CN103214400A - Preparation method of hexaflumuron - Google Patents
Preparation method of hexaflumuron Download PDFInfo
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- CN103214400A CN103214400A CN201310129728XA CN201310129728A CN103214400A CN 103214400 A CN103214400 A CN 103214400A CN 201310129728X A CN201310129728X A CN 201310129728XA CN 201310129728 A CN201310129728 A CN 201310129728A CN 103214400 A CN103214400 A CN 103214400A
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- oxyethyl group
- chloride
- phenylurea
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- RGNPBRKPHBKNKX-UHFFFAOYSA-N hexaflumuron Chemical compound C1=C(Cl)C(OC(F)(F)C(F)F)=C(Cl)C=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F RGNPBRKPHBKNKX-UHFFFAOYSA-N 0.000 title abstract 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 45
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 30
- ZVCDLGYNFYZZOK-UHFFFAOYSA-M sodium cyanate Chemical compound [Na]OC#N ZVCDLGYNFYZZOK-UHFFFAOYSA-M 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 24
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 15
- 239000011592 zinc chloride Substances 0.000 claims abstract description 15
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000012065 filter cake Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- QRHUZEVERIHEPT-UHFFFAOYSA-N 2,6-difluorobenzoyl chloride Chemical compound FC1=CC=CC(F)=C1C(Cl)=O QRHUZEVERIHEPT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 7
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- LUBJCRLGQSPQNN-UHFFFAOYSA-N 1-Phenylurea Chemical compound NC(=O)NC1=CC=CC=C1 LUBJCRLGQSPQNN-UHFFFAOYSA-N 0.000 claims description 52
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 30
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 30
- 229910052731 fluorine Inorganic materials 0.000 claims description 30
- 239000011737 fluorine Substances 0.000 claims description 30
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 28
- 239000004202 carbamide Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 17
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 7
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- AJSHDAOMUKXVDC-UHFFFAOYSA-N butan-1-amine;sulfuric acid Chemical compound CCCC[NH3+].OS([O-])(=O)=O AJSHDAOMUKXVDC-UHFFFAOYSA-N 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 3
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- 235000013877 carbamide Nutrition 0.000 claims 11
- 150000003672 ureas Chemical class 0.000 claims 3
- 239000000047 product Substances 0.000 abstract description 23
- 238000000034 method Methods 0.000 abstract description 6
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 4
- 238000004821 distillation Methods 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- PJUKOQFWMMLIMU-UHFFFAOYSA-N [3,5-dichloro-4-(1,1,2,2-tetrafluoroethoxy)phenyl]urea Chemical compound ClC=1C=C(C=C(C1OC(C(F)F)(F)F)Cl)NC(=O)N PJUKOQFWMMLIMU-UHFFFAOYSA-N 0.000 abstract 2
- 238000005406 washing Methods 0.000 abstract 2
- JIPDPVQPKLVDIU-UHFFFAOYSA-N 3,5-dichloro-4-(1,1,2,2-tetrafluoroethoxy)aniline Chemical compound NC1=CC(Cl)=C(OC(F)(F)C(F)F)C(Cl)=C1 JIPDPVQPKLVDIU-UHFFFAOYSA-N 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 15
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 9
- 239000001110 calcium chloride Substances 0.000 description 9
- 229910001628 calcium chloride Inorganic materials 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000004587 chromatography analysis Methods 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 8
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 8
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 7
- 238000010907 mechanical stirring Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- -1 isocyanide acyl ester compound Chemical class 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- HRYILSDLIGTCOP-UHFFFAOYSA-N N-benzoylurea Chemical class NC(=O)NC(=O)C1=CC=CC=C1 HRYILSDLIGTCOP-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 231100000004 severe toxicity Toxicity 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- AVRQBXVUUXHRMY-UHFFFAOYSA-N 2,6-difluorobenzamide Chemical compound NC(=O)C1=C(F)C=CC=C1F AVRQBXVUUXHRMY-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- 241000255967 Helicoverpa zea Species 0.000 description 1
- 241000258937 Hemiptera Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003630 growth substance Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000003151 ovacidal effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a preparation method of hexaflumuron. The preparation method of hexaflumuron taking 3, 5-dichloro-4-(1,1,2,2-tetrafluoroethoxy) aniline and sodium cyanate as raw materials comprises the following steps of: (1) adding a phase transfer catalyst in an acetic acid aqueous solution, reacting for 1-12 hours at 0-80 DEG C, filtering reaction liquid to obtain filter cakes, washing and drying to obtain 3,5-dichloro-4-(1,1,2,2-tetrafluoroethoxy) phenylurea; and (2) in an organic solvent, reacting the mixture of anhydrous zinc chloride and anhydrous trichloride taken as a catalyst and 3, 5-dichloro-4-(1,1,2,2-tetrafluoroethoxy) phenylurea and 2,6-difluorobenzoyl chloride taken as raw materials for 1-24 hours at 65-150 DEG C, vacuumizing in the reaction process to remove hydrogen chloride gas, after reaction is ended, recovering the solvent through reduced pressure distillation, after cooling, adding a sodium bicarbonate solution with the mass fraction of 5%, adjusting the pH to 7-8, stirring for 30 minutes, filtering reaction liquid to obtain filter cakes, washing, drying and recrystallizing to obtain hexaflumuron. The preparation method of hexaflumuron has the advantages of being simple and reasonable in process, little in side reaction and having high safety, high reaction yield and high product purity, great industrialization potential and great social economic benefits, and can easily realize purification of products.
Description
Technical field
The present invention relates to a kind of preparation method of compound, relate in particular to a kind of preparation method of substituted benzoyl urea insect growth regulator(IGR) fluorine bell urea.
Background technology
Fluorine bell urea belongs to the benzoyl urea sterilant, is chitin synthesis inhibitor, has very high desinsection and ovicidal activity, and quick-acting, especially prevents and treats bollworm.Be used for cotton, potato and fruit tree and prevent and treat multiple Coleoptera, Diptera, Homoptera insect.
At present, the synthetic method of fluorine bell urea mainly contains two kinds: (1) earlier by 2,6-difluorobenzamide and phosgene or oxalyl chloride generate 2, the 6-difluoro benzoyl isocyanate, and then with 3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) aniline reaction makes; (2) earlier by 3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) aniline and phosgene or oxalyl chloride generate 3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) phenyl isocyanate, and then with 2, the reaction of 6-difluoro benzamide makes.In the above method, oxalyl chloride is colourless fuming liquid, meets water or pure vigorous reaction and decomposites hydrogenchloride, and stronger toxicity and corrodibility are arranged, and operating environment is poor, and costs an arm and a leg, and production cost is higher; Though the phosgene low price, production cost is lower, because the phosgene severe toxicity, there are potential safety hazard in inconvenience transportation and metering; In addition, above method has all at first made isocyanide acyl ester compound, and this compounds is stable inadequately, and autohemagglutination is difficult to store easily.
Guo Xi has just waited the people, and (the triphosgene method is synthesized fluorine bell urea, organic fluorine industry, 2009 the 2nd phases, 5-6) adopt triphosgene to replace the synthetic fluorine bell urea of phosgene, the result shows triphosgene and 2, and both reactions of 6-difluorobenzamide are difficult, and adopt triphosgene earlier with 3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) aniline synthetic 3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) phenyl isocyanate, with 2, the reaction of 6-difluorobenzamide can make fluorine bell urea again, and this method still fails to overcome intermediate 3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) the easy autohemagglutination of phenyl isocyanate, by product is more, the difficulty that product is not easy to purify still has a small amount of triphosgene can decompose the generation phosgene in reaction process and last handling process, causes potential safety hazard easily.
Summary of the invention
The objective of the invention is that prior art poor stability, the easy autohemagglutination of intermediate, by product are more in order to solve, product is difficult for the deficiency of purifying, provide a kind of technology advantages of simple, safe, side reaction is few, product purification easily, reaction yield and the high fluorine bell urea preparation method of product purity.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of preparation method of fluorine bell urea, described preparation method comprises the following steps:
(1) in the acetic acid aqueous solution of massfraction 20-60%, adds 3 shown in the formula I, 5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) aniline and 3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) phase-transfer catalyst of aniline quality 1-5% is under the agitation condition, drip the Zassol aqueous solution of massfraction 5-30%, react 1-12h down at 0-80 ℃, reaction solution is cooled to 0-5 ℃ of after-filtration with the water dilution of 1-3 times of volume then, filter cake washes with water to neutrality, obtain 3 shown in the formula II after the drying, 5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) phenylurea;
(2) with step (1) make 3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) phenylurea and 2, the 6-difluoro benzoyl chloride is a raw material, in organic solvent, add 3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) phenylurea and 2, Zinc Chloride Anhydrous and the aluminum trichloride (anhydrous) mixture of 6-difluoro benzoyl chloride total mass 5-30% are catalyzer, react 1-24h down in 65-150 ℃, vacuumize the hydrogen chloride gas of getting rid of generation with water pump in the reaction process, reaction finishes through vacuum distillation recovered solvent, after the cooling, the sodium hydrogen carbonate solution that slowly adds massfraction 5%, regulate pH to 7-8, stir 30min, filter, filter cake is washed with water to neutrality, gets the fluorine bell urea shown in the formula III with the 80-95% ethyl alcohol recrystallization again.
As preferably, the phase-transfer catalyst described in the step (1) is one of following: benzyltriethylammoinium chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride.
As preferably, in the step (1) in the acetic acid solution in contained acetate and the Zassol solution mol ratio of contained Zassol be 1-4:1,3, the mol ratio of 5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) aniline and Zassol is 1:1.05-1.5.
Further, in the step (1) in the acetic acid solution in contained acetate and the Zassol solution mol ratio of contained Zassol be 1.5-2.5:1.
As preferably, catalyzer is evenly pulverized by the mixed of mass ratio 5:1 by Zinc Chloride Anhydrous and aluminum trichloride (anhydrous) and is made in the step (2).
As preferably, organic solvent described in the step (2) is one of following: chlorobenzene, benzene,toluene,xylene, tetrahydrofuran (THF), 2-methyltetrahydrofuran.
As preferably, in the step (2) 2,6-difluoro benzoyl chloride and 3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) phenylurea mol ratio is 1-1.25:1.
Further, in the step (2) 2,6-difluoro benzoyl chloride and 3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) phenylurea mol ratio is 1.02-1.1:1.
As preferably, the acetic acid aqueous solution massfraction is 30-50% in the step (1); The massfraction of the Zassol aqueous solution that is dripped is 10～20%; Under 30-50 ℃ of condition, react 2-5h.
As preferably, catalyst consumption is 3 in the step (2), 5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) phenylurea and 2, and the 5-15% of 6-difluoro benzoyl chloride total mass reacts 6-10h under 90-120 ℃ of condition.
The present invention compared with prior art has following beneficial effect:
(1) under the effect of phase-transfer catalyst, uses Zassol and 3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) aniline is raw material synthetic 3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) phenylurea, reaction conditions gentleness, yield height, because Zassol is made by urea and yellow soda ash, and is cheap, good stability, in hot water, be decomposed into volatile salt, yellow soda ash and urea, to people, animal, fish safety.
(2) with 3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) phenylurea and 2,6-difluoro benzoyl chloride are the synthetic fluorine bell urea of raw material, and technology is simple, and by product is few, and product is easy to purify.
It is raw material that the present invention has effectively avoided adopting the oxalyl chloride or the phosgene of severe toxicity, and used main raw material is cheap and easy to get, and is safe, and the production process three wastes are few, and the purity height of product has bigger implementary value and economic results in society.
(4) embodiment
The present invention is described further below in conjunction with specific embodiment, and agents useful for same is commercial analytical pure among following each embodiment, and used instrument and equipment all are commercial conventional instrument and equipment, unless specified otherwise, each solution is the aqueous solution among the embodiment.
The content of fluorine bell urea adopts high performance liquid chromatography to detect, and concrete testing conditions is as follows: Lichrospher C18 post, 4.6mm * 250mm; Column temperature: room temperature; Moving phase: acetonitrile-water (volume ratio is 68:32); Flow velocity: 1ml/min; Detect wavelength: 254nm.
Fusing point detects: adopt fusing point instrument (WRS-3, Shanghai precision instrumentation company limited).
Embodiment 1
A kind of preparation method of fluorine bell urea, described preparation method comprises the following steps:
Step (1): with 7.8g(0.12mol) Zassol is dissolved in and is configured to 5% the Zassol aqueous solution in the 148.2ml water, with 7.14g(0.12mol) acetate is dissolved in and is configured to 20% acetic acid aqueous solution in the 28.56ml water, mechanical stirring is being housed, in the 500ml there-necked flask of constant pressure funnel and thermometer, add the above-mentioned acetic acid aqueous solution that configures successively, 0.278g benzyltriethylammoinium chloride, add 27.803g(0.1mol again) 3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) aniline, stir and slowly drip the above-mentioned Zassol aqueous solution that configures down, promptly have the off-white color solid to separate out, after dropwising, continuation is at 0 ℃ of reaction 12h, stopped reaction slowly pours into reaction solution in the beaker that 176.7ml water is housed under the agitation condition and dilutes, and is cooled to 0 ℃, filter, filter cake is washed with water to neutrality, and vacuum-drying obtains off-white color solid 3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) phenylurea 27.74g, the yield of step (1) reaction is 86.4%;
Step (2): with 2,6-difluoro benzoyl chloride 16.85g(0.1mol) is dissolved in 25ml in advance with standby in the dry toluene of crossing of Calcium Chloride Powder Anhydrous, Zinc Chloride Anhydrous and aluminum trichloride (anhydrous) mix the back by mass ratio 5:1 and pulverize, seal standby, the add-on of Zinc Chloride Anhydrous and aluminum trichloride (anhydrous) is a reactant 3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) phenylurea and 2,5% of 6-difluoro benzoyl chloride total mass, mechanical stirring is being housed, reflux condensing tube (the Calcium Chloride Powder Anhydrous drying tube that connects suitable for reading), in the 250ml four-hole boiling flask of constant pressure funnel and thermometer, add 3 successively, 5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) phenylurea 32.10g(0.1mol), 100ml is in advance with the dry toluene stirring and dissolving of crossing of Calcium Chloride Powder Anhydrous, add 2.45g Zinc Chloride Anhydrous and aluminum trichloride (anhydrous) mixture, be warming up to 40 ℃, slowly drip above-mentioned configure 2, the toluene solution of 6-difluoro benzoyl chloride, after dropwising, be warming up to 105 ℃ of stirring reaction 12h, vacuumize the eliminating hydrogen chloride gas with water pump in the reaction process, behind the stopped reaction, toluene solvant is reclaimed in underpressure distillation, cooling then, the sodium hydrogen carbonate solution that slowly adds massfraction 5% again, conditioned reaction liquid pH to 7.0, stir 30min, filter, filter cake be washed with water to neutral must slightly pinkish solid, the solid phase prod that makes is put in the 500ml single port flask, add the 400ml massfraction and be 80% ethanolic soln and 2g gac, reflux 30min, filtered while hot, filtrate are cooled to 0 ℃, separate out solid, filter, vacuum-drying obtains white solid 37.14g, i.e. product fluorine bell urea, reaction yield 80.5%, product fusing point: 202-204 ℃, it is 98.6% that efficient liquid phase chromatographic analysis gets content.
Embodiment 2
Step (1): with 15.6g(0.24mol) Zassol is dissolved in and is configured to 15% the Zassol aqueous solution in the 88.4ml water, with 30g(0.5mol) acetate is dissolved in and is configured to 40% acetic acid aqueous solution in the 45ml water, mechanical stirring is being housed, in the 500ml there-necked flask of constant pressure funnel and thermometer, add the above-mentioned acetic acid aqueous solution that configures successively, 2.78g Tetrabutyl amonium bromide adds 55.606g(0.2mol) 3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) aniline, stir down, slowly drip the above-mentioned Zassol aqueous solution that configures, promptly there is the off-white color solid to separate out, dropwises the back and continue at 80 ℃ of reaction 1h, stopped reaction, under the agitation condition reaction solution is slowly poured in the beaker that 400ml water is housed, dilution is cooled to 5 ℃, filters, and filter cake is washed with water to neutrality, drying obtains off-white color solid 3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) phenylurea product 58.11g, step (1) reaction yield is 90.5%;
Step (2) is with 2,6-difluoro benzoyl chloride 21.068g(0.125mol) is dissolved in 25ml in advance with standby in the dry dimethylbenzene of crossing of Calcium Chloride Powder Anhydrous, Zinc Chloride Anhydrous and aluminum trichloride (anhydrous) mix the back by mass ratio 5:1 and pulverize, seal standby, the add-on of Zinc Chloride Anhydrous and aluminum trichloride (anhydrous) is a reactant 3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) phenylurea and 2,30% of 6-difluoro benzoyl chloride total mass, mechanical stirring is being housed, reflux condensing tube (the Calcium Chloride Powder Anhydrous drying tube that connects suitable for reading), in the 250ml four-hole boiling flask of constant pressure funnel and thermometer, add 3 successively, 5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) phenylurea 32.10g(0.1mol), 100ml is in advance with the dry dimethylbenzene stirring and dissolving of crossing of Calcium Chloride Powder Anhydrous, add 15.95g Zinc Chloride Anhydrous and aluminum trichloride (anhydrous) mixture, be warming up to 40 ℃, slowly drip above-mentioned configure 2, the xylene solution of 6-difluoro benzoyl chloride, after dropwising, be warming up to 150 ℃ of stirring reaction 1h, vacuumize the eliminating hydrogen chloride gas with water pump in the reaction process, behind the stopped reaction, xylene solvent is reclaimed in underpressure distillation, cooling then, slowly add massfraction again and be 5% sodium hydrogen carbonate solution, conditioned reaction liquid pH to 8.0, stir 30min, filter, filter cake be washed with water to neutral must slightly pinkish solid, the solid phase prod that makes is put in the 500ml single port flask, adding 400ml massfraction is 95% ethanolic soln and 2g gac, reflux 30min, filtered while hot, filtrate is cooled to 5 ℃, separate out solid, filter, drying obtains white solid 37.61g, it is product fluorine bell urea, reaction yield 82.0%, product fusing point: 202.5-204 ℃, efficient liquid phase chromatographic analysis gets content 99.0%.
Embodiment 3
Step (1): with 19.5g(0.3mol) Zassol is dissolved in and is configured to 30% the Zassol aqueous solution in the 45.5ml water, with 30g(0.5mol) acetate is dissolved in and is configured to 60% acetic acid aqueous solution in the 20ml water, mechanical stirring is being housed, in the 500ml there-necked flask of constant pressure funnel and thermometer, add the above-mentioned acetic acid aqueous solution that configures successively, 1.39g tetrabutylammonium chloride, add 55.61g(0.2mol) 3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) aniline, stir and slowly drip the above-mentioned Zassol aqueous solution that configures down, promptly there is the off-white color solid to separate out, dropwises continuation at 40 ℃ of reaction 6h, stopped reaction, stir down reaction solution slowly to be poured into and dilute in the beaker that 150ml water is housed, be cooled to 2.5 ℃, filter, filter cake is washed with water to neutrality, drying obtains off-white color solid 3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) phenylurea product 59.68g, step (1) reaction yield is 92.95%;
Step (2): with 2,6-difluoro benzoyl chloride 18.54g(0.11mol) is dissolved in 25ml in advance with standby in the dry benzene of crossing of Calcium Chloride Powder Anhydrous, Zinc Chloride Anhydrous and aluminum trichloride (anhydrous) mix the back by mass ratio 5:1 and pulverize, seal standby, the add-on of Zinc Chloride Anhydrous and aluminum trichloride (anhydrous) is a reactant 3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) phenylurea and 2,15% of 6-difluoro benzoyl chloride total mass, mechanical stirring is being housed, reflux condensing tube (the Calcium Chloride Powder Anhydrous drying tube that connects suitable for reading), in the 250ml four-hole boiling flask of constant pressure funnel and thermometer, add 3 successively, 5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) phenylurea 32.10g(0.1mol), 100ml is in advance with the dry benzene stirring and dissolving of crossing of Calcium Chloride Powder Anhydrous, add 7.6g Zinc Chloride Anhydrous and aluminum trichloride (anhydrous) mixture, be warming up to 40 ℃, slowly drip above-mentioned configure 2, the benzole soln of 6-difluoro benzoyl chloride is warming up to 65 ℃ of following stirring reaction 24h after dropwising, vacuumize the eliminating hydrogen chloride gas with water pump in the reaction process, behind the stopped reaction, benzene solvent is reclaimed in underpressure distillation, then cooling, slowly add massfraction again and be 5% sodium hydrogen carbonate solution, regulate pH to 7.5, stir 30min, filter, filter cake be washed with water to neutral must slightly pinkish solid, the solid phase prod that makes is put in the 500ml single port flask, and adding 400ml massfraction is 85% ethanolic soln and 2g gac, reflux 30min, filtered while hot, filtrate is cooled to 2.5 ℃, separates out solid, filters, dry, obtain white solid 39.89g, i.e. product fluorine bell urea, reaction yield 86.5%, product fusing point: 202.7-204 ℃, efficient liquid phase chromatographic analysis gets content 99.1%.
Embodiment 4
Step (1): elementary operation is with the step (1) of embodiment 2, difference is: 3, and 5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) addition of aniline is 63.55g(0.228mol), i.e. Zassol and 3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) mol ratio of aniline is 1.05:1, and the yield of step (1) is 88.2%;
Step (2): elementary operation is with the step (2) of embodiment 2, step (2) product fluorine bell urea reaction yield 82.0%, and product fusing point: 202.5-204 ℃, efficient liquid phase chromatographic analysis gets content 99.0%.
Embodiment 5
Step (1): elementary operation is with the step (1) of embodiment 2, and difference is: after dripping Zassol solution, in 60 ℃ of reaction 2h, the yield of step (1) is 91.5%;
Step (2): elementary operation is with the step (2) of embodiment 2, step (2) product fluorine bell urea reaction yield 82.0%, and product fusing point: 202.5-204 ℃, efficient liquid phase chromatographic analysis gets content 99.0%.
Embodiment 6
Step (1): elementary operation is with the step (1) of embodiment 3, and the reaction yield of step (1) is 92.95%;
Step (2): elementary operation is with the step (2) of embodiment 3, and difference is: 3, and 5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) addition of phenylurea is 29.43g(0.0917mol), promptly 2,6-difluoro benzoyl chloride and 3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) mol ratio of phenylurea is 1.2:1, and the reaction yield of step (2) is 87.0%, product fusing point: 202.7-204.0 ℃, efficient liquid phase chromatographic analysis gets content 99.1%.
Embodiment 7
Step (1): elementary operation is with the step (1) of embodiment 3, and the reaction yield of step (1) is 92.95%;
Step (2): elementary operation is with the step (2) of embodiment 3, difference is: the add-on of Zinc Chloride Anhydrous and aluminum trichloride (anhydrous) is a reactant 3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) phenylurea and 2,20% of 6-difluoro benzoyl chloride total mass, the reaction yield of step (2) is 86.0%, and product fusing point: 202.2-204 ℃, efficient liquid phase chromatographic analysis gets content 98.9%.
Embodiment 8
Step (1), elementary operation is with the step (1) of embodiment 1, and the reaction yield of step (1) is 86.4%;
Step (2), elementary operation is with the step (2) of embodiment 1, and difference is: 2, after 6-difluoro benzoyl chloride solution dropwised, the reaction times was 4h, and the reaction yield of step (2) is 78.6%, product fusing point: 202.0-204.0 ℃, efficient liquid phase chromatographic analysis gets content 98.6%.
The present invention is not restricted to the described embodiments; what describe in the foregoing description and the specification sheets is for principle of the present invention is described; without departing from the spirit and scope of the present invention; the present invention also has the changes and improvements of various unsubstantialities; as phase-transfer catalyst can also be 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride; organic solvent can also be chlorobenzene, tetrahydrofuran (THF), 2-methyltetrahydrofuran, and these all fall in the scope of protection of present invention.
Claims (10)
1. the preparation method of a fluorine bell urea is characterized in that, described preparation method comprises the following steps:
(1) in the acetic acid aqueous solution of massfraction 20-60%, adds 3 shown in the formula I, 5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) aniline and 3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) phase-transfer catalyst of aniline quality 1-5% is under the agitation condition, drip the Zassol aqueous solution of massfraction 5-30%, react 1-12h down at 0-80 ℃, reaction solution is cooled to 0-5 ℃ of after-filtration with the water dilution of 1-3 times of volume then, filter cake washes with water to neutrality, obtain 3 shown in the formula II after the drying, 5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) phenylurea;
(2) with step (1) make 3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) phenylurea and 2, the 6-difluoro benzoyl chloride is a raw material, in organic solvent, add 3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) phenylurea and 2, Zinc Chloride Anhydrous and the aluminum trichloride (anhydrous) mixture of 6-difluoro benzoyl chloride total mass 5-30% are catalyzer, react 1-24h down in 65-150 ℃, vacuumize the hydrogen chloride gas of getting rid of generation with water pump in the reaction process, reaction finishes through vacuum distillation recovered solvent, after the cooling, the sodium hydrogen carbonate solution that slowly adds massfraction 5%, regulate pH to 7-8, stir 30min, filter, filter cake is washed with water to neutrality, gets the fluorine bell urea shown in the formula III with the 80-95% ethyl alcohol recrystallization again.
2. the preparation method of a kind of fluorine bell urea according to claim 1, it is characterized in that the phase-transfer catalyst described in the step (1) is one of following: benzyltriethylammoinium chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride.
3. the preparation method of a kind of fluorine bell urea according to claim 1, it is characterized in that, in the step (1) in the acetic acid aqueous solution in contained acetate and the Zassol solution mol ratio of contained Zassol be 1-4:1,3,5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) mol ratio of aniline and Zassol is 1:1.05-1.5.
4. the preparation method of a kind of fluorine bell urea according to claim 3 is characterized in that, in the step (1) in the acetic acid solution in contained acetate and the Zassol solution mol ratio of contained Zassol than being 1.5-2.5:1.
5. according to the preparation method of claim 1 or 2 or 3 or 4 described a kind of fluorine bell ureas, it is characterized in that catalyzer is evenly pulverized by the mixed of mass ratio 5:1 by Zinc Chloride Anhydrous and aluminum trichloride (anhydrous) and made in the step (2).
6. according to the preparation method of claim 1 or 2 or 3 or 4 described a kind of fluorine bell ureas, it is characterized in that organic solvent described in the step (2) is one of following: chlorobenzene, benzene,toluene,xylene, tetrahydrofuran (THF), 2-methyltetrahydrofuran.
7. according to the preparation method of claim 1 or 2 or 3 or 4 described a kind of fluorine bell ureas, it is characterized in that, in the step (2) 2,6-difluoro benzoyl chloride and 3, the mol ratio of 5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) phenylurea is 1-1.25:1.
8. the preparation method of a kind of fluorine bell urea according to claim 7 is characterized in that, in the step (2) 2, and 6-difluoro benzoyl chloride and 3, the mol ratio of 5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) phenylurea is 1.02-1.1:1.
9. the preparation method of a kind of fluorine bell urea according to claim 1 is characterized in that, the acetic acid aqueous solution massfraction is 30-50% in the step (1); The massfraction of the Zassol aqueous solution that is dripped is 10-20%; Under 30-50 ℃ of condition, react 2-5h.
10. the preparation method of a kind of fluorine bell urea according to claim 1 is characterized in that, catalyst consumption is 3 in the step (2), 5-two chloro-4-(1,1,2,2-tetrafluoro oxyethyl group) phenylurea and 2, the 5-15% of 6-difluoro benzoyl chloride total mass reacts 6-10h under 90-120 ℃ of condition.
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| CN103539705A (en) * | 2013-10-23 | 2014-01-29 | 浙江闰土研究院有限公司 | Clean production process of m-carbamidoaniline hydrochloride |
| CN113243382A (en) * | 2021-05-18 | 2021-08-13 | 江苏东南植保有限公司 | Emamectin benzoate and hexaflumuron water dispersible granule and preparation method and preparation device thereof |
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| CN113243382A (en) * | 2021-05-18 | 2021-08-13 | 江苏东南植保有限公司 | Emamectin benzoate and hexaflumuron water dispersible granule and preparation method and preparation device thereof |
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