CN102424671A - Synthesis method of 4-chloro-2-cyano-1-dimethylamino-sulfonyl-5-(4-methylphenyl)imidazo - Google Patents
Synthesis method of 4-chloro-2-cyano-1-dimethylamino-sulfonyl-5-(4-methylphenyl)imidazo Download PDFInfo
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Abstract
The invention discloses a synthesis method of 4-chloro-2-cyano-1-dimethylamino-sulfonyl-5-(4-methylphenyl)imidazo, which aims to solve the technical problems of long reaction time, low yield and environment pollution of the prior art. The method is used for preparing 2,2-dichloro-4'-methyl acetophenone as an intermediate through an acylation reaction of methylbenzene and dchloroethanoyl chloride and preparing 4(5)-chloro-2-cyano-5(4)-(4-methylphenyl)imidazo as an intermediate by taking ethyl acetate and the like as solvent, N-succinchlorimide as chlorinating agent and sodium dithionite and the like as reductant. The synthesis method has short reaction time, high yield and total yield up to 61.7% and is mainly used for preparing the 4-chloro-2-cyano-1-dimethylamino-sulfonyl-5-(4-methylphenyl)imidazo.
Description
Technical field
The present invention relates to the compound method of a kind of 4-chloro-2-cyanic acid-1-dimethylamino alkylsulfonyl-5-(4-aminomethyl phenyl) imidazoles.
Background technology
4-chloro-2-cyanic acid-1-dimethylamino alkylsulfonyl-5-(4-aminomethyl phenyl) imidazoles (being cyanogen frost azoles) is a kind of novel imidazole series bactericidal agent by the exploitation of Japanese Ishihara Sangyo Kaisha, Ltd..It is the mitochondrial respiratory suppressor factor, acts on the Q of plastosome complex compound
iThe position is different from the Q that the methyl acrylic ester sterilant acts on the plastosome complex compound
0The position, be in the disinfectant use in agriculture of having developed unique one act on Q
iThe sterilant at position has brand-new mechanism of action, is difficult for producing cross resistance with the other types sterilant.Its characteristics are that also it is the sterilant of a high reactivity, low toxicity, and have very strong preventive effect, after the dispenser lasting period long, resistance of rainwater washing against, safe, few to crop pollution, environmentally friendly etc. to people and animals and other beneficial organisms.Cyanogen frost azoles is widely used in oidium and the tomato of crops such as control cucumber, grape, the late blight of potatoes and other crops at home and abroad.
At present, the disclosed cyanogen frost of document azoles compound method mainly contains following three kinds: 1) the described employing n-Butyl Lithium of patent BR8801098A1 is in 2 methods of introducing cyanic acid of imidazole ring.The starting material n-Butyl Lithium that this method is used costs an arm and a leg, and the low temperature of reaction needed-70 ℃, severe reaction conditions; 2) the described utilization of patent EP0365030A1 generates imide structure in 2 methods of introducing cyanic acid of imidazole ring.This method reaction conditions is comparatively gentle, but the starting material 1-methoxyl group-1-imino--2 that uses, the 2-diethoxyethane is difficult for preparation, and price is more expensive; 3) the described employing oxalic dialdehyde of patent EP0705823A1 cyclization utilizes 2 methods of introducing cyanic acid of aldoxime base at imidazole ring again.Adopt this kind method, reaction conditions is comparatively gentle, and the prices of raw and semifnished materials are also relatively cheap, compare with preceding two patents, and total yield of products is higher.This method 4-chloro-2-cyanic acid-1-dimethylamino alkylsulfonyl-5-(4-aminomethyl phenyl) imidazoles total recovery still can only reach 42.5%, and the reaction times is longer, reaches 18～33 hours but adopt; Adopt N in the reaction in addition, dinethylformamide is made solvent, and reaction finishes afterreaction liquid and directly enters in the water; Solvent can't reclaim; Not only cause the waste of solvent, and wastewater discharge is strengthened, caused the huge pollution of environment.
Summary of the invention
The objective of the invention is to solve deficiency of the prior art and defective, the compound method of 4-chloro-2-cyanic acid-1-dimethylamino alkylsulfonyl-5-(4-aminomethyl phenyl) imidazoles that a kind of yield is high, generated time is short, three waste discharge is few is provided.
Synthetic route of the present invention is following:
The present invention is a raw material with the dichloroacetyl chloride, may further comprise the steps:
A. toluene and aluminum trichloride (anhydrous) are joined in the reaction flask, drip dichloroacetyl chloride, dropping temperature is at 0～50 ℃; Be warming up to 60～100 ℃ after dropwising, reacted 1～3 hour, be cooled to room temperature; Reaction solution is poured in the trash ice, be stirred to ice and dissolve fully, leave standstill separatory; Remove water, organic phase is steamed earlier and is removed excess toluene, absolute ethyl alcohol recrystallization; Obtain 2,2-two chloro-4 '-methyl acetophenone, the mol ratio of dichloroacetyl chloride, aluminum chloride, toluene is 1.0: 1.0～2.0: 2.0～10.0;
B. with 2; 2-two chloro-4 '-methyl acetophenone, the inorganic salt of azanol and methyl alcohol and the water mixed solvent that volume ratio is 2: 1 join in the reaction flask, and back flow reaction 1～2 hour adds glyoxal water solution; Continued back flow reaction 1～2 hour; Be cooled to room temperature, cross and filter 1-hydroxyl-4 (5)-(4-aminomethyl phenyl)-2-oximido methyne imidazoles-3-oxygen, the inorganic salt of said azanol are oxammonium hydrochloride or oxammonium sulfate; 2,2-two chloro-4 '-methyl acetophenone and azanol, oxalic dialdehyde, the mol ratio of methyl alcohol is 1.0: 3.0～8.0: 1.0～2.0: 15.0～20.0;
C. 1-hydroxyl-4 (5)-(4-aminomethyl phenyl)-2-oximido methyne imidazoles-3-oxygen and organic solvent are joined in the reaction flask, dripping thionyl chloride, dropping temperature is 0～50 ℃; Be warming up to 10～80 ℃ after dropwising, reacted 1～2 hour, be cooled to room temperature; Add N-chlorosuccinimide, reductive agent, be warming up to 30～80 ℃, reacted 1～2 hour; Be cooled to room temperature, add entry and stir, leave standstill separatory; Remove water, organic phase is steamed and is desolventized, and uses recrystallizing methanol; Get 4 (5)-chloro-2-cyanic acid-5 (4)-(4-aminomethyl phenyl) imidazoles, wherein said organic solvent is ETHYLE ACETATE, chloroform or 1, the 2-ethylene dichloride; Said reductive agent is V-Brite B, S-WAT or sodium sulfite anhy 96, and the mol ratio of 1-hydroxyl-4 (5)-(4-aminomethyl phenyl)-2-oximido methyne imidazoles-3-oxygen, sulfur oxychloride, N-chlorosuccinimide, reductive agent, organic solvent is 1.0: 1.0～4.0: 1.0～2.0: 1.0～2.0: 15.0～20.0;
D. 4 (5)-chloro-2-cyanic acid-5 (4)-(4-aminomethyl phenyl) imidazoles and ETHYLE ACETATE are joined in the reaction flask, add Anhydrous potassium carbonate and N, TMSDMA N dimethylamine base SULPHURYL CHLORIDE; Back flow reaction 1～6 hour; Steam and remove ETHYLE ACETATE, be cooled to room temperature, add entry and stir; Filter; Get 4-chloro-2-cyanic acid-1-dimethylamino alkylsulfonyl-5-(4-aminomethyl phenyl) imidazoles with re-crystallizing in ethyl acetate, 4 (5)-chloro-2-cyanic acid-5 (4)-(4-aminomethyl phenyl) imidazoles and Anhydrous potassium carbonate, N, the mol ratio of TMSDMA N dimethylamine base SULPHURYL CHLORIDE, ETHYLE ACETATE is 1.0: 1.0～3.0: 1.0～2.0: 15.0～20.0;
If step c and steps d all adopt ETHYLE ACETATE as solvent, also can link up and operate, that is: after the reaction of step c finishes; Be cooled to room temperature, add entry and stir, leave standstill separatory; Remove water, organic phase reflux divides water, is cooled to room temperature; Add Anhydrous potassium carbonate and N, TMSDMA N dimethylamine base SULPHURYL CHLORIDE carries out like the described operation of steps d then.So also can obtain target compound, and the two-step reaction total recovery that links up operation exceeds 6% than the total recovery of separate operation.
Advantage of the present invention: 1) reaction times foreshortens to 5 hours by 18 hours of prior art; 2) total yield of products is increased to 61.7% by 42.5% of prior art; 3) reaction solvent can recycling, has practiced thrift cost, has reduced wastewater discharge simultaneously, has reduced environmental stress.
Embodiment
Below in conjunction with embodiment the present invention is done further explain.
Embodiment 1
A.2,2-two chloro-4 '-methyl acetophenone synthetic
In the 1000ml four-hole boiling flask of TM, whisking appliance and reflux condensing tube is housed, add 450ml toluene, 80.1g aluminum trichloride (anhydrous), drip the 88.5g dichloroacetyl chloride, dropping temperature is controlled at 25 ± 5 ℃; Be warming up to 80 ℃ after dropwising, reacted 2 hours, reaction solution is poured in the 500g trash ice; Be stirred to ice and dissolve fully, separatory steams organic phase except that toluene; With 50ml absolute ethyl alcohol recrystallization, get the 115.7g white solid.
B.1-hydroxyl-4 (5)-(4-aminomethyl phenyl)-2-oximido methyne imidazoles-3-oxygen is synthetic
, the 1000ml four-hole boiling flask of TM, whisking appliance and reflux condensing tube adds 64.1g 2 in being housed, 2-two chloro-4 '-methyl acetophenone, 104.3g oxammonium hydrochloride, 200ml methyl alcohol, 100ml water, be warming up to backflow; Reacted 2 hours, and added 47.9g 40% glyoxal water solution, back flow reaction 2 hours; Be cooled to room temperature; Filter, drying gets the 62.2g white solid.
C.4 (5)-chloro-2-cyanic acid-5 (4)-(4-aminomethyl phenyl) imidazoles is synthetic
In the 500ml four-hole boiling flask of TM, whisking appliance and reflux condensing tube is housed, add 48.9g 1-hydroxyl-4 (5)-(4-aminomethyl phenyl)-2-oximido methyne imidazoles-3-oxygen, 300ml ETHYLE ACETATE, controlled temperature drips the 23.8g sulfur oxychloride at 25 ± 5 ℃; Be warming up to 50 ℃ after dropwising, reacted 1 hour, reduce to room temperature; Add 26.7g N-chlorosuccinimide, 52.2g V-Brite B, be warming up to backflow, reacted 2 hours; Reduce to room temperature, add 300ml water, separatory; Organic phase is steamed except that ETHYLE ACETATE, and recrystallizing methanol gets the 38.5g faint yellow solid.
D.4-chloro-2-cyanic acid-1-dimethylamino alkylsulfonyl-5-(4-aminomethyl phenyl) imidazoles (cyanogen frost azoles) is synthetic
, the 500ml four-hole boiling flask of reflux condensing tube, whisking appliance and TM adds 35.4g 4 (5)-chloro-2-cyanic acid-5 (4)-(4-aminomethyl phenyl) imidazoles, 250ml ETHYLE ACETATE, 27.6g Anhydrous potassium carbonate, 28.7g N in being housed, TMSDMA N dimethylamine base SULPHURYL CHLORIDE, and back flow reaction was steamed and is removed ETHYLE ACETATE in 6 hours; Be cooled to room temperature; Add 300ml water and stir, filter re-crystallizing in ethyl acetate; Obtain the 46.4g white solid, 150.4 ℃～151.7 ℃ of fusing points.
Cyanogen frost azoles total recovery is 59.5%, and content is 99.0%.
Embodiment 2
A.2,2-two chloro-4 '-methyl acetophenone synthetic
In the 1000ml four-hole boiling flask of TM, whisking appliance and reflux condensing tube is housed, add 450ml toluene, 80.1g aluminum trichloride (anhydrous), drip the 88.5g dichloroacetyl chloride, dropping temperature is controlled at 25 ± 5 ℃; Be warming up to 80 ℃ after dropwising, reacted 2 hours, reaction solution is poured in the 500g trash ice; Be stirred to ice and dissolve fully, separatory steams organic phase except that toluene; With 50ml absolute ethyl alcohol recrystallization, get the 115.7g white solid.
B.1-hydroxyl-4 (5)-(4-aminomethyl phenyl)-2-oximido methyne imidazoles-3-oxygen is synthetic
, the 1000ml four-hole boiling flask of TM, whisking appliance and reflux condensing tube adds 64.1g 2 in being housed, 2-two chloro-4 '-methyl acetophenone, 104.3g oxammonium hydrochloride, 200ml methyl alcohol, 100ml water, be warming up to backflow; Reacted 2 hours, and added 47.9g 40% glyoxal water solution, back flow reaction 2 hours; Be cooled to room temperature; Filter, drying gets the 62.2g white solid.
C.4-chloro-2-cyanic acid-1-dimethylamino alkylsulfonyl-5-(4-aminomethyl phenyl) imidazoles (cyanogen frost azoles) is synthetic
In the 500ml four-hole boiling flask of TM, whisking appliance and reflux condensing tube is housed, add 48.9g 1-hydroxyl-4 (5)-(4-aminomethyl phenyl)-2-oximido methyne imidazoles-3-oxygen, 300ml ETHYLE ACETATE, controlled temperature drips the 23.8g sulfur oxychloride at 25 ± 5 ℃, is warming up to 50 ℃ after dropwising; Reacted 1 hour, and reduced to room temperature, add 26.7g N-chlorosuccinimide, 52.2g V-Brite B, be warming up to backflow; Reacted 2 hours, and reduced to room temperature, add 300ml water, separatory; Organic phase reflux divides water, is cooled to room temperature, adds 30.0g Anhydrous potassium carbonate, 31.2g N, TMSDMA N dimethylamine base SULPHURYL CHLORIDE; Back flow reaction 6 hours is steamed and is removed ETHYLE ACETATE, is cooled to room temperature, adds 300ml water and stirs; Filter, re-crystallizing in ethyl acetate obtains the 54.7g white solid.
Cyanogen frost azoles total recovery is 61.7%, and content is 98.1%.
Embodiment 3
Method and embodiment 1 are basic identical, and different is that " oxammonium hydrochloride " replaces with oxammonium sulfate among the step b, and cyanogen frost azoles total recovery is 59.5%, and content is 98.4%.
Embodiment 4
Method and embodiment 1 are basic identical, and different is that " ETHYLE ACETATE " replaces with chloroform among the step c, and cyanogen frost azoles total recovery is 55.6%, and content is 98.4%.
Embodiment 5
Method and embodiment 1 are basic identical, and different is that used among the step c " ETHYLE ACETATE " replaces with 1, the 2-ethylene dichloride, and cyanogen frost azoles total recovery is 55.8%, content is 98.0%.
Embodiment 6
Method and embodiment 1 are basic identical, and different is that used among the step c " V-Brite B " replaced with S-WAT, and cyanogen frost azoles total recovery is 59.4%, and content is 98.9%.
Embodiment 7
Method and embodiment 1 are basic identical, and different is that used among the step c " V-Brite B " replaced with sodium sulfite anhy 96, and cyanogen frost azoles total recovery is 59.3%, and content is 98.8%.
The finished product to above embodiment carry out the structure evaluation: IR (KBr, cm
-1): 1180,1392 (sulfoamido stretching vibrations) 1447,1474,1497,1556 (phenyl ring skeletal vibration), 2242 (C ≡ N stretching vibrations); 1H NMR (500MHz, CDCl
3, δ ppm): 2.424 (s, 9H, CH
3), 7.378-7.394 (d, 2H, ph-H), 7.444-7.460 (d, 2H, ph-H).
The finished product to above embodiment carry out ultimate analysis (%):
Theoretical value: C48.03, H4.00, N17.00;
Measured value: C48.00, H3.95, N16.97.
The said structure appraising datum has confirmed that the compound that above embodiment obtains is a cyanogen frost azoles.
Claims (2)
1. the compound method of 4-chloro-2-cyanic acid-1-dimethylamino alkylsulfonyl-5-(4-aminomethyl phenyl) imidazoles is characterized in that step is following:
A. toluene and aluminum trichloride (anhydrous) are joined in the reaction flask, drip dichloroacetyl chloride, dropping temperature is warming up to 60～100 ℃ at 0～50 ℃ after dropwising; Reacted 1～3 hour, and be cooled to room temperature, reaction solution is poured in the trash ice, be stirred to ice and dissolve fully; Leave standstill separatory, remove water, organic phase is steamed earlier and is removed excess toluene, uses the absolute ethyl alcohol recrystallization; Obtain 2,2-two chloro-4 '-methyl acetophenone, the mol ratio of dichloroacetyl chloride, aluminum chloride, toluene is 1: 1～2: 2～10;
B. with 2; 2-two chloro-4 '-methyl acetophenone, the inorganic salt of azanol and methyl alcohol and the water mixed solvent that volume ratio is 2: 1 join in the reaction flask, and back flow reaction 1～2 hour adds glyoxal water solution; Continued back flow reaction 1～2 hour; Be cooled to room temperature, cross and filter 1-hydroxyl-4 (5)-(4-aminomethyl phenyl)-2-oximido methyne imidazoles-3-oxygen, the inorganic salt of said azanol are oxammonium hydrochloride or oxammonium sulfate; 2,2-two chloro-4 '-methyl acetophenone and azanol, oxalic dialdehyde, the mol ratio of methyl alcohol is 1: 3～8: 1～2: 15～20;
C. 1-hydroxyl-4 (5)-(4-aminomethyl phenyl)-2-oximido methyne imidazoles-3-oxygen and organic solvent are joined in the reaction flask, dripping thionyl chloride, dropping temperature is 0～50 ℃; Be warming up to 10～80 ℃ after dropwising, reacted 1～2 hour, be cooled to room temperature; Add N-chlorosuccinimide, reductive agent, be warming up to 30～80 ℃, reacted 1～2 hour; Be cooled to room temperature, add entry and stir, leave standstill separatory; Remove water, organic phase is steamed and is desolventized, and uses recrystallizing methanol; Get 4 (5)-chloro-2-cyanic acid-5 (4)-(4-aminomethyl phenyl) imidazoles, wherein said organic solvent is ETHYLE ACETATE, chloroform or 1, the 2-ethylene dichloride; Said reductive agent is V-Brite B, S-WAT or sodium sulfite anhy 96, and the mol ratio of 1-hydroxyl-4 (5)-(4-aminomethyl phenyl)-2-oximido methyne imidazoles-3-oxygen, sulfur oxychloride, N-chlorosuccinimide, reductive agent, organic solvent is 1: 1～4: 1～2: 1～2: 15～20;
D. 4 (5)-chloro-2-cyanic acid-5 (4)-(4-aminomethyl phenyl) imidazoles and ETHYLE ACETATE are joined in the reaction flask, add Anhydrous potassium carbonate and N, TMSDMA N dimethylamine base SULPHURYL CHLORIDE; Back flow reaction 1～6 hour; Steam and remove ETHYLE ACETATE, be cooled to room temperature, add entry and stir; Filter; Get 4-chloro-2-cyanic acid-1-dimethylamino alkylsulfonyl-5-(4-aminomethyl phenyl) imidazoles with re-crystallizing in ethyl acetate, 4 (5)-chloro-2-cyanic acid-5 (4)-(4-aminomethyl phenyl) imidazoles and Anhydrous potassium carbonate, N, the mol ratio of TMSDMA N dimethylamine base SULPHURYL CHLORIDE, ETHYLE ACETATE is 1: 1～3: 1～2: 15～20.
2. according to the compound method of the said 4-chloro-of claim 1 2-cyanic acid-1-dimethylamino alkylsulfonyl-5-(4-aminomethyl phenyl) imidazoles; It is characterized in that: dropping temperature described in the step a is 0～30 ℃, and the mol ratio of dichloroacetyl chloride and aluminum chloride, toluene is 1: 1～1.5: 4～8; Among the step b 2,2-two chloro-4 '-methyl acetophenone, azanol, oxalic dialdehyde mol ratio be 1: 3～6: 1～1.5; 0～30 ℃ of the dropping temperature of sulfur oxychloride described in the step c; Be warming up to 20～50 ℃ after dropwising; Be warming up to 40～70 ℃ after adding N-chlorosuccinimide, reductive agent; Solvent for use is ETHYLE ACETATE or chloroform, and used reductive agent is V-Brite B or S-WAT, and the mol ratio of 1-hydroxyl-4 (5)-(4-aminomethyl phenyl)-2-oximido methyne imidazoles-3-oxygen and sulfur oxychloride, N-chlorosuccinimide, reductive agent is 1: 1～3: 1～1.5: 1～1.5; 4 (5)-chloro-2-cyanic acid-5 (4)-(4-aminomethyl phenyl) imidazoles and Anhydrous potassium carbonate, N in the steps d, the mol ratio of TMSDMA N dimethylamine base SULPHURYL CHLORIDE is 1: 1～2: 1～1.5.3,, it is characterized in that the organic solvent of step c adopts ETHYLE ACETATE, after the reaction of step c finishes according to the compound method of the said 4-chloro-of claim 1 2-cyanic acid-1-dimethylamino alkylsulfonyl-5-(4-aminomethyl phenyl) imidazoles; Be cooled to room temperature, add entry and stir, leave standstill separatory; Remove water, organic phase reflux divides water, is cooled to room temperature; Add Anhydrous potassium carbonate and N; TMSDMA N dimethylamine base SULPHURYL CHLORIDE is proceeded the described operation of steps d, obtains 4-chloro-2-cyanic acid-1-dimethylamino alkylsulfonyl-5-(4-aminomethyl phenyl) imidazoles.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936678A (en) * | 2014-04-23 | 2014-07-23 | 西安近代化学研究所 | Synthesis method of 4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulfonamide |
| CN107382871A (en) * | 2017-06-06 | 2017-11-24 | 无锡市稼宝药业有限公司 | The synthetic method of cyazofamid |
| CN107602477A (en) * | 2017-10-25 | 2018-01-19 | 西安近代化学研究所 | A kind of process for purification of cyazofamid active compound |
| WO2018154582A1 (en) | 2017-02-23 | 2018-08-30 | Adama Makhteshim Ltd. | Process for the preparation of 2-cyanoimidazole compounds |
| CN109400534A (en) * | 2018-10-17 | 2019-03-01 | 兰博尔开封科技有限公司 | A kind of production improvement technique of 1- hydroxyl -4- (4 '-aminomethyl phenyl) -2- first oxime imidazoles -3- oxide |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0653421A1 (en) * | 1993-11-12 | 1995-05-17 | Ishihara Sangyo Kaisha Ltd. | Process for preparing 2-cyanoimidazole compounds |
| EP0705823A1 (en) * | 1994-09-08 | 1996-04-10 | Ishihara Sangyo Kaisha Ltd. | Process for producing 1-substituted-2-cyanoimidazole compounds |
-
2011
- 2011-11-04 CN CN201110344498.XA patent/CN102424671B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0653421A1 (en) * | 1993-11-12 | 1995-05-17 | Ishihara Sangyo Kaisha Ltd. | Process for preparing 2-cyanoimidazole compounds |
| EP0705823A1 (en) * | 1994-09-08 | 1996-04-10 | Ishihara Sangyo Kaisha Ltd. | Process for producing 1-substituted-2-cyanoimidazole compounds |
Non-Patent Citations (5)
| Title |
|---|
| SHINSUKE SANO ET AL.: "Development of a Novel Fungicide, Cyazofamid", 《J.PESTIC.SCI.》, vol. 32, no. 2, 31 December 2007 (2007-12-31), pages 137 - 138 * |
| TAKESHI OHSHIMA ET AL.: "Development of a Novel Fungicide, Cyazofamid", 《J.PESTIC. SCI.》, vol. 29, no. 2, 31 December 2004 (2004-12-31), pages 136 - 138 * |
| 宁斌科等: "氰霜唑的合成、表征与晶体结构", 《应用化工》, vol. 39, no. 9, 30 September 2010 (2010-09-30), pages 1351 - 1354 * |
| 许诚等: "杀菌剂氰霜唑的合成与表征", 《应用化工》, vol. 38, no. 7, 31 July 2009 (2009-07-31) * |
| 许诚等: "杀菌剂氰霜唑的合成进展", 《农药科学与管理》, vol. 30, no. 10, 31 December 2009 (2009-12-31), pages 40 - 41 * |
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| CN109400534B (en) * | 2018-10-17 | 2020-11-03 | 兰博尔开封科技有限公司 | Production process of 1-hydroxy-4- (4' -methylphenyl) -2-methoxy oxime imidazole-3-oxide |
| CN109400534A (en) * | 2018-10-17 | 2019-03-01 | 兰博尔开封科技有限公司 | A kind of production improvement technique of 1- hydroxyl -4- (4 '-aminomethyl phenyl) -2- first oxime imidazoles -3- oxide |
| CN115745893A (en) * | 2022-11-16 | 2023-03-07 | 西安近代化学研究所 | Method for synthesizing 2-cyano-5-aryl-1H-imidazole compound |
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