CN102424671B - 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 synthetic method of the chloro-2-cyano group-1-of a kind of 4-dimethylamino-sulfonyl-5-(4-aminomethyl phenyl) imidazoles.
Background technology
The chloro-2-cyano group-1-of 4-dimethylamino-sulfonyl-5-(4-aminomethyl phenyl) imidazoles (being cyazofamid) is a kind of novel imidazole series bactericidal agent of being developed by Japanese Ishihara Sangyo Kaisha, Ltd..It is mitochondrial respiratory inhibitor, acts on the Q of plastosome complex compound
iposition, is different from methyl acrylic ester sterilant and acts on the Q of plastosome complex compound
0position, 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 other types sterilant.Its feature is also that it is the sterilant of a high reactivity, low toxicity, and has very strong preventive effect, after dispenser the lasting period long, resistance of rainwater washing against, to people and animals and other beneficial organisms safe, few to crop pollution, environmentally friendly etc.Cyazofamid is widely used in the late blight of the oidium of the crops such as control cucumber, grape and tomato, potatoes and other crops at home and abroad.
At present, the disclosed cyazofamid synthetic method of document mainly contains following three kinds: 1) the employing n-Butyl Lithium described in patent BR8801098A1 is in the method for 2 introducing cyano group of imidazole ring.The starting material n-Butyl Lithium that this method is used is expensive, and the low temperature of reaction needed-70 ℃, severe reaction conditions; 2) utilization described in patent EP0365030A1 generates the method for imide structure at 2 introducing cyano group of imidazole ring.This method reaction conditions is comparatively gentle, but starting material 1-methoxyl group-1-imino--2 that use, 2-diethoxyethane is difficult for preparation, and price is more expensive; 3) the employing oxalic dialdehyde cyclization described in patent EP0705823A1, recycling aldoxime base is in the method for 2 introducing cyano group of imidazole ring.Adopt this kind of method, reaction conditions is comparatively gentle, and the prices of raw and semifnished materials are also relatively cheap, and compared with the first two patent, total yield of products is higher.But adopt the method 4-chloro-2-cyano group-1-dimethylamino-sulfonyl-5-(4-aminomethyl phenyl) imidazoles total recovery still can only reach 42.5%; and the reaction times is longer; reach 18～33 hours; in reaction, adopt DMF to make solvent in addition, reaction finishes rear reaction solution and directly enters in water; solvent cannot reclaim; not only cause the waste of solvent, and wastewater discharge is strengthened, caused the huge pollution of environment.
Summary of the invention
The object of the invention is to solve deficiency of the prior art and defect, the synthetic method of the chloro-2-cyano group-1-of 4-dimethylamino-sulfonyl-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 as follows:
The present invention, take dichloroacetyl chloride as raw material, comprises the following steps:
A. toluene and aluminum trichloride (anhydrous) are joined in reaction flask, drip dichloroacetyl chloride, dropping temperature is at 0～50 ℃, after dropwising, be warming up to 60～100 ℃, react 1～3 hour, be cooled to room temperature, reaction solution is poured in trash ice, be stirred to ice and dissolve completely, leave standstill separatory, remove water, organic phase is first steamed except excess toluene, and dehydrated alcohol recrystallization, obtains 2, the chloro-4 '-methyl acetophenone of 2-bis-, the mol ratio of dichloroacetyl chloride, aluminum chloride, toluene is 1.0: 1.0～2.0: 2.0～10.0;
B. by 2, the chloro-4 '-methyl acetophenone of 2-bis-, the inorganic salt of azanol and volume ratio are that methyl alcohol and the water mixed solvent of 2: 1 joins in reaction flask, back flow reaction 1～2 hour, add glyoxal water solution, continue back flow reaction 1～2 hour, be cooled to room temperature, filter to obtain 1-hydroxyl-4 (5)-(4-aminomethyl phenyl)-2-oximido methyne imidazoles-3-oxygen, the inorganic salt of described azanol are oxammonium hydrochloride or oxammonium sulfate, 2, 2-bis-is 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 reaction flask, drip sulfur oxychloride, dropping temperature is 0～50 ℃, after dropwising, be warming up to 10～80 ℃, react 1～2 hour, be cooled to room temperature, add N-chlorosuccinimide, reductive agent, be warming up to 30～80 ℃, react 1～2 hour, be cooled to room temperature, add water to stir, leave standstill separatory, remove water, organic phase is steamed and is desolventized, by recrystallizing methanol, obtain 4 (5)-chloro-2-cyano group-5 (4)-(4-aminomethyl phenyl) imidazoles, wherein said organic solvent is ethyl acetate, chloroform or 1, 2-ethylene dichloride, described reductive agent is V-Brite B, S-WAT or sodium bisulfite, 1-hydroxyl-4 (5)-(4-aminomethyl phenyl)-2-oximido methyne imidazoles-3-oxygen, sulfur oxychloride, N-chlorosuccinimide, reductive agent, the mol ratio of 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-cyano group-5 (4)-(4-aminomethyl phenyl) imidazoles and ethyl acetate are joined in reaction flask, add Anhydrous potassium carbonate and N, N dimethylamine base SULPHURYL CHLORIDE, back flow reaction 1～6 hour, steam except ethyl acetate, be cooled to room temperature, add water to stir, filter, obtain the chloro-2-cyano group-1-of 4-dimethylamino-sulfonyl-5-(4-aminomethyl phenyl) imidazoles by re-crystallizing in ethyl acetate, 4 (5)-chloro-2-cyano group-5 (4)-(4-aminomethyl phenyl) imidazoles and Anhydrous potassium carbonate, N, N dimethylamine base SULPHURYL CHLORIDE, the mol ratio of ethyl acetate is 1.0: 1.0～3.0: 1.0～2.0: 15.0～20.0,
If step c and steps d all adopt ethyl acetate as solvent, also can link up and operate, that is:, after the reaction of step c finishes, be cooled to room temperature, add water to stir, leave standstill separatory, remove water, organic phase reflux divides water, be cooled to room temperature, add Anhydrous potassium carbonate and N, N dimethylamine base SULPHURYL CHLORIDE, then carries out the operation as described in steps d.So also can obtain target compound, and the total recovery that two-step reaction links up operation exceeds 6% than the total recovery of separate operation.
Advantage of the present invention: 1) reaction times foreshortens to 5 hours in 18 hours by prior art; 2) total yield of products is increased to 61.7% by 42.5% of prior art; 3) reaction solvent can recycling, has saved cost, has reduced wastewater discharge simultaneously, has reduced environmental stress.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
A.2, the chloro-4 '-methyl acetophenone of 2-bis-is synthetic
In the 1000ml four-hole boiling flask that thermometer, agitator and reflux condensing tube are housed, add 450ml toluene, 80.1g aluminum trichloride (anhydrous), drip 88.5g dichloroacetyl chloride, dropping temperature is controlled at 25 ± 5 ℃, is warming up to 80 ℃ after dropwising, and reacts 2 hours, reaction solution is poured in 500g trash ice, be stirred to ice and dissolve completely, separatory, steams organic phase except toluene, with 50ml dehydrated alcohol recrystallization, obtain 115.7g white solid.
B.1-synthesizing of hydroxyl-4 (5)-(4-aminomethyl phenyl)-2-oximido methyne imidazoles-3-oxygen
In the 1000ml four-hole boiling flask that thermometer, agitator and reflux condensing tube are housed, add 64.1g 2, the chloro-4 '-methyl acetophenone of 2-bis-, 104.3g oxammonium hydrochloride, 200ml methyl alcohol, 100ml water, be warming up to backflow, react 2 hours, add 47.9g 40% glyoxal water solution, back flow reaction 2 hours, be cooled to room temperature, filter, dry, obtain 62.2g white solid.
C.4 synthesizing of (5)-chloro-2-cyano group-5 (4)-(4-aminomethyl phenyl) imidazoles
Thermometer is being housed, in the 500ml four-hole boiling flask of agitator and reflux condensing tube, add 48.9g 1-hydroxyl-4 (5)-(4-aminomethyl phenyl)-2-oximido methyne imidazoles-3-oxygen, 300ml ethyl acetate, control temperature at 25 ± 5 ℃, drip 23.8g sulfur oxychloride, after dropwising, be warming up to 50 ℃, react 1 hour, be down to room temperature, add 26.7g N-chlorosuccinimide, 52.2g V-Brite B, be warming up to backflow, react 2 hours, be down to room temperature, add 300ml water, separatory, organic phase is steamed except ethyl acetate, recrystallizing methanol, obtain 38.5g faint yellow solid.
D.4-chloro-2-cyano group-1-dimethylamino-sulfonyl-5-(4-aminomethyl phenyl) imidazoles (cyazofamid) is synthetic
In the 500ml four-hole boiling flask that reflux condensing tube, agitator and thermometer are housed, add 35.4g 4 (5)-chloro-2-cyano group-5 (4)-(4-aminomethyl phenyl) imidazoles, 250ml ethyl acetate, 27.6g Anhydrous potassium carbonate, 28.7g N, N dimethylamine base SULPHURYL CHLORIDE, back flow reaction is steamed except ethyl acetate for 6 hours, be cooled to room temperature, add 300ml water and stir, filter re-crystallizing in ethyl acetate, obtain 46.4g white solid, 150.4 ℃～151.7 ℃ of fusing points.
Cyazofamid total recovery is 59.5%, and content is 99.0%.
Embodiment 2
A.2, the chloro-4 '-methyl acetophenone of 2-bis-is synthetic
In the 1000ml four-hole boiling flask that thermometer, agitator and reflux condensing tube are housed, add 450ml toluene, 80.1g aluminum trichloride (anhydrous), drip 88.5g dichloroacetyl chloride, dropping temperature is controlled at 25 ± 5 ℃, is warming up to 80 ℃ after dropwising, and reacts 2 hours, reaction solution is poured in 500g trash ice, be stirred to ice and dissolve completely, separatory, steams organic phase except toluene, with 50ml dehydrated alcohol recrystallization, obtain 115.7g white solid.
B.1-synthesizing of hydroxyl-4 (5)-(4-aminomethyl phenyl)-2-oximido methyne imidazoles-3-oxygen
In the 1000ml four-hole boiling flask that thermometer, agitator and reflux condensing tube are housed, add 64.1g 2, the chloro-4 '-methyl acetophenone of 2-bis-, 104.3g oxammonium hydrochloride, 200ml methyl alcohol, 100ml water, be warming up to backflow, react 2 hours, add 47.9g 40% glyoxal water solution, back flow reaction 2 hours, be cooled to room temperature, filter, dry, obtain 62.2g white solid.
C.4-chloro-2-cyano group-1-dimethylamino-sulfonyl-5-(4-aminomethyl phenyl) imidazoles (cyazofamid) is synthetic
Thermometer is being housed, in the 500ml four-hole boiling flask of agitator and reflux condensing tube, add 48.9g 1-hydroxyl-4 (5)-(4-aminomethyl phenyl)-2-oximido methyne imidazoles-3-oxygen, 300ml ethyl acetate, control temperature at 25 ± 5 ℃, drip 23.8g sulfur oxychloride, after dropwising, be warming up to 50 ℃, react 1 hour, be down to room temperature, add 26.7g N-chlorosuccinimide, 52.2g V-Brite B, be warming up to backflow, react 2 hours, be down to room temperature, add 300ml water, separatory, organic phase reflux divides water, be cooled to room temperature, add 30.0g Anhydrous potassium carbonate, 31.2g N, N dimethylamine base SULPHURYL CHLORIDE, back flow reaction 6 hours, steam except ethyl acetate, be cooled to room temperature, adding 300ml water stirs, filter, re-crystallizing in ethyl acetate, obtain 54.7g white solid.
Cyazofamid total recovery is 61.7%, and content is 98.1%.
Embodiment 3
Method is substantially the same manner as Example 1, and difference is that in step b, " oxammonium hydrochloride " replaces with oxammonium sulfate, and cyazofamid total recovery is 59.5%, and content is 98.4%.
Embodiment 4
Method is substantially the same manner as Example 1, and difference is that in step c, " ethyl acetate " replaces with chloroform, and cyazofamid total recovery is 55.6%, and content is 98.4%.
Embodiment 5
Method is substantially the same manner as Example 1, and difference is that " ethyl acetate " used in step c replaces with 1,2-ethylene dichloride, and cyazofamid total recovery is 55.8%, and content is 98.0%.
Embodiment 6
Method is substantially the same manner as Example 1, and difference is that " V-Brite B " used in step c replaced with to S-WAT, and cyazofamid total recovery is 59.4%, and content is 98.9%.
Embodiment 7
Method is substantially the same manner as Example 1, and difference is that " V-Brite B " used in step c replaced with to sodium bisulfite, and cyazofamid total recovery is 59.3%, and content is 98.8%.
The finished product of above embodiment are carried out to Structural Identification: 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 of above embodiment are carried out to ultimate analysis (%):
Theoretical value: C48.03, H4.00, N17.00;
Measured value: C48.00, H3.95, N16.97.
Said structure appraising datum has confirmed that the compound that above embodiment obtains is cyazofamid.
Claims (2)
1. a synthetic method for the chloro-2-cyano group-1-of 4-dimethylamino-sulfonyl-5-(4-aminomethyl phenyl) imidazoles, is characterized in that step is as follows:
A. toluene and aluminum trichloride (anhydrous) are joined in reaction flask, drip dichloroacetyl chloride, dropping temperature is at 0～50 ℃, after dropwising, be warming up to 60～100 ℃, react 1～3 hour, be cooled to room temperature, reaction solution is poured in trash ice, be stirred to ice and dissolve completely, leave standstill separatory, remove water, organic phase is first steamed except excess toluene, uses dehydrated alcohol recrystallization, obtains 2, the chloro-4 '-methyl acetophenone of 2-bis-, the mol ratio of dichloroacetyl chloride, aluminum trichloride (anhydrous), toluene is 1: 1～2: 2～10;
B. by 2, the inorganic salt of the chloro-4 '-methyl acetophenone of 2-bis-, azanol and methyl alcohol and the water mixed solvent that volume ratio is 2: 1 join in reaction flask, back flow reaction 1～2 hour, add glyoxal water solution, continue back flow reaction 1～2 hour, be cooled to room temperature, filter to obtain 1-hydroxyl-4 (5)-(4-aminomethyl phenyl)-2-oximido methyne imidazoles-3-oxygen, the inorganic salt of described azanol are oxammonium hydrochloride or oxammonium sulfate, the mol ratio of the chloro-4 '-methyl acetophenone of 2,2-bis-and azanol, oxalic dialdehyde, 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 reaction flask, drip sulfur oxychloride, dropping temperature is 0～50 ℃, after dropwising, be warming up to 10～80 ℃, react 1～2 hour, be cooled to room temperature, add N-chlorosuccinimide, reductive agent, be warming up to 30～80 ℃, react 1～2 hour, be cooled to room temperature, add water to stir, leave standstill separatory, remove water, organic phase is steamed and is desolventized, by recrystallizing methanol, obtain 4 (5)-chloro-2-cyano group-5 (4)-(4-aminomethyl phenyl) imidazoles, wherein said organic solvent is ethyl acetate, chloroform or 1, 2-ethylene dichloride, described reductive agent is V-Brite B, S-WAT or sodium bisulfite, 1-hydroxyl-4 (5)-(4-aminomethyl phenyl)-2-oximido methyne imidazoles-3-oxygen, sulfur oxychloride, N-chlorosuccinimide, reductive agent, the mol ratio of organic solvent is 1: 1～4: 1～2: 1～2: 15～20,
D. 4 (5)-chloro-2-cyano group-5 (4)-(4-aminomethyl phenyl) imidazoles and ethyl acetate are joined in reaction flask, add Anhydrous potassium carbonate and N, N dimethylamine base SULPHURYL CHLORIDE, back flow reaction 1～6 hour, steam except ethyl acetate, be cooled to room temperature, add water to stir, filter, obtain the chloro-2-cyano group-1-of 4-dimethylamino-sulfonyl-5-(4-aminomethyl phenyl) imidazoles by re-crystallizing in ethyl acetate, 4 (5)-chloro-2-cyano group-5 (4)-(4-aminomethyl phenyl) imidazoles and Anhydrous potassium carbonate, N, N dimethylamine base SULPHURYL CHLORIDE, the mol ratio of ethyl acetate is 1: 1～3: 1～2: 15～20.
2. the synthetic method of the chloro-2-cyano group-1-of 4-dimethylamino-sulfonyl-5-(4-aminomethyl phenyl) imidazoles according to claim 1, it is characterized in that: dropping temperature described in step a is 0～30 ℃, the mol ratio of dichloroacetyl chloride and aluminum trichloride (anhydrous), toluene is 1: 1～1.5: 4～8; In step b 2, the chloro-4 '-methyl acetophenone of 2-bis-, azanol, oxalic dialdehyde mol ratio be 1: 3～6: 1～1.5; 0～30 ℃ of the dropping temperature of sulfur oxychloride described in step c, after dropwising, be warming up to 20～50 ℃, after adding N-chlorosuccinimide, reductive agent, be warming up to 40～70 ℃, solvent for use is ethyl acetate or chloroform, reductive agent used 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-cyano group-5 (4) in steps d-(4-aminomethyl phenyl) imidazoles and Anhydrous potassium carbonate, N, the mol ratio of N dimethylamine base SULPHURYL CHLORIDE is 1: 1～2: 1～1.5.
3, the synthetic method of the chloro-2-cyano group-1-of 4-dimethylamino-sulfonyl-5-(4-aminomethyl phenyl) imidazoles according to claim 1; the organic solvent that it is characterized in that step c adopts ethyl acetate; after the reaction of step c finishes; be cooled to room temperature; add water to stir; leave standstill separatory; remove water; organic phase reflux divides water; be cooled to room temperature, add Anhydrous potassium carbonate and N, N dimethylamine base SULPHURYL CHLORIDE; proceed the operation described in steps d, obtain the chloro-2-cyano group-1-of 4-dimethylamino-sulfonyl-5-(4-aminomethyl phenyl) imidazoles.
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| CN103936678B (en) * | 2014-04-23 | 2016-04-27 | 西安近代化学研究所 | The chloro-2-cyano group of a kind of 4--N, the synthetic method of N-dimethyl-5-(4 '-aminomethyl phenyl)-1H-imidazoles-1-sulphonamide |
| PL3583094T3 (en) * | 2017-02-23 | 2022-01-03 | Adama Makhteshim Ltd. | Process for the preparation of 2-cyanoimidazole compounds |
| 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 |
| 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 |
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| 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 |
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| EP0653421A1 (en) * | 1993-11-12 | 1995-05-17 | Ishihara Sangyo Kaisha Ltd. | Process for preparing 2-cyanoimidazole compounds |
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