CN103965124A - Synthetic method for triazoline-ketone - Google Patents
Synthetic method for triazoline-ketone Download PDFInfo
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- CN103965124A CN103965124A CN201410178956.0A CN201410178956A CN103965124A CN 103965124 A CN103965124 A CN 103965124A CN 201410178956 A CN201410178956 A CN 201410178956A CN 103965124 A CN103965124 A CN 103965124A
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- 238000010189 synthetic method Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims abstract description 24
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 19
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229940067157 phenylhydrazine Drugs 0.000 claims abstract description 18
- 238000007599 discharging Methods 0.000 claims abstract description 11
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZVCDLGYNFYZZOK-UHFFFAOYSA-M sodium cyanate Chemical compound [Na]OC#N ZVCDLGYNFYZZOK-UHFFFAOYSA-M 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000005660 chlorination reaction Methods 0.000 claims description 15
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- 238000009413 insulation Methods 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 4
- 239000003643 water by type Substances 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 3
- 239000012954 diazonium Substances 0.000 claims description 3
- 150000001989 diazonium salts Chemical class 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 235000010288 sodium nitrite Nutrition 0.000 claims description 3
- FFSJPOPLSWBGQY-UHFFFAOYSA-N triazol-4-one Chemical compound O=C1C=NN=N1 FFSJPOPLSWBGQY-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 235000019628 coolness Nutrition 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 9
- 239000013067 intermediate product Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 150000002576 ketones Chemical class 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000005086 pumping Methods 0.000 abstract 3
- 239000005708 Sodium hypochlorite Substances 0.000 abstract 2
- 238000005580 one pot reaction Methods 0.000 abstract 1
- -1 chloro-2-fluorophenyl Chemical group 0.000 description 6
- 238000005070 sampling Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 235000011150 stannous chloride Nutrition 0.000 description 4
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 3
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 150000007857 hydrazones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005492 Carfentrazone-ethyl Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- MLKCGVHIFJBRCD-UHFFFAOYSA-N ethyl 2-chloro-3-{2-chloro-5-[4-(difluoromethyl)-3-methyl-5-oxo-4,5-dihydro-1H-1,2,4-triazol-1-yl]-4-fluorophenyl}propanoate Chemical group C1=C(Cl)C(CC(Cl)C(=O)OCC)=CC(N2C(N(C(F)F)C(C)=N2)=O)=C1F MLKCGVHIFJBRCD-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D249/12—Oxygen or sulfur atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a synthetic method for triazoline-ketone and relates to the field of ketone synthetic production technology. The synthetic method comprises the following steps in sequence: a. synthesizing phenylhydrazine; b. synthesizing the triazoline-ketone; c. chloridizing; d. fluorating. The synthetic method is characterized in that the synthesis of the triazoline-ketone specifically comprises the following steps: (1) putting 79 parts of the phenylhydrazine by weight in a 3 # kettle, pumping 100 parts of tertiary butanol by weight, and pumping 70 parts of acetaldehyde and 45 parts of tertiary butanol by weight in an acetaldehyde metering tank; (2) putting 60 parts of sodium cyanate and 83 parts of water by weight in the 3 # kettle; (3) separating the water below; (4) starting to stir and pumping 320 parts of sodium hypochlorite by weight in a sodium hypochlorite metering tank; (5) separating the water below; (6) adding 200 parts of water by weight in the 3 # kettle; (7) adding 200 parts of water by weight in the 3 # kettle for cooling and discharging. According to the invention, the reaction condition is mild; by adopting the one-pot method, intermediate products don't need to be separated and can be directly synthesized, so that the operation is simple, the yield is high, and the reaction temperature is moderate.
Description
Technical field:
The present invention relates to containing ketone synthetic production technical field, specifically a kind of synthetic method of Triazolinones.
Background technology:
1-(the chloro-2-fluorophenyl of 4-)-3-methyl-4-difluoromethyl-1,2,4-triazoline-5-ketone is the one of Triazolinones, is the synthetic important intermediate of highy potent herbicide carfentrazoneethyl, in the production of weedicide, has a wide range of applications.Existing this Triazolinones mainly contains low temperature fluorate method and two kinds of synthesis modes of high-temperature fluorination method, but pure in some drawbacks in existing synthetic method, in the building-up process of existing intermediate phenylhydrazine, adopt the sub-reduction of tin protochloride, need a large amount of hydrochloric acid, it is also cumbersome reclaiming tin protochloride.Taking phenylhydrazine as raw material, generate hydrazone, then 1-(2-fluorophenyl)-3-methyl isophthalic acid while carrying out synthetic intermediate, 2,4-triazoline-5-ketone, need to adopt two reactors, and intermediate product need to separate, complex operation, yield is low.The trimethyl carbinol recovery problem that reaction is reclaimed, the trimethyl carbinol that reaction is reclaimed, because containing superoxide, can not directly be used, and processes inconvenient.In chlorination reaction, conventional solvent cannot carry out chlorination as chloro thing solvent, and reaction yield is very low.
Summary of the invention:
Technical problem to be solved by this invention is to provide a kind of intermediate 1-(2-fluorophenyl)-3-methyl isophthalic acid, a reactor of the synthetic employing of 2,4-triazoline-5-ketone, intermediate product is without separation, simple to operate, the synthetic method of the Triazolinones that yield is high.
The technical problem solving adopts following technical scheme:
A synthetic method for Triazolinones, comprises the following steps successively: a, phenylhydrazine synthetic, and b, Triazolinones synthetic, c, chlorination, d, fluoridize, and it is characterized in that: the synthetic of described Triazolinones specifically comprises:
The synthetic of described Triazolinones specifically comprises:
(1), in 3# still, drop into phenylhydrazine 79 weight parts, the suction trimethyl carbinol 100 weight parts, open and stir cooling, simultaneously to acetaldehyde test tank suction 70 weight part acetaldehyde and the 45 weight part trimethyl carbinols, when approximately 25 DEG C of still temperature, drip the mixing solutions of the trimethyl carbinol of acetaldehyde and extraction, keep temperature to add for 0.5 hour, continue holding temperature 0.5 hour;
(2), drop into Zassol 60 weight parts, water 83 weight parts in 3# still, 5 DEG C of insulations 7 hours;
(3), leave standstill 0.5 hour, separate lower layer of water;
(4), open and stir, open the cooling of chuck refrigerated water, simultaneously to clorox test tank suction clorox 320 weight parts, 15 DEG C drip clorox, control temperature below 20 DEG C, within approximately 5 hours, add, and continue insulation 3 hours;
(5), leave standstill 0.5 hour, separate lower layer of water;
(6), to 200 weight parts that add water in 3# still, decompression precipitation ,-0.095MPa, 60 DEG C of end;
(7), again to the 200 weight parts coolings that add water in 3# still, be cooled to 30 DEG C, discharging, discharging obtains 1-(2-fluorophenyl)-3-methyl isophthalic acid, 2,4-triazoline-5-ketone.
The synthetic of described phenylhydrazine comprises the following steps:
(1), in 2# still, drop into hydrochloric acid 153 weight parts, inject 306 weight parts waters to water measuring tank simultaneously, take out 70 weight part aniline to aniline test tank, water is put into 2# still, within approximately 0.5 hour, add, continue to be cooled to 10 DEG C, starting to drip 50 weight part concentration is 30% sodium nitrite solution, approximately 1 hour time, 10 DEG C of left and right of temperature control, reaction finishes reaction solution to squeeze into test tank;
(2), in 1# still, drop into sodium bisulfite 125 weight parts, inject 227.5 weight parts waters to water measuring tank simultaneously, water is put into still, open to stir and be cooled to 10 DEG C, take out ammoniacal liquor 60 weight parts to ammoniacal liquor test tank, drip ammoniacal liquor, temperature control is below 30 DEG C, approximately 0.5 hour, continue to be cooled to 5 DEG C;
(3), drip diazonium salt solution to 1# still, temperature control is below 20 DEG C, approximately 1 hour time, regulates PH=8-10;
(4), take out 204 weight part hydrochloric acid to hydrochloric acid test tank, while being warming up to 40 DEG C to 1# still, open tail gas absorbing system, drip hydrochloric acid, within approximately 40 minutes, add, be warming up to 40-45 DEG C, be incubated 2 hours;
(5), 1# still reaction finishes, cooling, takes out 233 weight part ammoniacal liquor to ammoniacal liquor test tank, drips ammoniacal liquor, temperature control, below 50 DEG C, adds for approximately 1 hour, regulates PH=4-5, is cooled to 35 DEG C, discharging, is phenylhydrazine.
Described chlorination comprises the following steps:
(1), check system resistance to air loss and be ready to gas defence articles for use;
(2), drop into triazolone 120 weight parts, acetonitrile 360 weight parts to 4# reactor, open and stir, pass into steam to chuck and be warming up to 37 DEG C;
(3), pass into chlorine 100 weight parts, by 40 DEG C of recirculated water control temperature of reaction, speed DEG C is 6 weight part/10 minute, 90 minutes logical finishing;
(4), insulation 2 hours;
(5), be successively cooled to 15 DEG C with recirculated water and refrigerated water, discharging, use totally 80 weight part acetonitrile washing leaching cakes, send oven dry, obtain 1-(the chloro-2-fluorophenyl of 4-)-3-methyl isophthalic acid, 2,4-triazoline-5-ketone.
Described fluoridizing comprises the following steps:
(1), check system resistance to air loss;
(2), drop into chlorination 75 weight parts, salt of wormwood 40 weight parts, dimethyl formamide 750 weight parts to 5# reactor, open and stir, pass into steam to chuck and heat up;
(3), pass into difluorochloromethane 75 weight parts, the chemical formula of difluorochloromethane is reduced to F22 temperature 115 DEG C of left and right, approximately 1.5 hours time, is cooled to 80 DEG C after maintaining 0.5 hour;
(4), suction filtration 50 DEG C time, filter cake washs with dimethyl formamide, filtrate is sent 6# precipitation still;
(5), ethanol suction alcohol meter measuring tank, negative pressure precipitation under-0.095MPa, 100-120 DEG C has taken off, and with circulating water cooling to 80 DEG C, adds ethanol, is warming up to 70 DEG C, stops stirring refrigerated water cooling;
(6), suction filtration 0 DEG C time, obtain final product 1-(the chloro-2-fluorophenyl of 4-)-3-methyl-4-difluoromethyl-1,2,4-triazoline-5-ketone.
Described adjusting PH regulates with acid or ammoniacal liquor by passing into.
After the building-up reactions of described Triazolinones, the trimethyl carbinol is reclaimed, and the trimethyl carbinol after reclaiming is carried out to alkaline purification.
A, phenylhydrazine synthetic, b, Triazolinones synthetic, c, chlorination, d, the chemical equation of fluoridizing are:
Synthesizing of phenylhydrazine
Triazolinones is synthetic
Chlorination
Fluoridize
The invention has the beneficial effects as follows:
1, in the building-up process of hydrazine, adopting sodium bisulfite is reductive agent, and reaction process is easily controlled, and reduce the conventional tin protochloride Asia that adopts, and needs a large amount of hydrochloric acid, and it is also cumbersome reclaiming tin protochloride.
2, react with acetaldehyde with hydrazine, generate hydrazone, be reacted into ring with Zassol, reaction conditions gentleness adopts one kettle way simultaneously, and intermediate product does not need to separate, and directly carries out next step and synthesizes, and simple to operate, yield is high, and temperature of reaction is moderate.
3, the trimethyl carbinol recovery problem that reaction is reclaimed, the trimethyl carbinol that reaction is reclaimed, because containing superoxide, can not directly be used, and needs to process, and the present invention adopts alkali treatment method, has effectively solved corresponding problem.
4, in chlorination reaction, conventional solvent cannot carry out chlorination as chloro thing solvent, and it is solvent that the present invention adopts acetonitrile, effectively raises reaction yield, reclaims acetonitrile simultaneously and applies mechanically.
Embodiment:
For technique means, creation characteristic that the present invention is realized, reach object and effect is easy to understand, below in conjunction with specific examples, further set forth the present invention.
A synthetic method for Triazolinones, comprises the following steps successively: a, phenylhydrazine synthetic, and b, Triazolinones synthetic, c, chlorination, d, fluoridize;
The synthetic of Triazolinones specifically comprises:
(1), in 3#2000L still, drop into phenylhydrazine 79kg, suction trimethyl carbinol 100kg, open and stir cooling, simultaneously to acetaldehyde test tank suction 70kg acetaldehyde and the 45kg trimethyl carbinol, when approximately 25 DEG C of still temperature, drip the mixing solutions of the trimethyl carbinol of acetaldehyde and extraction, keep temperature to add for 0.5 hour, continue holding temperature 0.5 hour, it is qualified that sampling gas spectrum is surveyed transformation efficiency 99%;
(2), in 3#2000L still, drop into Zassol 60 weight parts, water 83 weight parts, 5 DEG C of insulations 7 hours, it is qualified that sampling liquid spectrum is surveyed transformation efficiency 99%;
(3), leave standstill 0.5 hour, separate lower layer of water;
(4), open and stir, open the cooling of chuck refrigerated water, simultaneously to clorox test tank suction clorox 320kg, 15 DEG C drip clorox, control temperature below 20 DEG C, within approximately 5 hours, add, continue insulation 3 hours, it is qualified that sampling liquid spectrum is surveyed transformation efficiency 97%;
(5), leave standstill 0.5 hour, separate lower layer of water;
(6), to the 200kg that adds water in 3#2000L still, decompression precipitation ,-0.095MPa, 60 DEG C of end;
(7), again to the 200kg cooling that adds water in 3#2000L still, be cooled to 30 DEG C, discharging.
The synthetic of phenylhydrazine comprises the following steps:
(1), in 2#1000L still, drop into hydrochloric acid 153kg, inject 306L water to water measuring tank simultaneously, take out 70kg aniline to aniline test tank, water is put into 2#1000L still, within approximately 0.5 hour, add, continue to be cooled to 10 DEG C, starting to drip 50kg concentration is 30% sodium nitrite solution, approximately 1 hour time, 10 DEG C of left and right of temperature control, reaction finishes reaction solution to squeeze into test tank;
(2), in 1#2000L still, drop into sodium bisulfite 125kg, inject 227.5L part water to water measuring tank simultaneously, water is put into still, open stirring and be cooled to 10 DEG C, take out ammoniacal liquor 60kg to ammoniacal liquor test tank, drip ammoniacal liquor, temperature control, below 30 DEG C, approximately 0.5 hour, continues to be cooled to 5 DEG C;
(3), drip diazonium salt solution to 1#2000L still, temperature control is below 20 DEG C, approximately 1 hour time, regulates PH=9;
(4), take out 204kg hydrochloric acid to hydrochloric acid test tank, while being warming up to 40 DEG C to 1#2000L still, open tail gas absorbing system, drip hydrochloric acid, within approximately 40 minutes, add, be warming up to 42 DEG C, be incubated 2 hours;
(5), 1#2000L still reaction finishes, cooling, takes out 233kg ammoniacal liquor to ammoniacal liquor test tank, drips ammoniacal liquor, temperature control, below 50 DEG C, adds for approximately 1 hour, regulates PH=4, is cooled to 35 DEG C, discharging, is phenylhydrazine.
Chlorination comprises the following steps:
(1), check system resistance to air loss and be ready to gas defence articles for use;
(2), drop into triazolone 120kg, acetonitrile 360kg to 4#1000L reactor, open and stir, pass into steam to chuck and be warming up to 37 DEG C;
(3), pass into chlorine 100kg, by 40 DEG C of recirculated water control temperature of reaction, speed DEG C be 6kg/10 minute, 90 minutes logical complete;
(4), insulation 2 hours, sampling survey transformation efficiency 98% qualified;
(5), be successively cooled to 15 DEG C with recirculated water and refrigerated water, discharging, with common 80kg acetonitrile washing leaching cake, send oven dry, dries to obtain 113kg, content 95%.
Fluoridize and comprise the following steps:
(1), check system resistance to air loss;
(2), drop into chlorination 75kg, salt of wormwood 40kg, dimethyl formamide 750kg to 5#1000L reactor, open and stir, pass into steam to chuck and heat up;
(3), pass into difluorochloromethane 75kg, temperature is 115 DEG C of left and right, approximately 1.5 hours time, be cooled to 80 DEG C after maintaining 0.5 hour, it is qualified that transformation efficiency 98.5% is surveyed in sampling;
(4), suction filtration 50 DEG C time, filter cake washs with dimethyl formamide, filtrate is sent 6#500L precipitation still;
(5), ethanol suction alcohol meter measuring tank, negative pressure precipitation under-0.095MPa, 110 DEG C have taken off, and with circulating water cooling to 80 DEG C, add ethanol, are warming up to 70 DEG C, stop stirring refrigerated water cooling;
(6), suction filtration 0 DEG C time, dry 57kg, content 95%.
Regulate PH to regulate with acid or ammoniacal liquor by passing into.
After the building-up reactions of Triazolinones, the trimethyl carbinol is reclaimed, and the trimethyl carbinol after reclaiming is carried out to alkaline purification.
More than show and described ultimate principle of the present invention and 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; that in above-described embodiment and specification sheets, describes 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.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (6)
1. a synthetic method for Triazolinones, comprises the following steps successively: a, phenylhydrazine synthetic, and b, Triazolinones synthetic, c, chlorination, d, fluoridize, and it is characterized in that: the synthetic of described Triazolinones specifically comprises:
(1), in 3# still, drop into phenylhydrazine 79 weight parts, the suction trimethyl carbinol 100 weight parts, open and stir cooling, simultaneously to acetaldehyde test tank suction 70 weight part acetaldehyde and the 45 weight part trimethyl carbinols, when approximately 25 DEG C of still temperature, drip the mixing solutions of the trimethyl carbinol of acetaldehyde and extraction, keep temperature to add for 0.5 hour, continue holding temperature 0.5 hour;
(2), drop into Zassol 60 weight parts, water 83 weight parts in 3# still, 5 DEG C of insulations 7 hours;
(3), leave standstill 0.5 hour, separate lower layer of water;
(4), open and stir, open the cooling of chuck refrigerated water, simultaneously to clorox test tank suction clorox 320 weight parts, 15 DEG C drip clorox, control temperature below 20 DEG C, within approximately 5 hours, add, and continue insulation 3 hours;
(5), leave standstill 0.5 hour, separate lower layer of water;
(6), to 200 weight parts that add water in 3# still, decompression precipitation ,-0.095MPa, 60 DEG C of end;
(7), again to the 200 weight parts coolings that add water in 3# still, be cooled to 30 DEG C, discharging.
2. the synthetic method of a kind of Triazolinones according to claim 1, is characterized in that: the synthetic of described phenylhydrazine comprises the following steps:
(1), in 2# still, drop into hydrochloric acid 153 weight parts, inject 306 weight parts waters to water measuring tank simultaneously, take out 70 weight part aniline to aniline test tank, water is put into 2# still, within approximately 0.5 hour, add, continue to be cooled to 10 DEG C, starting to drip 50 weight part concentration is 30% sodium nitrite solution, approximately 1 hour time, 10 DEG C of left and right of temperature control, reaction finishes reaction solution to squeeze into test tank;
(2), in 1# still, drop into sodium bisulfite 125 weight parts, inject 227.5 weight parts waters to water measuring tank simultaneously, water is put into still, open to stir and be cooled to 10 DEG C, take out ammoniacal liquor 60 weight parts to ammoniacal liquor test tank, drip ammoniacal liquor, temperature control is below 30 DEG C, approximately 0.5 hour, continue to be cooled to 5 DEG C;
(3), drip diazonium salt solution to 1# still, temperature control is below 20 DEG C, approximately 1 hour time, regulates PH=8-10;
(4), take out 204 weight part hydrochloric acid to hydrochloric acid test tank, while being warming up to 40 DEG C to 1# still, open tail gas absorbing system, drip hydrochloric acid, within approximately 40 minutes, add, be warming up to 40-45 DEG C, be incubated 2 hours;
(5), 1# still reaction finishes, cooling, takes out 233 weight part ammoniacal liquor to ammoniacal liquor test tank, drips ammoniacal liquor, temperature control, below 50 DEG C, adds for approximately 1 hour, regulates PH=4-5, is cooled to 35 DEG C, discharging, is phenylhydrazine.
3. the synthetic method of a kind of Triazolinones according to claim 1, is characterized in that: described chlorination comprises the following steps:
(1), check system resistance to air loss and be ready to gas defence articles for use;
(2), drop into triazolone 120 weight parts, acetonitrile 360 weight parts to 4# reactor, open and stir, pass into steam to chuck and be warming up to 37 DEG C;
(3), pass into chlorine 100 weight parts, by 40 DEG C of recirculated water control temperature of reaction, speed DEG C is 6 weight part/10 minute, 90 minutes logical finishing;
(4), insulation 2 hours;
(5), be successively cooled to 15 DEG C with recirculated water and refrigerated water, discharging, use totally 80 weight part acetonitrile washing leaching cakes, send oven dry.
4. the synthetic method of a kind of Triazolinones according to claim 1, is characterized in that: described fluoridizing comprises the following steps:
(1), check system resistance to air loss;
(2), drop into chlorination 75 weight parts, salt of wormwood 40 weight parts, dimethyl formamide 750 weight parts to 5# reactor, open and stir, pass into steam to chuck and heat up;
(3), pass into difluorochloromethane 75 weight parts, temperature is 115 DEG C of left and right, approximately 1.5 hours time, is cooled to 80 DEG C after maintaining 0.5 hour;
(4), suction filtration 50 DEG C time, filter cake washs with dimethyl formamide, filtrate is sent 6# precipitation still;
(5), ethanol suction alcohol meter measuring tank, negative pressure precipitation under-0.095MPa, 100-120 DEG C has taken off, and with circulating water cooling to 80 DEG C, adds ethanol, is warming up to 70 DEG C, stops stirring refrigerated water cooling;
(6), suction filtration 0 DEG C time.
5. the synthetic method of a kind of Triazolinones according to claim 2, is characterized in that: described adjusting PH regulates with acid or ammoniacal liquor by passing into.
6. the synthetic method of a kind of Triazolinones according to claim 1, is characterized in that: after the building-up reactions of described Triazolinones, the trimethyl carbinol is reclaimed, and the trimethyl carbinol after reclaiming is carried out to alkaline purification.
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| CN107629015A (en) * | 2017-08-23 | 2018-01-26 | 连云港世杰农化有限公司 | One kind synthesis 1（2,4 dichlorophenyls）The method of the ketone of 3 methyl, 4 difluoromethyl, 1,2,4 triazole 5 |
| CN107698529A (en) * | 2017-08-23 | 2018-02-16 | 连云港世杰农化有限公司 | One kind synthesis 1（2,4 dichlorophenyls）The method of the ketone of 3 methyl, 4 difluoromethyl, 1,2,4 triazole 5 |
| CN113402472A (en) * | 2021-06-16 | 2021-09-17 | 山东潍坊润丰化工股份有限公司 | Synthetic method of sulfentrazone intermediate |
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