to tetrafluoro benzyl, its structural formula is as follows:
European patent EP 949663 (1999) proposes two-step approach preparation to tetrafluoro benzyl, EP970938 (2000), Ru2032654 (1995) propose the method for preparation to tetrafluoro benzyl equally, but these preparation method's agents useful for same are cheap not, serious environmental pollution can be caused simultaneously, sometimes also need to use high pressure reaction assembly.
Japanese Patent JP200159700 (2000) proposes to use HF synthesis to tetrafluoro benzyl, but need use high pressure reaction assembly, and the fluorizating agent used is HF, is not easy to control reaction process, is also unfavorable for environmental protection simultaneously.
World Intellectual Property Organization WO982473 (1998) proposes solventless method preparation to tetrafluoro benzyl, but the difficulty being difficult to stir can be brought like this, under the condition do not stirred, 240 DEG C are reacted 7 days, target product productive rate is only 54%, and part can be decomposed to form block to tetrafluoro benzyl, is insoluble to and common are machine solvent, be difficult to cleaning reaction still.
Chinese patent CN1702062 (2005) proposes to use dimethylbenzene to do the operational path of solvent preparation to tetrafluoro benzyl, but need reaction 48 hours, only 60% is reached to tetrafluoro benzyl productive rate, in last handling process also relatively not easily, dimethylbenzene with easily azeotrope is formed to tetrafluoro benzyl, be difficult to purification target product.
The invention provides a kind of preparation method to tetrafluoro benzyl, it have employed microwave technology, prepares high yield and highly purified to tetrafluoro benzyl within a short period of time, thus solves contaminate environment of the prior art, length consuming time, needs the problems such as reaction under high pressure.
Summary of the invention
Technical problem solved by the invention is: provide a kind of preparation method to tetrafluoro benzyl newly, and in order to solve existing preparation to the contaminate environment existed in tetrafluoro benzyl technology, length consuming time, productive rate is low, cost is high and need the problems such as reaction under high pressure.
For the technical scheme solving the problems of the technologies described above employing is:
Provide a kind of novel method preparing tetrafluoro benzyl, by being 1:(4 ~ 16 by mol ratio) be dissolved in organic solvent to the KF after four benzyl chlorides and microwave treatment, add phase-transfer catalyst, mass ratio is phase-transfer catalyst: to four benzyl chlorides=(1 ~ 20): 100, it is made fully to mix, in 90 ~ 150 DEG C of reactions 5 ~ 200 minutes under microwave action.After adding a small amount of salt of wormwood, then react 0.1 ~ 50 hour at 130 ~ 200 DEG C.By middle control analysis, can obtain tetrafluoro benzyl product.Wherein, the power of described KF microwave treatment is 700 ~ 1000W, the consumption preferred molar ratio of KF is KF: react four benzyl chlorides=7:1, described organic solvent is tetramethylene sulfone, DMF, N, N-N,N-DIMETHYLACETAMIDE, one in methyl-sulphoxide or its mixture, preferred N,N-dimethylacetamide.Described organic solvent be (2 ~ 10) to the mass ratio of four benzyl chlorides: 1, preferred 5:1.In addition, phase-transfer catalyst is one in crown ether-like, tetraphenyl halogenation phosphine class, quaternary ammonium salt or its mixture, and wherein preferred mass is than being 18-hat-6 ethers: the mixture of tetraphenylphosphonium chloride=1:2, and every mole to four benzyl chlorides phase-transfer catalyst 5g; And acid binding agent salt of wormwood be (0.005 ~ 0.1) to the mol ratio of four benzyl chlorides: 1.
The chemical equation of above-mentioned reaction is as follows:
The invention has the beneficial effects as follows: compared with prior art, after the present invention adopts microwave treatment KF first, react with to four benzyl chlorides, and use microwave to prepare tetrafluoro benzyl as initiator, reaction times is shortened greatly, and products obtained therefrom purity is higher, and productive rate is better, reaction process can be carried out at ambient pressure, no longer needs high-tension apparatus; The solvent viscosity used is little, so no longer need comparatively multi-solvent just can realize being uniformly mixed, the usage quantity of the solvent reduced, and then the cost saved, in addition, use two kinds of phase-transfer catalysts to carry out composite, achieve synergistic effect, make better to react between two-phase, thus the scale operation making present method can be used for tetrafluoro benzyl.
Embodiment
The invention provides a kind of novel method prepared tetrafluoro benzyl, by being 1:(4 ~ 16 by mol ratio) be dissolved in organic solvent to the KF after four benzyl chlorides and microwave treatment, add phase-transfer catalyst, mass ratio is phase-transfer catalyst: to four benzyl chlorides=(1 ~ 20): 100, it is made fully to mix, in 90 ~ 150 DEG C of reactions 5 ~ 200 minutes under microwave action.After adding a small amount of salt of wormwood, then react 0.1 ~ 50 hour at 130 ~ 200 DEG C.By middle control analysis, can obtain tetrafluoro benzyl product.Wherein, the power of described KF microwave treatment is 200 ~ 1000W, the consumption preferred molar ratio of KF is KF: react four benzyl chlorides=7:1, described organic solvent is tetramethylene sulfone, DMF, N, N-N,N-DIMETHYLACETAMIDE, one in methyl-sulphoxide or its mixture, preferred N,N-dimethylacetamide.Described organic solvent be (2 ~ 10) to the mass ratio of four benzyl chlorides: 1, preferred 5:1.In addition, phase-transfer catalyst is one in crown ether-like, tetraphenyl halogenation phosphine class, quaternary ammonium salt or its mixture, and wherein preferred mass is than being 18-hat-6 ethers: the mixture of tetraphenylphosphonium chloride=1:2, and every mole to four benzyl chlorides phase-transfer catalyst 5g; Finally, the preferred 1mol of the consumption of acid binding agent salt of wormwood adds salt of wormwood 2.0g in four benzyl chlorides.
Below by embodiment, the invention will be further described
Embodiment 1: prepare the optimum proportioning to tetrafluoro benzyl and reaction conditions
20.30g (0.35mol) KF powder is placed in microwave, is process 3 times under the condition of 700W at microwave output power, each 5 minutes.Then the KF processed is added in the there-necked flask of 100mL fast, then in flask, add 0.08g18-hat-6 ethers, 0.17g tetraphenylphosphonium chloride, 12.20g (0.05mol) successively to four benzyl chlorides, finally add 61gN, N-N,N-DIMETHYLACETAMIDE.Reactor is placed in ultrasonic wave, ultrasonic 20 minutes, reaction mass is fully mixed.Under the effect of microwave, at 125 DEG C, use magnetic stirrer 1 hour.0.1gK is added in reaction system
2cO
3, then temperature is risen to 160 DEG C.Be incubated 18 hours at such a temperature.After reaction terminates, sampling, is shown by gas chromatographic analysis, and after removing solvent peak, be 86.55% to the concentration of tetrafluoro benzyl, all the other are difluoride.Aftertreatment is carried out to product, obtains pure in tetrafluoro benzyl,
1hNMR analyzes display: 1HNMR, δ 6.68 (t,
2j
fH=54,2H), 7.61 (s, 4H).
Embodiment 2: the consumption maximum value investigating KF
46.40g (0.8mol) KF powder is placed in microwave, is process 3 times under the condition of 700W at microwave output power, each 5 minutes.Then the KF processed is added in the there-necked flask of 100mL fast, then in flask, add 0.08g18-hat-6 ethers, 0.17g tetraphenylphosphonium chloride, 12.20g (0.05mol) successively to four benzyl chlorides, finally add 61gN, N-N,N-DIMETHYLACETAMIDE.Reactor is placed in ultrasonic wave, ultrasonic 20 minutes, reaction mass is fully mixed.Under the effect of microwave, at 125 DEG C, use magnetic stirrer 1 hour.0.1gK is added in reaction system
2cO
3, then temperature is risen to 160 DEG C.Be incubated 18 hours at such a temperature.After reaction terminates, sampling, is shown by gas chromatographic analysis, after removing solvent peak, is 65.15% to the concentration of tetrafluoro benzyl.
Embodiment 3: investigate KF consumption minimum value
11.60g (0.2mol) KF powder is placed in microwave, is process 3 times under the condition of 700W at microwave output power, each 5 minutes.Then the KF processed is added in the there-necked flask of 100mL fast, then in flask, add 0.08g18-hat-6 ethers, 0.17g tetraphenylphosphonium chloride, 12.20g (0.05mol) successively to four benzyl chlorides, finally add 61gN, N-N,N-DIMETHYLACETAMIDE.Reactor is placed in ultrasonic wave, ultrasonic 20 minutes, reaction mass is fully mixed.Under the effect of microwave, at 125 DEG C, use magnetic stirrer 1 hour.0.1gK is added in reaction system
2cO
3, then temperature is risen to 160 DEG C.Be incubated 18 hours at such a temperature.After reaction terminates, sampling, is shown by gas chromatographic analysis, after removing solvent peak, is 61.67% to the concentration of tetrafluoro benzyl.
Embodiment 4: adopt organic solvent sulfolane preparation to tetrafluoro benzyl
20.30g (0.35mol) KF powder is placed in microwave, is process 3 times under the condition of 700W at microwave output power, each 5 minutes.Then the KF processed is added in the there-necked flask of 100mL fast, then in flask, add 0.08g18-hat-6 ethers, 0.17g tetraphenylphosphonium chloride, 12.20g (0.05mol) successively to four benzyl chlorides, finally add 61g tetramethylene sulfone.Reactor is placed in ultrasonic wave, ultrasonic 20 minutes, reaction mass is fully mixed.Under the effect of microwave, at 125 DEG C, use magnetic stirrer 1 hour.0.1gK is added in reaction system
2cO
3, then temperature is risen to 160 DEG C.Be incubated 18 hours at such a temperature.After reaction terminates, sampling, is shown by gas chromatographic analysis, after removing solvent peak, is 55.13% to the concentration of tetrafluoro benzyl.
Embodiment 5: adopt the preparation of organic solvent DMF to tetrafluoro benzyl
20.30g (0.35mol) KF powder is placed in microwave, is process 3 times under the condition of 700W at microwave output power, each 5 minutes.Then the KF processed is added in the there-necked flask of 100mL fast, then in flask, add 0.08g18-hat-6 ethers, 0.17g tetraphenylphosphonium chloride, 12.20g (0.05mol) successively to four benzyl chlorides, finally add 61gN, dinethylformamide.Reactor is placed in ultrasonic wave, ultrasonic 20 minutes, reaction mass is fully mixed.Under the effect of microwave, at 125 DEG C, use magnetic stirrer 1 hour.0.1gK is added in reaction system
2cO
3, then temperature is risen to 160 DEG C.Be incubated 18 hours at such a temperature.After reaction terminates, sampling, is shown by gas chromatographic analysis, after removing solvent peak, is 38.36% to the concentration of tetrafluoro benzyl.
Embodiment 6: adopt the preparation of organic solvent methyl-sulphoxide to tetrafluoro benzyl
20.30g (0.35mol) KF powder is placed in microwave, is process 3 times under the condition of 700W at microwave output power, each 5 minutes.Then the KF processed is added in the there-necked flask of 100mL fast, then in flask, add 0.08g18-hat-6 ethers, 0.17g tetraphenylphosphonium chloride, 12.20g (0.05mol) successively to four benzyl chlorides, finally add 61g methyl-sulphoxide.Reactor is placed in ultrasonic wave, ultrasonic 20 minutes, reaction mass is fully mixed.Under the effect of microwave, at 125 DEG C, use magnetic stirrer 1 hour.0.1gK is added in reaction system
2cO
3, then temperature is risen to 160 DEG C.Be incubated 18 hours at such a temperature.After reaction terminates, sampling, is shown by gas chromatographic analysis, after removing solvent peak, is 21.46% to the concentration of tetrafluoro benzyl.
Embodiment 7: on the impact on tetrafluoro benzyl productive rate when investigation phase-transfer catalyst 18-hat-6 ethers and tetraphenylphosphonium chloride mass ratio are 10:1
20.30g (0.35mol) KF powder is placed in microwave, is process 3 times under the condition of 700W at microwave output power, each 5 minutes.Then the KF processed is added in the there-necked flask of 100mL fast, then in flask, add 0.24g18-hat-6 ethers, 0.02g tetraphenylphosphonium chloride, 12.20g (0.05mol) successively to four benzyl chlorides, finally add 61gN, N-N,N-DIMETHYLACETAMIDE.Reactor is placed in ultrasonic wave, ultrasonic 20 minutes, reaction mass is fully mixed.Under the effect of microwave, at 125 DEG C, use magnetic stirrer 1 hour.0.1gK is added in reaction system
2cO
3, then temperature is risen to 160 DEG C.Be incubated 18 hours at such a temperature.After reaction terminates, sampling, is shown by gas chromatographic analysis, after removing solvent peak, is 17.89% to the concentration of tetrafluoro benzyl.
Embodiment 8: on the impact on tetrafluoro benzyl productive rate when investigation phase-transfer catalyst 18-hat-6 ethers and tetraphenylphosphonium chloride mass ratio are 1:5
20.30g (0.35mol) KF powder is placed in microwave, is process 3 times under the condition of 700W at microwave output power, each 5 minutes.Then the KF processed is added in the there-necked flask of 100mL fast, then in flask, add 0.04g18-hat-6 ethers, 0.20g tetraphenylphosphonium chloride, 12.20g (0.05mol) successively to four benzyl chlorides, finally add 61g tetramethylene sulfone.Reactor is placed in ultrasonic wave, ultrasonic 20 minutes, reaction mass is fully mixed.Under the effect of microwave, at 125 DEG C, use magnetic stirrer 1 hour.0.1gK is added in reaction system
2cO
3, then temperature is risen to 160 DEG C.Be incubated 18 hours at such a temperature.After reaction terminates, sampling, is shown by gas chromatographic analysis, after removing solvent peak, is 36.97% to the concentration of tetrafluoro benzyl.
Embodiment 9: investigate consumption of organic solvent minimum value
20.30g (0.35mol) KF powder is placed in microwave, is process 3 times under the condition of 700W at microwave output power, each 5 minutes.Then the KF processed is added in the there-necked flask of 100mL fast, in flask, add 0.08g18-be more successively preced with-6 ethers, 0.17g tetraphenylphosphonium chloride, 12.20g (0.05mol) to four benzyl chlorides, finally add 24.40gN, N-N,N-DIMETHYLACETAMIDE.Reactor is placed in ultrasonic wave, ultrasonic 20 minutes, reaction mass is fully mixed.Under the effect of microwave, at 125 DEG C, use magnetic stirrer 1 hour.0.1gK is added in reaction system
2cO
3, then temperature is risen to 160 DEG C.Be incubated 18 hours at such a temperature.After reaction terminates, sampling, is shown by gas chromatographic analysis, after removing solvent peak, is 17.23% to the concentration of tetrafluoro benzyl.
Embodiment 10: investigate consumption of organic solvent maximum value
20.30g (0.35mol) KF powder is placed in microwave, is process 3 times under the condition of 700W at microwave output power, each 5 minutes.Then the KF processed is added in the there-necked flask of 100mL fast, then in flask, add 0.08g18-hat-6 ethers, 0.17g tetraphenylphosphonium chloride, 12.20g (0.05mol) successively to four benzyl chlorides, finally add 122gN, N-N,N-DIMETHYLACETAMIDE.Reactor is placed in ultrasonic wave, ultrasonic 20 minutes, reaction mass is fully mixed.Under the effect of microwave, at 110 DEG C, use magnetic stirrer 1 hour.0.1gK is added in reaction system
2cO
3, then temperature is risen to 160 DEG C.Be incubated 18 hours at such a temperature.After reaction terminates, sampling, is shown by gas chromatographic analysis, after removing solvent peak, is 41.69% to the concentration of tetrafluoro benzyl.
Embodiment 11: investigate each reactant react under microwave action needed for minimum temperature
20.30g (0.35mol) KF powder is placed in microwave, is process 3 times under the condition of 700W at microwave output power, each 5 minutes.Then the KF processed is added in the there-necked flask of 100mL fast, then in flask, add 0.08g18-hat-6 ethers, 0.17g tetraphenylphosphonium chloride, 12.20g (0.05mol) successively to four benzyl chlorides, finally add 61gN, N-N,N-DIMETHYLACETAMIDE.Reactor is placed in ultrasonic wave, ultrasonic 20 minutes, reaction mass is fully mixed.Under the effect of microwave, at 90 DEG C, use magnetic stirrer 1 hour.0.1gK is added in reaction system
2cO
3, then temperature is risen to 160 DEG C.Be incubated 18 hours at such a temperature.After reaction terminates, sampling, is shown by gas chromatographic analysis, after removing solvent peak, is 31.45% to the concentration of tetrafluoro benzyl.
Embodiment 12: investigate each reactant react under microwave action needed for top temperature
20.30g (0.35mol) KF powder is placed in microwave, is process 3 times under the condition of 700W at microwave output power, each 5 minutes.Then the KF processed is added in the there-necked flask of 100mL fast, then in flask, add 0.08g18-hat-6 ethers, 0.17g tetraphenylphosphonium chloride, 12.20g (0.05mol) successively to four benzyl chlorides, finally add 61gN, N-N,N-DIMETHYLACETAMIDE.Reactor is placed in ultrasonic wave, ultrasonic 20 minutes, reaction mass is fully mixed.Under the effect of microwave, at 200 DEG C, use magnetic stirrer 1 hour.0.1gK is added in reaction system
2cO
3, then temperature is risen to 160 DEG C.Be incubated 18 hours at such a temperature.After reaction terminates, sampling, is shown by gas chromatographic analysis, after removing solvent peak, is 23.12% to the concentration of tetrafluoro benzyl.
Embodiment 13: salt of wormwood is required maximum amount in preparation is to tetrafluoro benzyl process
20.30g (0.35mol) KF powder is placed in microwave, is process 3 times under the condition of 700W at microwave output power, each 5 minutes.Then the KF processed is added in the there-necked flask of 100mL fast, then in flask, add 0.08g18-hat-6 ethers, 0.17g tetraphenylphosphonium chloride, 12.20g (0.05mol) successively to four benzyl chlorides, finally add 61gN, N-N,N-DIMETHYLACETAMIDE.Reactor is placed in ultrasonic wave, ultrasonic 20 minutes, reaction mass is fully mixed.Under the effect of microwave, at 125 DEG C, use magnetic stirrer 1 hour.1.20gK is added in reaction system
2cO
3, then temperature is risen to 160 DEG C.Be incubated 18 hours at such a temperature.After reaction terminates, sampling, is shown by gas chromatographic analysis, after removing solvent peak, is 15.21% to the concentration of tetrafluoro benzyl.
Embodiment 14: salt of wormwood is required minimum quantity in preparation is to tetrafluoro benzyl process
20.30g (0.35mol) KF powder is placed in microwave, is process 3 times under the condition of 700W at microwave output power, each 5 minutes.Then the KF processed is added in the there-necked flask of 100mL fast, then in flask, add 0.08g18-hat-6 ethers, 0.17g tetraphenylphosphonium chloride, 12.20g (0.05mol) successively to four benzyl chlorides, finally add 61gN, N-N,N-DIMETHYLACETAMIDE.Reactor is placed in ultrasonic wave, ultrasonic 20 minutes, reaction mass is fully mixed.Under the effect of microwave, at 125 DEG C, use magnetic stirrer 1 hour.0.007gK is added in reaction system
2cO
3, then temperature is risen to 160 DEG C.Be incubated 18 hours at such a temperature.After reaction terminates, sampling, is shown by gas chromatographic analysis, after removing solvent peak, is 10.21% to the concentration of tetrafluoro benzyl.
Embodiment 15: add K
2cO
3the maximum value of rear desired reaction temperature
20.30g (0.35mol) KF powder is placed in microwave, is process 3 times under the condition of 700W at microwave output power, each 5 minutes.Then the KF processed is added in the there-necked flask of 100mL fast, then in flask, add 0.08g18-hat-6 ethers, 0.17g tetraphenylphosphonium chloride, 12.20g (0.05mol) successively to four benzyl chlorides, finally add 61gN, N-N,N-DIMETHYLACETAMIDE.Reactor is placed in ultrasonic wave, ultrasonic 20 minutes, reaction mass is fully mixed.Under the effect of microwave, at 125 DEG C, use magnetic stirrer 1 hour.0.1gK is added in reaction system
2cO
3, then temperature is risen to 200 DEG C.Be incubated 18 hours at such a temperature.After reaction terminates, sampling, is shown by gas chromatographic analysis, after removing solvent peak, is 40.44% to the concentration of tetrafluoro benzyl.
Embodiment 16: add K
2cO
3the minimum value of rear desired reaction temperature
20.30g (0.35mol) KF powder is placed in microwave, is process 3 times under the condition of 700W at microwave output power, each 5 minutes.Then the KF processed is added in the there-necked flask of 100mL fast, then in flask, add 0.08g18-hat-6 ethers, 0.17g tetraphenylphosphonium chloride, 12.20g (0.05mol) successively to four benzyl chlorides, finally add 61gN, N-N,N-DIMETHYLACETAMIDE.Reactor is placed in ultrasonic wave, ultrasonic 20 minutes, reaction mass is fully mixed.Under the effect of microwave, at 125 DEG C, use magnetic stirrer 1 hour.0.1gK is added in reaction system
2cO
3, then temperature is risen to 130 DEG C.Be incubated 18 hours at such a temperature.After reaction terminates, sampling, is shown by gas chromatographic analysis, after removing solvent peak, is 2.27% to the concentration of tetrafluoro benzyl.
Embodiment 17: add K
2cO
3the maximum value in rear required reaction times
20.30g (0.35mol) KF powder is placed in microwave, is process 3 times under the condition of 700W at microwave output power, each 5 minutes.Then the KF processed is added in the there-necked flask of 100mL fast, then in flask, add 0.08g18-hat-6 ethers, 0.17g tetraphenylphosphonium chloride, 12.20g (0.05mol) successively to four benzyl chlorides, finally add 61gN, N-N,N-DIMETHYLACETAMIDE.Reactor is placed in ultrasonic wave, ultrasonic 20 minutes, reaction mass is fully mixed.Under the effect of microwave, at 125 DEG C, use magnetic stirrer 1 hour.0.1gK is added in reaction system
2cO
3, then temperature is risen to 160 DEG C.Be incubated 50 hours at such a temperature.After reaction terminates, sampling, is shown by gas chromatographic analysis, after removing solvent peak, is 4.27% to the concentration of tetrafluoro benzyl.
Embodiment 18: add K
2cO
3the minimum value in rear required reaction times
20.30g (0.35mol) KF powder is placed in microwave, is process 3 times under the condition of 700W at microwave output power, each 5 minutes.Then the KF processed is added in the there-necked flask of 100mL fast, then in flask, add 0.08g18-hat-6 ethers, 0.17g tetraphenylphosphonium chloride, 12.20g (0.05mol) successively to four benzyl chlorides, finally add 61gN, N-N,N-DIMETHYLACETAMIDE.Reactor is placed in ultrasonic wave, ultrasonic 20 minutes, reaction mass is fully mixed.Under the effect of microwave, at 125 DEG C, use magnetic stirrer 1 hour.0.1gK is added in reaction system
2cO
3, then temperature is risen to 160 DEG C.Be incubated 0.1 hour at such a temperature.After reaction terminates, sampling, is shown by gas chromatographic analysis, after removing solvent peak, is 2.27% to the concentration of tetrafluoro benzyl.
Embodiment 19: investigate and be only suitable for single-phase transfer catalyst 18-hat-6 ethers to the impact on tetrafluoro benzyl productive rate
20.30g (0.35mol) KF powder is placed in microwave, is process 3 times under the condition of 700W at microwave output power, each 5 minutes.Then the KF processed is added in the there-necked flask of 100mL fast, then in flask, add 0.50g18-hat-6 ethers, 12.20g (0.05mol) successively to four benzyl chlorides, finally add 61gN, N-N,N-DIMETHYLACETAMIDE.Reactor is placed in ultrasonic wave, ultrasonic 20 minutes, reaction mass is fully mixed.Under the effect of microwave, at 125 DEG C, use magnetic stirrer 1 hour.0.1gK is added in reaction system
2cO
3, then temperature is risen to 160 DEG C.Be incubated 18 hours at such a temperature.After reaction terminates, sampling, is shown by gas chromatographic analysis, after removing solvent peak, is 20.46% to the concentration of tetrafluoro benzyl.
Embodiment 20: investigate and be only suitable for single-phase transfer catalyst tetraphenylphosphonium chloride to the impact on tetrafluoro benzyl productive rate
20.30g (0.35mol) KF powder is placed in microwave, is process 3 times under the condition of 700W at microwave output power, each 5 minutes.Then the KF processed is added in the there-necked flask of 100mL fast, then in flask, add 0.50g tetraphenylphosphonium chloride, 12.20g (0.05mol) successively to four benzyl chlorides, finally add 61gN, N-N,N-DIMETHYLACETAMIDE.Reactor is placed in ultrasonic wave, ultrasonic 20 minutes, reaction mass is fully mixed.Under the effect of microwave, at 125 DEG C, use magnetic stirrer 1 hour.0.1gK is added in reaction system
2cO
3, then temperature is risen to 160 DEG C.Be incubated 18 hours at such a temperature.After reaction terminates, sampling, is shown by gas chromatographic analysis, after removing solvent peak, is 25.46% to the concentration of tetrafluoro benzyl.
Embodiment 21: investigate the importance using ultrasonic wave to mix reactant
20.30g (0.35mol) KF powder is placed in microwave, is process 3 times under the condition of 700W at microwave output power, each 5 minutes.Then the KF processed is added in the there-necked flask of 100mL fast, then in flask, add 0.08g18-hat-6 ethers, 0.17g tetraphenylphosphonium chloride, 12.20g (0.05mol) successively to four benzyl chlorides, finally add 61gN, N-N,N-DIMETHYLACETAMIDE.Under the effect of microwave, at 125 DEG C, use magnetic stirrer 1 hour.0.1gK is added in reaction system
2cO
3, then temperature is risen to 160 DEG C.Be incubated 18 hours at such a temperature.After reaction terminates, sampling, is shown by gas chromatographic analysis, after removing solvent peak, is 3.27% to the concentration of tetrafluoro benzyl.
Embodiment 22: investigate initiator---minimum time amount needed for microwave action
20.30g (0.35mol) KF powder is placed in microwave, is process 3 times under the condition of 700W at microwave output power, each 5 minutes.Then the KF processed is added in the there-necked flask of 100mL fast, then in flask, add 0.08g18-hat-6 ethers, 0.17g tetraphenylphosphonium chloride, 12.20g (0.05mol) successively to four benzyl chlorides, finally add 61gN, N-N,N-DIMETHYLACETAMIDE.Reactor is placed in ultrasonic wave, ultrasonic 20 minutes, reaction mass is fully mixed.Under the effect of microwave, at 125 DEG C, use magnetic stirrer 5min.0.1gK is added in reaction system
2cO
3, then temperature is risen to 160 DEG C.Be incubated 18 hours at such a temperature.After reaction terminates, sampling, is shown by gas chromatographic analysis, after removing solvent peak, is 13.27% to the concentration of tetrafluoro benzyl.
Embodiment 23: investigate initiator---maximum amount needed for microwave action
20.30g (0.35mol) KF powder is placed in microwave, is process 3 times under the condition of 700W at microwave output power, each 5 minutes.Then the KF processed is added in the there-necked flask of 100mL fast, then in flask, add 0.08g18-hat-6 ethers, 0.17g tetraphenylphosphonium chloride, 12.20g (0.05mol) successively to four benzyl chlorides, finally add 61gN, N-N,N-DIMETHYLACETAMIDE.Reactor is placed in ultrasonic wave, ultrasonic 20 minutes, reaction mass is fully mixed.Under the effect of microwave, at 125 DEG C, use magnetic stirrer 200min.0.1gK is added in reaction system
2cO
3, then temperature is risen to 160 DEG C.Be incubated 18 hours at such a temperature.After reaction terminates, sampling, is shown by gas chromatographic analysis, after removing solvent peak, is 8.27% to the concentration of tetrafluoro benzyl.
Embodiment 24: investigate the importance of KF being carried out to microwave treatment
29.00g (0.50mol) KF is joined in the there-necked flask of 100mL, then in flask, adds 0.50g18-hat-6 ethers, 12.20g (0.05mol) successively to four benzyl chlorides, finally add 61gN, N-N,N-DIMETHYLACETAMIDE.Reactor is placed in ultrasonic wave, ultrasonic 20 minutes, reaction mass is fully mixed.Under the effect of microwave, at 125 DEG C, use magnetic stirrer 1 hour.0.1gK is added in reaction system
2cO
3, then temperature is risen to 160 DEG C.Be incubated 18 hours at such a temperature.After reaction terminates, sampling, is shown by gas chromatographic analysis, and after removing solvent peak, driftlessness product generates.
Embodiment 25: investigate initiator---the importance of microwave action
20.30g (0.35mol) KF powder is placed in microwave, is process 3 times under the condition of 700W at microwave output power, each 5 minutes.Then the KF processed is added in the there-necked flask of 100mL fast, then in flask, add 0.08g18-hat-6 ethers, 0.17g tetraphenylphosphonium chloride, 12.20g (0.05mol) successively to four benzyl chlorides, finally add 61gN, N-N,N-DIMETHYLACETAMIDE.Reactor is placed in ultrasonic wave, ultrasonic 20 minutes, reaction mass is fully mixed.Magnetic stirrer is used 1 hour at 125 DEG C.0.1gK is added in reaction system
2cO
3, then temperature is risen to 160 DEG C.Be incubated 18 hours at such a temperature.After reaction terminates, sampling, is shown by gas chromatographic analysis, and driftlessness product generates.
More than show and describe ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (8)
1. the preparation method to tetrafluoro benzyl, it is characterized in that: by being 1:(4 ~ 16 by mol ratio) be dissolved in organic solvent to the KF after four benzyl chlorides and microwave treatment, add phase-transfer catalyst, mass ratio is phase-transfer catalyst: to four benzyl chlorides=(1 ~ 20): 100, make it fully mix, in 90 ~ 150 DEG C of reactions 5 ~ 200 minutes under microwave action, after adding salt of wormwood, then react 0.1 ~ 50 hour at 130 ~ 200 DEG C, by middle control analysis, can obtain tetrafluoro benzyl product; Wherein, the power of described microwave treatment is 200 ~ 1000W, described organic solvent is tetramethylene sulfone, DMF, N, N-N,N-DIMETHYLACETAMIDE, one in methyl-sulphoxide or its mixture, described organic solvent be (2 ~ 10) to the mass ratio of four benzyl chlorides: 1, in addition, phase-transfer catalyst is one in crown ether-like, tetraphenyl halogenation phosphine class, quaternary ammonium salt or its mixture, acid binding agent salt of wormwood be (0.005 ~ 0.1) to the mol ratio of four benzyl chlorides: 1.
2. a kind of preparation method to tetrafluoro benzyl according to claim 1, is characterized in that: KF be 7:1 to the mol ratio of four benzyl chlorides.
3. a kind of preparation method to tetrafluoro benzyl according to claim 1, is characterized in that: described organic solvent is N,N-dimethylacetamide.
4. a kind of preparation method to tetrafluoro benzyl according to claim 1 or 3, is characterized in that: described organic solvent be 5:1 to the mass ratio of four benzyl chlorides.
5. a kind of preparation method to tetrafluoro benzyl according to claim 1, is characterized in that: described phase-transfer catalyst is the mixture that 18-is preced with-6 ethers and tetraphenylphosphonichloride chloride, and its mass ratio is 1:2, and every mole to four benzyl chlorides phase-transfer catalyst 5g.
6. a kind of preparation method to tetrafluoro benzyl according to claim 1, is characterized in that: the consumption of described acid binding agent salt of wormwood is that 1mol is to adding 2.0 milligrams, salt of wormwood in four benzyl chlorides.
7. a kind of preparation method to tetrafluoro benzyl according to claim 1, be is characterized in that: be dissolved in organic solvent to the KF after four benzyl chlorides and microwave treatment, after adding phase-transfer catalyst, is fully mixed by ultrasonic wave.
8. a kind of preparation method to tetrafluoro benzyl according to claim 1, is characterized in that: the power of described microwave treatment is 700W.
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