CN102276551A - Synthesis of heterocyclic long-chain amino substitution-containing cyanoacrylate compound and application thereof to pesticide - Google Patents
Synthesis of heterocyclic long-chain amino substitution-containing cyanoacrylate compound and application thereof to pesticide Download PDFInfo
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Abstract
The invention relates to synthesis of a heterocyclic long-chain amino substitution-containing cyanoacrylate compound and application thereof to a pesticide. The compound with a general formula (I) has excellent herbicidal activity on broadleaf weeds of rape, amaranthus retroflexus and the like in a corn field, shows superior selectivity for crops and can be used as a herbicide, wherein R1 is an alkyl group, an alcoxyl alkyl group, an aryloxy alkyl group, an alcoxyl alcoxyl alkyl group or an aryloxy aryloxy alkyl group; R2 is C1-C3 alkylthio group or a C1-C3 alkyl group; Het is a benzene ring, a pyridine ring, a thiazole ring, a pyrimidine ring, a pyridazine ring, a thiadiazole ring, a thiadiazine ring, a furan ring, a tetrahydrofuran ring, an oxazole ring, an isoxazole ring, an oxadiazole ring, a pyrazole ring, a thiophene ring, a pyrrole ring, a tetrahydropyrrole ring, a triazole ring or ferrocene, or the heterocyclic ring substituted by fluorine, chlorine, bromine, C1-C6 alkoxyl group or C1-C6 alkyl amino group; X is oxygen, nitrogen, sulfur, a sulfinyl group or a sulphonyl group; m is 1-12; and n is 0-12.
Description
Technical field
The present invention relates to contain the synthetic and application on agricultural chemicals that heterocycle long-chain amido replaces cyanoacrylate compound.
Background technology
Cyanoacrylate is that a class has and suppresses the active inhibitor of photosynthesis lightsystem (PS II) electron transport more by force.It is a very high class lightsystem (PS II) electron transfer inhibitor of up to the present finding of activity.3-protein d 1 and plastoquinone Q in its emulative replacement photosynthesis
BCombine, thus the transfer transport in the destruction photosynthesis.Because its mechanism of action is special, the selectivity height has eco-friendly characteristics, has become in recent years one of focus in pesticide research field both at home and abroad.Cyanoacrylate compound comes across 1969 as the report of weedicide the earliest, but also few about the research of this respect subsequently.What the cyanoacrylate activity that Hill reaction was up to the present reported was the highest is that structural formula is the compound of A.Chinese patent CN1089089A in 2002 has reported that the compd B with the pyridine ring substituted benzene ring demonstrates very high weeding activity, and it is to the inhibiting rate (ED of rape weeds
90) be higher than 5 times that contain benzene ring compound, simultaneously also far above the weeding activity of compd A.This is heterocycle to be introduced in the structure of cyanoacrylate first, and demonstrates very high weeding activity.Chinese patent CN1483320A in 2004 has reported with thiazole methylamino-cyanoacrylate compound to be a series of heterocycle methylamino cyanoacrylate compound C of representative again, give birth to the survey result and show that Compound C has very high weeding activity to broadleaf weeds and gramineous weeds, and crop is shown good selectivity.Chinese patent CN1594294A in 2005 is changed to fluorine atom with the chlorine atom of 6 of pyridine rings again and has synthesized a series of Compound D, they have very high weeding activity equally, and are that have even quite active with 6 cyanoacrylate compound for the chlorine atom of pyridine ring.Patent China CN101020677A had reported again tetrahydrofuran (THF) and furan nucleus has been introduced in the structure of cyanoacrylate in 2007, found this compounds E, and F not only has weeding activity but also has certain anti-microbial activity.The cyanoacrylate weedicide commercialization of also being unrealized at present is so the highly active weedicide of screening has the vast market development space from this compounds.
Summary of the invention
The purpose of this invention is to provide a kind of synthetic and weeding activity that contains the cyanoacrylate compound of heterocycle long-chain amido replacement, it is that cyanoacrylate compound is carried out composition optimizes, the amido that will contain different heterocycle long-chains replacements is incorporated in the structure of cyanoacrylate, has synthesized compound (I).Give birth to the survey result and show that compound (I) has very high weeding activity to broadleaf weeds and standing grain herbaceous weed, and crop is shown good selectivity.
The present invention is the compound of following logical formula I:
Wherein, R
1: alkyl, alkoxyalkyl, aryloxyalkyl group, alcoxyl alkoxyalkyl, fragrant oxygen aryloxyalkyl group; R
2: C
1-C
3Alkylthio, C
1-C
3Alkyl.Het: phenyl ring, pyridine ring, thiazole ring, pyrimidine ring, pyridazine ring, thiadiazoles ring, thiadiazine ring, furan nucleus, tetrahydrofuran (THF) Huan, oxazole ring, isoxazole ring, oxadiazole ring, pyrazoles ring, thiphene ring, pyrrole ring, Pyrrolidine ring, triazole ring, ferrocene, or above-mentioned heterocycle is by fluorine, chlorine, bromine, C
1-C
6Alkoxyl group or C
1-C
6Alkylamino radical replaces; X: oxygen, nitrogen, sulphur, sulfinyl, alkylsulfonyl; M:1-12; N:0-12.
The concrete synthetic route of The compounds of this invention (I) is as follows:
(1) thiadiazoles long-chain amine compound is synthetic
R
3Be C
1-C
5Alkyl, CF
3
(2) pyridine long-chain amine compound is synthetic
Wherein, R
4: C
1-C
5Alkyl, C
1-C
5Alkoxyl group, C
1-C
3Alkylthio, C
1-C
6Alkylamino radical, aryloxy, alcoxyl alkoxyalkyl, fragrant oxygen aryloxyalkyl group, fluorine, chlorine, bromine, trifluoromethyl.
(3) thiazole long-chain amine compound is synthetic
Wherein, R
5: C
1-C
5Alkyl, C
1-C
5Alkoxyl group, C
1-C
3Alkylthio, C
1-C
6Alkylamino radical, aryloxy, alcoxyl alkoxyalkyl, fragrant oxygen aryloxyalkyl group, fluorine, chlorine, bromine, trifluoromethyl.
(4) phenyl ring long-chain amine compound is synthetic
Wherein, R
6: C
1-C
5Alkyl, C
1-C
5Alkoxyl group, C
1-C
3Alkylthio, C
1-C
6Alkylamino radical, aryloxy, alcoxyl alkoxyalkyl, fragrant oxygen aryloxyalkyl group, fluorine, chlorine, bromine, trifluoromethyl.
(5) contain the synthetic of cyanoacrylate compound that heterocycle long-chain amido replaces
When X=S
Concrete synthetic route of the present invention is described in detail as follows:
The preparation method of part of compounds is through following step:
(1) 2-bromine (or chlorine)-1,3,4-thiadiazoles 5-methylthio group ethamine synthetic
Thiosemicarbazide and acetate, mol ratio is 1: 1, refluxed 3 hours in hydrochloric acid, regulating PH with sodium hydroxide then is that alkalescence obtains 2-amino-5-methyl isophthalic acid, 3, the 4-thiadiazoles, it obtains 2-bromo-5-methyl isophthalic acid with Sodium Nitrite, cuprous bromide (perhaps cuprous chloride) low-temp reaction again, and 3,4-thiadiazoles (perhaps 2-chloro-5-methyl isophthalic acid, 3, the 4-thiadiazoles).2-bromo-5-methyl isophthalic acid, 3,4-thiadiazoles (perhaps 2-chloro-5-methyl isophthalic acid, 3, the 4-thiadiazoles) in tetracol phenixin or acetonitrile, is initiator and NBS reaction, obtains 2-bromo-5-brooethyl-1,3 with AIBN or benzoyl peroxide, 4-thiadiazoles (perhaps 2-chloro-5-chloromethyl-1,3,4-thiadiazoles).
2-bromo-5-brooethyl-1,3,4-thiadiazoles (perhaps 2-chloro-5-chloromethyl-1,3,4-thiadiazoles) reacts under the condition of sodium alkoxide with Mercaptamine again and obtain 2-(2-bromo-1,3, the 4-thiadiazoles)-5-methylthio group ethamine [perhaps 2-(2-chloro-1,3,4-thiadiazoles)-5-methylthio group ethamine].
(2) one kettle way Synthetic 2-bromine (or chlorine)-1,3,4-thiadiazoles 5-methylthio group ethamine
Equimolar Monochloro Acetic Acid and thiosemicarbazide are mixed, and the ice bath cooling drips phosphorus oxychloride down, drips off reacting by heating 1 hour, cooling adds acid with its dissolving, and cryosel is bathed the aqueous solution of the following dropping of cooling Sodium Nitrite then, drip off room temperature reaction after 2 hours, add cupric chloride (perhaps cupric bromide), room temperature reaction 5 hours, extraction, just can obtain 2-chloro-5-chloromethyl-1,3,4-thiadiazoles (perhaps 2-bromo-5-brooethyl-1,3, the 4-thiadiazoles).
2-chloro-5-chloromethyl-1,3,4-thiadiazoles (perhaps 2-bromo-5-brooethyl-1,3,4-thiadiazoles) reacts under the condition of sodium alkoxide with Mercaptamine again and obtain 2-(2-chloro-1,3, the 4-thiadiazoles)-5-methylthio group ethamine [perhaps 2-(2-bromo-1,3,4-thiadiazoles)-5-methylthio group ethamine].
(3) 4-replaces-1,2,3-thiadiazoles-5-methylthio group ethamine synthetic
Methylcarbonate and hydrazine hydrate reaction obtain the carbazic acid methyl esters; and then obtain an intermediate hydrazone with corresponding substituted acyl ethyl acetate; cyclization obtains 4-replacement-1 under the thionyl chloride condition then; 2; 3-thiadiazoles-5-ethyl formate obtains corresponding alcohol with sodium borohydride reduction, obtains 4-replacement-5-chloromethyl-1 after the thionyl chloride chlorination; 2, the 3-thiadiazoles.
4-replacement-5-chloromethyl-1,2,3-thiadiazoles obtain 4-with Mercaptamine reaction under the condition that sodium alkoxide refluxes again and replace-1,2,3-thiadiazoles-5-methylthio group ethamine.
(4) 2-(2-substituted thiazole-5-)-methylthio group ethamine synthetic
2-replacement-5-5-chloromethyl thiazole and Mercaptamine react under the reflux conditions of sodium alkoxide just can obtain 2-(2-substituted thiazole-5-)-methylthio group ethamine.
(5) 2-(2-substituted pyridines-5-)-methylthio group ethamine synthetic
2-replacement-5-chloromethylpyridine and Mercaptamine react under the reflux conditions of sodium alkoxide just can obtain 2-(2-substituted pyridines-5-)-methylthio group ethamine.
(6) 2-cyano group-3,3-diformazan sulfenyl vinylformic acid ethoxy ethyl ester or 2-cyano group-3-methoxyl group-2-olefin(e) acid ethoxy ethyl ester and heterocycle long-chain methylamine, mol ratio is 1: 1, with ethanol, tetrahydrofuran (THF), acetonitrile, ethylene glycol monomethyl ether or ethylene glycol ethyl ether is solvent reflux 3 hours, precipitation, the column chromatography separation obtains target compound.
The application of cyanoacrylate compound (I) on agricultural chemicals that contains the thiadiazoles ring is as weedicide.Compound (I) can be used for the weeding of the broadleaf weedss such as rape, Amaranthus retroflexus in the corn field under 20 grams～100 gram/mu dosage, it to the cauline leaf processing activity of broad-leaved rape apparently higher than the soil treatment activity.
Substantive distinguishing features of the present invention can be embodied from following embodiment, but he should not to be considered as be any limitation of the invention.
Embodiment
Embodiment 1:2-cyano group-3,3-diformazan sulfenyl propylene ethyl ester synthetic
The potassium hydroxide powder and the 90mL anhydrous acetonitrile that in the 250mL reaction flask, add 8.2 gram (0.12mol) porphyrizes, ice bath is cooled to and drips 6.8 gram (0.06mol) ethyl cyanacetates about 5 ℃, stirring at room was dissolved in dropwise adding in the 15mL acetonitrile with 4.5 gram (0.06mol) dithiocarbonic anhydride after 1 hour, drip off room temperature reaction 4 hours.Then mixture is cooled to and drips 15.2 gram (0.12mol) methyl-sulfates about 5 ℃, drip off, room temperature reaction 4 hours adds 80mL water then, tells yellow oil, concentrates to be product.
Embodiment 2:2-cyano group-3,3-diformazan sulfenyl vinylformic acid ethoxy ethyl ester synthetic
The potassium hydroxide powder and the 90mL anhydrous acetonitrile that in the 250mL reaction flask, add 8.2 gram (0.12mol) porphyrizes, ice bath is cooled to and drips 9.5 gram (0.06mol) cyanoacetic acid ethoxy ethyl esters about 5 ℃, stirring at room was dissolved in dropwise adding in the 15mL acetonitrile with 4.5 gram (0.06mol) dithiocarbonic anhydride after 1 hour, drip off room temperature reaction 4 hours.Then mixture is cooled to and drips 15.2 gram (0.12mol) methyl-sulfates about 5 ℃, drip off, room temperature reaction 4 hours adds 80mL water then, tells yellow oil, concentrates to be product.
Synthesizing of embodiment 3:2-cyano group-3-methoxyl group-3-Jia Jibingxisuanyizhi
In the 100mL reaction flask, add 6.0 gram (0.053mol) ethyl cyanacetates, 5.15 gram (0.053mol) Magnesium Chloride Anhydrouss, 10.7 gram (0.106mol) triethylamines, cryosel is bathed and is cooled to about-15 ℃, drips 4.16 gram (0.053mol) Acetyl Chloride 98Min.s, drips off to keep the ice bath reaction after 5 hours, concentrate, add dilute hydrochloric acid and wash dichloromethane extraction, anhydrous magnesium sulfate drying, concentrate and obtain intermediate, the diethyl ether solution room temperature reaction 12 hours that adds diazomethane again concentrates, and obtains product.
Synthesizing of embodiment 4:2-cyano group-3-methoxyl group-3-methacrylic acid ethoxy ethyl ester
In the 100mL reaction flask, add 8.35 gram (0.053mol) gram ethyl cyanacetates, 5.15 gram (0.053mol) Magnesium Chloride Anhydrouss, 10.7 gram (0.106mol) triethylamines, cryosel is bathed and is cooled to about-15 ℃, drips 4.16 gram (0.053mol) Acetyl Chloride 98Min.s, drips off to keep the ice bath reaction after 5 hours, concentrate, add dilute hydrochloric acid and wash dichloromethane extraction, anhydrous magnesium sulfate drying, concentrate and obtain intermediate, the diethyl ether solution room temperature reaction 12 hours that adds diazomethane again concentrates, and obtains product.
Embodiment 5:2-chloro-5-methyl isophthalic acid, 3,4-thiadiazoles synthetic
In the 500mL reaction flask, add 5.76 gram (50mmol) 2-amino-5-methyl isophthalic acids, 3,4-thiadiazoles and 90ml concentrated hydrochloric acid, be cooled to 0 ℃, the aqueous solution of Dropwise 5 .30 gram (75mmol) Sodium Nitrite drips off, keep 0 ℃ of reaction 1 hour, drip the concentrated hydrochloric acid solution of 7.25 gram (50mmol) cuprous chlorides then, drip off room temperature reaction 2 hours.Dichloromethane extraction, anhydrous magnesium sulfate drying concentrates, and obtains 2-chloro-5-methyl isophthalic acid, and 3,4-thiadiazoles 5.16 grams, yield 76.53%.
Embodiment 6:2-chloro-5-brooethyl-1,3,4-thiadiazoles synthetic
In the 100mL reaction flask, add 3.41 gram (25.34mmol) 2-chloro-5-methyl isophthalic acids, 3, the 4-thiadiazoles, 5.41 gram (30.40mmol) NBS, the AIBN of catalytic amount, 60ml tetracol phenixin, reflux 6-10 hour, concentrate, column chromatography is separated, and obtains 2-chloro-5-brooethyl-1,3,4-thiadiazoles 2.43 grams, yield 44.93%.
(2-chloro-thiazole-5-) methylthio group ethamine is synthetic for embodiment 7:2-
Add 11.50g (0.1mol) Mercaptamine in the 500mL reaction flask, the 150mL dehydrated alcohol stirs, add 13.92g (0.2mol, 98%) sodium ethylate, room temperature reaction 1h post-heating backflow 2h, be cooled to room temperature, add 16.80g (0.1mol) 2-chloro-5 5-chloromethyl thiazoles, the about 6h of reflux, TLC monitor to there not being the raw material point in batches, filter, concentrate, add the extraction of 500mL methylene dichloride and 100mL water, organic phase is washed with saturated sodium bicarbonate solution successively, the saturated common salt washing, anhydrous magnesium sulfate drying filters, and concentrates, the column chromatography purifying, obtain yellow oil, the heavy 14.20g of product, yield 68.0%.
(the 2-chloropyridine-5-) methylthio group ethamine is synthetic for embodiment 8:2-
Add 11.50g (0.1mol) Mercaptamine in the 500mL reaction flask, the 150mL dehydrated alcohol stirs, add 13.92g (0.2mol, 98%) sodium ethylate, room temperature reaction 1h post-heating backflow 2h, be cooled to room temperature, add 16.40g (0.1mol) 2-chloro-5 chloromethylpyridine, the about 6h of reflux, TLC monitor to there not being the raw material point in batches, filter, concentrate, add the extraction of 500mL methylene dichloride and 100mL water, organic phase is used saturated sodium bicarbonate solution successively, the saturated common salt washing, anhydrous magnesium sulfate drying filters, and concentrates, the column chromatography purifying, obtain yellow oil, the heavy 15.80g of product, yield 78.0%.
The methylthio group of embodiment 8:2-cyano group-3-{2-[(2-diuril azoles-5-)]-ethylamino-}-3-methylthio group vinylformic acid ethoxy ethyl ester synthetic
In the 100mL reaction flask, add 0.80g (3.83mmol) intermediate 2-(the methylthio group ethamine of 2-chloropyridine-5-), 1.0g (3.83mmol) intermediate
2-cyano group-3,3-diformazan sulfenyl vinylformic acid ethoxy ethyl ester, the 30mL dehydrated alcohol stirs reflux, TLC detects, the raw material point back stopped reaction that disappears concentrates, and with 2: 1 (v/v) sherwood oils: ethyl acetate was an eluent, obtain the methylthio group of target compound 2-cyano group-3-{2-[(2-diuril azoles-5-) by silica gel (100-200 order) column chromatography for separation]-ethylamino-}-3-methylthio group vinylformic acid ethoxy ethyl ester 1.21g, yield 74.9%.
The methylsulfinyl of embodiment 9:2-cyano group-3-{2-[(2-diuril azoles-5-)]-ethylamino-}-3-methylthio group vinylformic acid ethoxy ethyl ester synthetic
In the 100mL reaction flask, add the methylthio group of 0.60g (1.42mmol) compound 2-cyano group-3-{2-[(2-diuril azoles-5-)]-ethylamino-}-3-methylthio group vinylformic acid ethoxy ethyl ester; the 30mL methylene dichloride; stir; the ice bath cooling down; add 0.29g (85% in batches; 1.43mmol) metachloroperbenzoic acid; add room temperature reaction to the disappearance of TLC detection raw material; add 5mL water, regulating PH with saturated sodium bicarbonate aqueous solution is 7-8, separatory; twice of dichloromethane extraction of water; merge organic phase, anhydrous magnesium sulfate drying filters; concentrate; with 1: 6 (v/v) sherwood oil: ethyl acetate was an eluent, separated obtaining the methylsulfinyl of target compound 2-cyano group-3-{2-[(2-diuril azoles-5-) by silica gel column chromatography]-ethylamino-}-3-methylthio group vinylformic acid ethoxy ethyl ester 0.56g, yield 89.9%.
The methyl sulphonyl of embodiment 10:2-cyano group-3-{2-[(2-diuril azoles-5-)]-ethylamino-}-3-methylthio group vinylformic acid ethoxy ethyl ester synthetic
In the 100mL reaction flask, add the methylthio group of 0.80g (1.90mmol) compound 2-cyano group-3-{2-[(2-diuril azoles-5-)]-ethylamino-}-3-methylthio group vinylformic acid ethoxy ethyl ester; the 30mL methylene dichloride; stir; the ice bath cooling down; add 0.78g (85% in batches; 3.84mmol) metachloroperbenzoic acid; add room temperature reaction to the disappearance of TLC detection raw material; add 5mL water, regulating pH with saturated sodium bicarbonate aqueous solution is 7-8, separatory; twice of dichloromethane extraction of water; merge organic phase, anhydrous magnesium sulfate drying filters; concentrate; with 1: 4 (v/v) sherwood oil: ethyl acetate was an eluent, separated obtaining the methyl sulphonyl of target compound 2-cyano group-3-{2-[(2-diuril azoles-5-) by silica gel column chromatography]-ethylamino-}-3-methylthio group vinylformic acid ethoxy ethyl ester 0.80g, yield 93.0%.
The methylthio group of embodiment 11:2-cyano group-3-{2-[(2-chloropyridine-5-)]-ethylamino-}-3-methylthio group vinylformic acid ethoxy ethyl ester synthetic
In the 100mL reaction flask, add 2.03g (10.0mmol) intermediate 2-(the methylthio group ethamine of 2-chloropyridine-5-), 2.61g (10.0mmol) intermediate 2-cyano group-3,3-diformazan sulfenyl vinylformic acid ethoxy ethyl ester, the 30mL dehydrated alcohol, stir, reflux, TLC detects, stopped reaction after raw material point disappears, concentrate, with 2: 1 (V/V) sherwood oils: ethyl acetate was an eluent, obtained the methylthio group of target compound 2-cyano group-3-{2-[(2-chloropyridine-5-) by silica gel (100-200 order) column chromatography for separation]-ethylamino-}-3-methylthio group vinylformic acid ethoxy ethyl ester 2.77g, yield 66.5%.
The methylsulfinyl of embodiment 12:2-cyano group-3-{2-[(2-chloropyridine-5-)]-ethylamino-}-3-methylthio group vinylformic acid ethoxy ethyl ester synthetic
In the 100mL reaction flask, add the methylthio group of 1.0g (2.40mmol) compound 2-cyano group-3-{2-[(2-chloropyridine-5-)]-ethylamino-}-3-methylthio group vinylformic acid ethoxy ethyl ester; the 30mL methylene dichloride; stir; the ice bath cooling down; add 0.49g (85% in batches; 2.41mmol) metachloroperbenzoic acid; add room temperature reaction to the disappearance of TLC detection raw material, add 5mL water, regulating pH with saturated sodium bicarbonate aqueous solution is 7-8; separatory; water merges organic phase, anhydrous magnesium sulfate drying with dichloromethane extraction twice; filter; concentrate, with 1: 15 (v/v) sherwood oil: ethyl acetate was an eluent, separated obtaining the methylsulfinyl of target compound 2-cyano group-3-{2-[(2-chloropyridine-5-) by silica gel column chromatography]-ethylamino-}-3-methylthio group vinylformic acid ethoxy ethyl ester; the heavy 0.91g of product, yield 87.6%.
The methyl sulphonyl of embodiment 13:2-cyano group-3-{2-[(2-chloropyridine-5-)]-ethylamino-}-3-methylthio group vinylformic acid ethoxy ethyl ester synthetic
In the 100mL reaction flask, add the methylthio group of 0.80g (1.92mmol) compound 2-cyano group-3-{2-[(2-chloropyridine-5-)]-ethylamino-}-3-methylthio group vinylformic acid ethoxy ethyl ester; the 30mL methylene dichloride; stir; the ice bath cooling down; add 0.90g (85% in batches; 4.43mmol) metachloroperbenzoic acid; add room temperature reaction to the disappearance of TLC detection raw material; add 5mL water, regulating pH with saturated sodium bicarbonate aqueous solution is 7-8, separatory; twice of dichloromethane extraction of water; merge organic phase, anhydrous magnesium sulfate drying filters; concentrate; with 1: 6 (v/v) sherwood oil: ethyl acetate was an eluent, separated obtaining the methyl sulphonyl of target compound 2-cyano group-3-{2-[(2-chloropyridine-5-) by silica gel column chromatography]-ethylamino-}-3-methylthio group vinylformic acid ethoxy ethyl ester 0.78g, yield 90.5%.
With similar method synthetic compound (I).Concrete outcome sees Table 1, table 2.
The materialization data of table 1 part of compounds (I) and ultimate analysis value (perhaps high resolution mass spectrum data)
| 46 | pyridine | C 2H 4OCH 3 | Et | SO 2 | 2 | 1 | 82.1 | 108-109 | 49.07(49.09) | 5.38(5.33) | 10.03(10.10) |
| 47 | pyridine | C 2H 4OC 2H 5 | Pr-i | SO 2 | 2 | 1 | 80.7 | 114-115 | 51.25(51.40) | 6.17(5.90) | 9.28(9.47) |
| 48 | pyridine | C 2H 4OCH 3 | Pr-i | SO 2 | 2 | 1 | 85.3 | 100-102 | 50.09(50.29) | 5.84(5.63) | 9.79(9.77) |
The nuclear magnetic data table of table 2 part of compounds (I)
| Compound | 1H?NMR(400MHz?CDCl 3) |
| 1 | 1.21(t，3H，J＝7.0Hz，OCH 2CH 3)，2.68(s，3H，CH 3S)，2.72(t，2H，J＝6.6Hz，SCH 2CH 2NH)，3.57(q，2H，J＝7.0Hz， OCH 2CH 3)，3.70(t，2H，J＝5.0Hz，CH 2O)，3.79(q，2H，J＝6.4Hz，SCH 2CH 2NH)，3.89(s，2H，CH 2S)，4.31(t，2H，J ＝5.0Hz，OCH 2)，7.39(s，1H，Thiadiazole-H)，10.17(br，1H，CH 2NH). 13C?NMR(100MHz，CDCl 3) |
| 2 | 2.67(s，3H，CH 3S)，2.75(t，2H，J＝6.5Hz，SCH 2CH 2NH)，3.39(s，3H，OCH 3)，3.65(t，2H，J＝4.8Hz，CH 2O)，3.82(q， 2H，J＝6.3Hz，SCH 2CH 2NH)，3.93(s，2H，CH 2S)，4.30(t，2H，J＝4.8Hz，OCH 2)，7.42(s，1H，Thiadiazole-H)， 10.14(br，1H，CH 2NH). |
| 3 | 1.19(t，3H，J＝7.0Hz，OCH 2CH 3)，2.29(s，3H，CH 3C＝C)，2.76(t，2H，J＝6.5Hz，SCH 2CH 2NH)，3.53-3.60(m，4H， SCH 2CH 2NH，OCH 2CH 3)，3.68(t，2H，J＝5.0Hz，CH 2O)，3.92(s，2H，CH 2S)，4.28(t，2H，J＝5.0Hz，OCH 2)，7.40(s， 1H，Thiadiazole-H)，10.07(br，1H，CH 2NH). 13C?NMR(100MHz，CDCl 3) |
| 4 | 2.21(s，3H，CH 3C＝C)，2.67(t，2H，J＝6.4Hz，SCH 2CH 2NH)，3.32(s，3H，OCH 3)，3.42-3.50(m，2H，SCH 2CH 2NH)， 3.57(t，2H，J＝4.8Hz，CH 2O)，3.82(s，2H，CH 2S)，4.23(t，2H，J＝4.8Hz，OCH2)，7.32(s，1H，Thiadiazole-H)，9.99(br， 1H，CH 2NH). |
| 5 | 1.19(t，3H，J＝7.0Hz，OCH 2CH 3)，1.24(t，3H，J＝7.5Hz，CH 3CH 2C＝C)，2.61(q，2H，J＝7.5Hz，CH 3CH 2C＝C)，2.78(t， 2H，J＝6.2Hz，SCH 2CH 2NH)，3.53-3.61(m，4H，SCH 2CH 2NH，OCH2CH3)，3.68(t，2H，J＝4.6Hz，CH 2O)，3.94(s，2H， CH 2S)，4.28(t，2H，J＝4.6Hz，OCH 2)，7.42(s，1H，Thiadiazole-H)，10.02(br，1H，CH 2NH). |
| 6 | 1.24(t，3H，J＝7.5Hz，CH 3CH 2C＝C)，2.61(q，2H，J＝7.5Hz，CH 3CH 2C＝C)，2.76(t，2H，J＝6.4Hz，SCH 2CH 2NH)， 3.39(s，3H，OCH 3)，3.51-3.59(m，2H，SCH 2CH 2NH)，3.64(t，2H，J＝4.6Hz，CH 2O)，3.92(s，2H，CH 2S)，4.30(t，2H，J ＝4.6Hz，OCH 2)，7.41(s，1H，Thiadiazole-H)，10.02(bt，1H，CH 2NH). |
| 7 | 1.20(t，3H，J＝7.0Hz，OCH 2CH 3)，1.39(d，6H，J＝7.2Hz，CH(CH 3) 2)，2.75(t，2H，J＝6.6Hz，SCH 2CH 2NH)， 3.11-3.14(m，1H，CH(CH 3) 2)，3.54-3.64(m，4H，SCH 2CH 2NH，OCH 2CH 3)，3.69(t，2H，J＝5.1Hz，CH 2O)，3.92(s，2H， CH 2S)，4.28(t，2H，J＝5.1Hz，OCH 2)，7.41(s，1H，Thiadiazole-H)，10.34(br，1H，CH 2NH). |
| 8 | 1.30(d，6H，J＝7.0Hz，CH(CH 3) 2)，2.66(t，2H，J＝6.3Hz，SCH 2CH 2NH)，2.96-3.08(m，1H，CH(CH 3) 2)，3.31(s，3H， OCH 3)，3.52-3.56(m，4H，SCH 2CH 2NH，CH 2CH 2O)，3.85(s，2H，CH 2S)，4.21(t，2H，J＝4.8Hz，OCH 2)，7.33(s，1H， Thiadiazole-H)，10.30(br，1H，CH 2NH). |
| 9 | 1.19(t，3H，J＝7.0Hz，OCH 2CH 3)，2.69(s，3H，CH 3S)，2.87-2.94(m，1H，O＝SCH 2CH 2NH)，3.00-3.07(m，1H， O＝SCH 2CH 2NH)，3.55(q，2H，J＝7.0Hz，OCH 2CH 3)，3.67(s，2H，J＝4.7Hz，CH 2O)，4.04-4.16(m，2H， O＝SCH 2CH 2NH)，4.20(d，1H，J＝14.5Hz，CH 2S＝O)，4.28(t，2H，J＝4.7Hz，OCH 2)，4.39(d，1H，J＝14.4Hz， CH 2S＝O)，7.56(s，1H，Thiazole-H)，10.15(br，1H，CH 2NH). |
| 10 | 2.67(s，3H，CH 3S)，2.75(t，2H，J＝6.5Hz，SCH 2CH 2NH)，3.39(s，3H，OCH 3)，3.65(t，2H，J＝4.8Hz，CH 2O)，3.82(q， 2H，J＝6.3Hz，SCH 2CH 2NH)，3.93(s，2H，CH 2S)，4.30(t，2H，J＝4.8Hz，OCH 2)，7.42(s，1H，Thiadiazole-H)， 10.14(br，1H，CH 2NH). |
| 11 | 1.19(t，3H，J＝7.0Hz，OCH 2CH 3)，2.29(s，3H，CH 3C＝C)，2.76(t，2H，J＝6.5Hz，SCH 2CH 2NH)，3.53-3.60(m，4H， SCH 2CH 2NH，OCH 2CH 3)，3.68(t，2H，J＝5.0Hz，CH 2O)，3.92(s，2H，CH 2S)，4.28(t，2H，J＝5.0Hz，OCH 2)，7.40(s， 1H，Thiadiazole-H)，10.07(br，1H，CH 2NH). |
| 12 | 2.21(s，3H，CH 3C＝C)，2.67(t，2H，J＝6.4Hz，SCH 2CH 2NH)，3.32(s，3H，OCH 3)，3.42-3.50(m，2H，SCH 2CH 2NH)， 3.57(t，2H，J＝4.8Hz，CH 2O)，3.82(s，2H，CH 2S)，4.23(t，2H，J＝4.8Hz，OCH 2)，7.32(s，1H，Thiadiazole-H)，9.99(br， 1H，CH 2NH). |
| 13 | 1.19(t，3H，J＝7.0Hz，OCH 2CH 3)，1.24(t，3H，J＝7.5Hz，CH 3CH 2C＝C)，2.61(q，2H，J＝7.5Hz，CH 3CH 2C＝C)，2.78(t， 2H，J＝6.2Hz，SCH 2CH 2NH)，3.53-3.61(m，4H，SCH 2CH 2NH，OCH 2CH 3)，3.68(t，2H，J＝4.6Hz，CH 2O)，3.94(s， 2H，CH 2S)，4.28(t，2H，J＝4.6Hz，OCH 2)，7.42(s，1H，Thiadiazole-H)，10.02(br，1H，CH 2NH). |
| 14 | 1.24(t，3H，J＝7.5Hz，CH 3CH 2C＝C)，2.61(q，2H，J＝7.5Hz，CH 3CH 2C＝C)，2.76(t，2H，J＝6.4Hz，SCH 2CH 2NH)， 3.39(s，3H，OCH 3)，3.51-3.59(m，2H，SCH 2CH 2NH)，3.64(t，2H，J＝4.6Hz，CH 2O)，3.92(s，2H，CH 2S)，4.30(t，2H， J＝4.6Hz，OCH 2)，7.41(s，1H，Thiadiazole-H)，10.02(br，1H，CH 2NH). |
| 15 | 1.20(t，3H，J＝7.0Hz，OCH 2CH 3)，1.39(d，6H，J＝7.2Hz，CH(CH 3) 2)，2.75(t，2H，J＝6.6Hz，SCH 2CH 2NH)， 3.11-3.14(m，1H，CH(CH 3) 2)，3.54-3.64(m，4H，SCH 2CH 2NH，OCH 2CH 3)，3.69(t，2H，J＝5.1Hz，CH 2O)，3.92(s，2H， CH 2S)，4.28(t，2H，J＝5.1Hz，OCH 2)，7.41(s，1H，Thiadiazole-H)，10.34(br，1H，CH 2NH). |
| 16 | 1.30(d，6H，J＝7.0Hz，CH(CH 3) 2)，2.66(t，2H，J＝6.3Hz，SCH 2CH 2NH)，2.96-3.08(m，1H，CH(CH 3) 2)，3.31(s，3H， OCH 3)，3.52-3.56(m，4H，SCH 2CH 2NH，CH 2CH 2O)，3.85(s，2H，CH 2S)，4.21(t，2H，J＝4.8Hz，OCH 2)，7.33(s，1H， Thiadiazole-H)，10.30(br，1H，CH 2NH). |
| 17 | 1.20(t，3H，J＝6.7Hz，OCH 2CH 3)，2.71(s，3H，CH 3S)，3.28(t，2H，J＝6.0Hz，SO 2CH 2CH 2NH)，3.56(q，2H，J＝ 6.7Hz，OCH 2CH 3)，3.69(t，2H，J＝5.0Hz，CH 2O)，4.13-4.16(m，2H，SO 2CH 2CH 2NH)，4.31(t，2H，J＝5.0Hz，OCH 2)， 4.47(s，2H，CH 2SO 2)，7.60(s，1H，Thiazole-H)，10.18(br，1H，CH 2NH). |
| 18 | 2.71(s，3H，CH 3S)，3.32(m，2H，SO 2CH 2CH 2NH)，3.39(s，3H，OCH 3)，3.65(t，2H，J＝5.0Hz，CH 2O)，4.09-4.14(m， 2H，SO 2CH 2CH 2NH)，4.32(t，2H，J＝5.0Hz，OCH 2)，4.50(s，2H，CH 2SO 2)，7.61(s，1H，Thiazole-H)，10.17(br，1H， CH 2NH) |
| 19 | 1.12(t，3H，J＝6.9Hz，OCH 2CH 3)，2.27(s，3H，CH 3C＝C)，3.21(t，2H，J＝5.5Hz，，SO 2CH 2CH 2NH)，3.48(q，2H，J＝ 6.9Hz，，OCH 2CH 3)，3.60(t，2H，J＝4.4Hz，CH 2O)，3.83(q，2H，J＝5.5Hz，SO 2CH 2CH 2NH)，4.22(t，2H，J＝4.4Hz， OCH 2)，4.39(s，2H，CH 2SO 2)，7.55(s，1H，Thiazole-H)，10.03(br，1H，CH 2NH). |
| 20 | 2.35(s，3H，CH 3C＝C)，3.28(t，2H，J＝6.3H?z，SO 2CH 2CH 2NH)，3.38(s，3H，OCH 3)，3.64(t，2H，J＝4.7Hz，CH 2O)， 3.90(q，2H，J＝6.3Hz，SO 2CH 2CH 2NH)，4.31(t，2H，J＝4.7Hz，OCH 2)，4.45(s，2H，CH 2SO 2)，7.62(s，1H， Thiazole-H)，10.11(br，1H，CH 2NH). |
| 21 | 1.18(t，3H，J＝7.0Hz，OCH 2CH 3)，1.26(t，3H，J＝6.5Hz，CH 3CH 2C＝C)，2.64(q，2H，J＝6.5Hz，CH 3CH 2C＝C)，3.35(t， 2H，J＝5.5Hz，SO 2CH 2CH 2NH)，3.54(q，2H，J＝6.9Hz，OCH 2CH 3)，3.67(t，2H，J＝4.4Hz，CH 2O)，3.90(q，2H，J＝ 5.5Hz，SO 2CH 2CH 2NH)，4.28(t，2H，J＝4.4Hz，OCH 2)，4.53(s，2H，CH2SO2)，7.63(s，1H，Thiazole-H)，10.04(br，1H， CH 2NH). |
| 22 | 1.26(t，3H，J＝7.6Hz，CH 3CH 2C＝C)，2.65(q，2H，J＝7.6Hz，CH 3CH 2C＝C)，3.29(t，2H，J＝6.3Hz，SO 2CH 2CH 2NH)， 3.39(s，3H，OCH 3)，3.64(t，2H，J＝4.8Hz，CH 2O)，3.90(q，2H，J＝6.3Hz，SO 2CH 2CH 2NH)，4.31(t，2H，J＝4.8Hz， OCH 2)，4.46(s，2H，CH 2SO 2)，7.62(s，1H，Thiazole-H)，10.05(br，1H，CH 2NH). |
| 23 | 1.11(t，3H，J＝6.0Hz，OCH 2CH 3)，1.33(d，6H，J＝5.5Hz，CH(CH 3) 2)，3.00-3.10(m，1H，CH(CH 3) 2)，3.26(t，2H，J＝ 5.5Hz，，SO 2CH 2CH 2NH)，3.47(q，2H，J＝6.0Hz，OCH 2CH 3)，3.60(t，2H，J＝4.4Hz，CH 2O)，3.88(q，2H，J＝5.5Hz， SO 2CH 2CH 2NH)，4.20(t，2H，J＝4.4Hz，OCH 2)，4.48(s，2H，CH 2SO 2)，7.56(s，1H，Thiazole-H)，10.31(br，1H， CH 2NH). |
| 24 | 1.41(d，6H，J＝7.1Hz，CH(CH 3) 2)，3.16-3.19(m，1H，CH(CH 3) 2)，3.37(s，3H，OCH 3)，3.38(t，2H，J＝6.0Hz， SO 2CH 2CH 2NH)，3.63(t，2H，J＝4.6Hz，CH 2O)，3.97(q，2H，J＝6.0Hz，SO 2CH 2CH 2NH)，4.28(t，2H，J＝4.6Hz， OCH 2)，4.60(s，2H，CH 2SO 2)，7.64(s，1H，Thiazole-H)，10.39(br，1H，CH 2NH). |
| 25 | 1.21(t，3H，J＝7.0Hz，OCH 2CH 3)，2.63(t，2H，J＝6.6Hz，SCH 2CH 2NH)，2.68(s，3H，CH 3S)，3.57(q，2H，J＝7.0Hz， OCH 2CH 3)，3.68-3.78(m，6H，CH 2SCH 2CH 2NH，CH 2O)，4.31(t，2H，J＝5.1Hz，OCH 2)，7.33(d，1H，J＝8.2Hz， Pyridine-H)，7.70(dd，1H，J＝2.5Hz，J＝8.2Hz，Pyridine-H)，8.31(d，1H，J＝2.3Hz，Pyridine-H)，10.17(br，1H， CH 2NH). |
| 26 | 2.63(t，2H，J＝6.6Hz，SCH 2CH 2NH)，2.67(s，3H，CH 3S)，3.40(s，3H，OCH 3)，3.65(t，2H，J＝4.8Hz，CH 2O)， 3.74-3.80(m，4H，CH 2SCH 2CH 2NH)，4.32(t，2H，J＝4.8Hz，OCH 2)，7.33(d，1H，J＝8.2Hz，Pyridine-H)，7.72(dd， 1H，J＝2.4Hz，J＝8.2Hz，Pyridine-H)，8.31(d，1H，J＝2.3Hz，Pyridine-H)，10.17(br，1H，CH 2NH). |
| 27 | 1.20(t，3H，J＝7.0Hz，OCH 2CH 3)，2.28(s，3H，CH 3C＝C)，2.67(t，2H，J＝6.4Hz，SCH 2CH 2NH)，3.49-3.59(m，4H， CH 2SCH 2CH 2NH，OCH 2CH 3)，3.69(t，2H，J＝5.0Hz，CH 2O)，3.74(s，2H，CH 2SCH 2CH 2NH)，4.29(t，2H，J＝5.0Hz， OCH 2)，7.33(d，1H，J＝8.1Hz，Pyridine-H)，7.71(dd，1H，J＝2.5Hz，J＝8.2Hz，Pyridine-H)，8.31(d，1H，J＝2.3Hz， Pyridine-H)，10.08(br，1H，CH 2NH). |
| 28 | 2.27(s，3H，CH 3C＝C)，2.65(t，2H，J＝6.5Hz，CH 2SCH 2CH 2NH)，3.41(s，3H，OCH 3)，3.49(q，2H，J＝6.3Hz， CH 2SCH 2CH 2NH)，3.65(t，2H，J＝4.9Hz，CH 2O)，3.72(s，2H，CH 2SCH 2CH 2NH)，4.32(t，2H，J＝4.9Hz，OCH 2)， 7.33(d，1H，J＝8.2Hz，Pyridine-H)，7.70(dd，1H，J＝2.5Hz，J＝8.3Hz，Pyridine-H)，8.30(d，1H，J＝2.2Hz， Pyridine-H)，10.08(br，1H，CH 2NH). |
| 29 | 1.18-1.28(m，6H，CH 3CH 2C＝C，OCH 2CH 3)，2.58(q，2H，J＝7.7Hz，CH 3CH 2C＝C)，2.68(t，2H，J＝6.4Hz， SCH 2CH 2NH)，3.49-3.60(m，4H，CH 2SCH 2CH 2NH，OCH 2CH 3)，3.69(t，2H，J＝5.1Hz，CH 2O)，3.75(s，2H， CH 2SCH 2CH 2NH)，4.30(t，2H，J＝5.1Hz，OCH 2)，7.33(d，1H，J＝8.6Hz，Pyridine-H)，7.72(dd，1H，J＝2.5Hz，J＝ 8.2Hz，Pyridine-H)，8.31(d，1H，J＝2.3Hz，Pyridine-H)，10.03(br，1H，CH 2NH). |
| 30 | 1.23(t，3H，J＝7.7Hz，CH 3CH 2C＝C)，2.58(q，2H，J＝7.7Hz，CH 3CH 2C＝C)，2.67(t，2H，J＝6.6Hz， CH 2SCH 2CH 2NH)，3.41(s，3H，OCH 3)，3.50(q，2H，J＝6.3Hz，CH 2SCH 2CH 2NH)，3.66(t，2H，J＝4.9Hz，CH 2O)， 3.73(s，2H，CH 2SCH 2CH 2NH)，4.31(t，2H，J＝4.9Hz，OCH 2)，7.33(d，1H，J＝8.2Hz，Pyridine-H)，7.70(dd，1H，J＝ 2.5Hz，J＝8.2Hz，Pyridine-H)，8.31(d，1H，J＝2.2Hz，Pyridine-H)，10.02(br，1H，CH 2NH). |
| 31 | 1.21(t，3H，J＝7.0Hz，OCH 2CH 3)，1.38(d，6H，J＝7.2Hz，CH(CH 3)2)，2.66(t，2H，J＝6.5Hz，CH 2SCH 2CH 2NH)， 2.90-3.18(m，1H，CH(CH 3) 2)，3.53-3.61(m，4H，CH 2SCH 2CH 2NH，OCH 2CH 3)，3.70(t，2H，J＝5.0Hz，CH 2O)，3.75(s， 2H，CH 2SCH 2CH 2NH)，4.30(t，2H，J＝5.0Hz，OCH 2)，7.34(d，1H，J＝8.2Hz，Pyridine-H)，7.72(dd，1H，J＝2.1Hz，J ＝8.2Hz，Pyridine-H)，8.31(d，1H，J＝1.7Hz，Pyridine-H)，10.39(br，1H，CH 2NH). |
| 32 | 1.38(d，6H，J＝7.2Hz，CH(CH 3) 2)，2.65(t，2H，J＝6.6Hz，CH 2SCH 2CH 2NH)，3.10-3.14(m，1H，CH(CH 3) 2)，3.41(s， 3H，OCH 3)，3.55(q，2H，J＝6.3Hz，CH 2SCH 2CH 2NH)，3.66(t，2H，J＝4.9Hz，CH 2O)，3.74(s，2H，CH 2SCH 2CH 2NH)， 4.31(t，2H，J＝4.9Hz，OCH 2)，7.33(d，1H，J＝8.2Hz，Pyridine-H)，7.71(dd，1H，J＝2.5Hz，J＝8.2Hz，Pyridine-H)， 8.31(d，1H，J＝2.3Hz，Pyridine-H)，10.38(b?r，1H，CH 2NH). |
| 33 | 1.18(t，3H，J＝6.9Hz，OCH 2CH 3)，2.68(s，3H，CH 3S)，2.89-2.93(m，1H，S＝OCH 2CH 2NH)，3.06-3.11(m，1H， S＝OCH 2CH 2NH)，3.54(q，2H，J＝6.8Hz，OCH 2CH 3)，3.67(t，3H，J＝4.9Hz，CH 2O)，3.99-4.11(m，2H， S＝OCH 2CH 2NH)，4.19(d，2H，J＝13.1Hz，CH 2S＝O)，4.28(t，2H，J＝4.9Hz，OCH 2)，7.39(d，1H，J＝8.1Hz， Pyridine-H)，7.74(d，1H，J＝7.9Hz，Pyridine-H)，8.36(s，1H，Pyridine-H)，10.17(br，1H，CH 2NH). |
| 34 | 2.68(s，3H，CH 3S)，2.89-2.95(m，1H，S＝OCH 2CH 2NH)，3.07-3.14(m，1H，S＝OCH 2CH 2NH)，3.37(s，3H，OCH 3)， 3.63(t，3H，J＝4.6Hz，CH 2O)，3.99-4.13(m，2H，S＝OCH 2CH 2NH)，4.20(d，2H，J＝13.4Hz，CH 2S＝O)，4.29(t，2H，J＝ 4.6Hz，OCH 2)，7.39(d，1H，J＝8.2Hz，Pyridine-H)，7.74(d，1H，J＝8.2Hz，Pyridine-H)，8.36(s，1H，Pyridine-H)， 10.16(br，1H，CH 2NH). |
| 35 | 1.18(t，3H，J＝7.0Hz，OCH 2CH 3)，2.34(s，3H，CH 3C＝C)，3.23(t，2H，J＝6.3Hz，S＝OCH 2CH 2NH)，3.55(q，2H，J＝ 7.0Hz，OCH 2CH 3)，3.67(t，3H，J＝4.9Hz，CH 2O)，3.90(q，2H，J＝6.3Hz，S＝OCH 2CH 2NH)，4.27-4.30(m，4H， CH 2S＝O，OCH 2)，7.43(d，1H，J＝8.2Hz，Pyridine-H)，7.74(d，1H，J＝8.3Hz，Pyridine-H)，8.41(s，1H，Pyridine-H)， 10.13(br，1H，CH 2NH). |
| 36 | 2.34(s，3H，CH 3C＝C)，2.91-2.94(m，1H，S＝OCH 2CH 2NH)，3.09-3.16(m，1H，S＝OCH 2CH 2NH)，3.35(s，3H，OCH 3)， 3.62(t，3H，J＝4.6Hz，CH 2O)，3.87-4.27(m，6H，OCH 2，CH 2S＝OCH 2CH 2NH)，7.39(d，1H，J＝8.1Hz，Pyridine-H)， 7.74(d，1H，J＝7.5Hz，Pyridine-H)，8.35(s，1H，Pyridine-H)，10.08(br，1H，CH 2NH). |
| 37 | 1.19(t，3H，J＝7.5Hz，OCH 2CH 3)，1.25(t，3H，J＝7.5Hz，CH 3CH 2C＝C)，2.62-2.66(m，2H，CH 3CH 2C＝C)， 2.85-3.04(m，2H，S＝OCH 2CH 2NH)，3.55(q，2H，J＝7.0Hz，OCH 2CH 3)，3.67(t，3H，J＝4.6Hz，CH 2O)，3.84-3.93(m， 2H，CH 2S＝OCH 2CH 2NH)，3.97(d，1H，J＝13.4Hz，CH 2S＝OCH 2CH 2NH)，4.15(d，1H，J＝13.4Hz， CH 2S＝OCH 2CH 2NH)，4.27(t，2H，J＝4.6Hz，OCH 2)，7.40(d，1H，J＝8.2Hz，Pyridine-H)，7.71(d，1H，J＝7.1Hz， Pyridine-H)，8.34(s，1H，Pyridine-H)，10.04(br，1H，CH 2NH). |
| 38 | 1.25(t，3H，J＝6.8Hz，CH 3CH 2C＝C)，2.57-2.65(m，2H，CH 3CH 2C＝C)，2.88-3.04(m，2H，S＝OCH 2CH 2NH)，3.38(s， 3H，OCH 3)，3.63(t，3H，J＝4.8Hz，CH 2O)，3.84-4.18(m，2H，CH 2S＝OCH 2CH 2NH)，4.28(t，2H，J＝4.8Hz，OCH 2)， 7.39(d，1H，J＝8.2Hz，Pyridine-H)，7.71(d，1H，J＝7.9Hz，Pyridine-H)，8.35(s，1H，Pyridine-H)，10.02(br，1H， CH 2NH). |
| 39 | 1.23(t，3H，J＝7.0Hz，OCH 2CH 3)，1.41(d，6H，J＝7.2Hz，CH(CH 3) 2)，2.86(m，2H，S＝OCH 2CH 2NH)，3.10-3.36(m， 1H，CH(CH 3) 2)，3.57(q，2H，J＝7.0Hz，OCH 2CH 3)，3.70(t，2H，J＝4.8Hz，CH 2O)，3.92-3.95(m，2H， CH 2S＝OCH 2CH 2NH)，4.10-4.14(m，2H，CH 2S＝OCH 2CH 2NH)，4.28(t，2H，J＝4.8Hz，OCH 2)，7.40(d，1H，J＝7.8Hz， Pyridine-H)，7.69(d，1H，J＝7.9Hz，Pyridine-H)，8.34(s，1H，Pyridine-H)，10.41(br，1H，CH 2NH). |
| 40 | 1.40(d，6H，J＝6.8Hz，CH(CH 3) 2)，2.86-3.20(m，3H，S＝OCH 2CH 2NH，CH(CH 3) 2)，3.37(s，3H，OCH 3)，3.63(t，2H，J ＝4.8Hz，CH 2O)，3.91-4.28(m，6H，J＝4.8Hz，OCH 2，CH 2S＝OCH 2CH 2NH)，7.40(d，1H，J＝7.8Hz，Pyridine-H)， 7.74(d，1H，J＝7.2Hz，Pyridine-H)，8.35(s，1H，Pyridine-H)，10.43(br，1H，CH 2NH). |
| 41 | 1.20(t，3H，J＝7.0Hz，OCH 2CH 3)，2.72(s，3H，CH 3S)，3.22(t，2H，J＝6.4Hz，SO 2CH 2CH 2NH)，3.56(q，2H，J＝7.0Hz， OCH 2CH 3)，3.69(t，2H，J＝5.0Hz，CH 2O)，4.14(q，2H，J＝6.4Hz，CH 2SO 2CH 2CH 2NH)，4.27(s，2H， CH 2SO 2CH 2CH 2NH)，4.31(t，2H，J＝5.0Hz，OCH 2)，7.43(d，1H，J＝8.3Hz，Pyridine-H)，7.80(dd，1H，J＝2.5Hz，J ＝8.3Hz，Pyridine-H)，8.40(d，1H，J＝2.4Hz，Pyridine-H)，10.22(b?r，1H，CH 2NH). |
| 42 | 2.70(s，3H，CH 3S)，3.29(t，2H，J＝6.3Hz，CH 2SO 2CH 2CH 2NH)，3.37(s，3H，OCH 3)，3.64(t，2H，J＝4.6Hz，CH 2O)， 4.15(q，2H，J＝6.2Hz，CH 2SO 2CH 2CH 2NH)，4.29-4.32(m，4H，CH 2SO 2CH 2CH 2NH?OCH 2)，7.42(d，1H，J＝8.2Hz， Pyridine-H)，7.81(dd，1H，J＝1.8Hz，J＝8.2Hz，Pyridine-H)，8.42(d，1H，J＝2.4Hz，Pyridine-H)，10.20(br，1H， CH 2NH). |
| 43 | 1.18(t，3H，J＝7.0Hz，OCH 2CH 3)，2.34(s，3H，CH 3C＝C)，3.23(t，2H，J＝6.2Hz，SO 2CH 2CH 2NH)，3.55(q，2H，J＝ 7.0Hz，OCH 2CH 3)，3.67(t，2H，J＝4.9Hz，CH 2O)，3.90(q，2H，J＝6.2Hz，CH 2SO 2CH 2CH 2NH)，4.28-4.31(m，4H， CH 2SO 2CH 2CH 2NH，OCH 2)，7.43(d，1H，J＝8.2Hz，Pyridine-H)，7.81(dd，1H，J＝1.9Hz，J＝8.2Hz，Pyridine-H)， 8.41(s，1H，Pyridine-H)，10.13(br，1H，CH 2NH). |
| 44 | 1H?NMR(400MHz，DMSO-d 6)，δ2.30(s，3H，CH 3C＝C)，3.27(s，3H，OCH 3)，3.50-3.55(m，4H，CH 2O， CH 2SO 2CH 2CH 2NH)，3.86(q，2H，J＝5.9Hz，CH 2SO 2CH 2CH 2NH)，4.20(t，2H，J＝4.0Hz，OCH 2)，4.67(s，2H， CH 2SO 2CH 2CH 2NH)，7.61(d，1H，J＝8.1Hz，Pyridine-H)，7.90(d，1H，J＝7.7Hz，Pyridine-H)，8.43(s，1H， Pyridine-H)，9.95(br，1H，CH 2NH). |
| 45 | 1.18(t，3H，J＝7.0Hz，OCH 2CH 3)，1.26(t，3H，J＝7.6Hz，CH 3CH 2C＝C)，2.64(q，2H，J＝7.6Hz，CH 3CH 2C＝C)，3.28(t， 2H，J＝6.2Hz，SO 2CH 2CH 2NH)，3.55(q，2H，J＝7.0Hz，OCH 2CH 3)，3.67(t，2H，J＝4.9Hz，CH 2O)，3.90(q，2H，J＝ 6.2Hz，CH 2SO 2CH 2CH 2NH)，4.28(t，2H，J＝4.9Hz，OCH 2)，4.31(s，2H，CH 2SO 2CH 2CH 2NH)，7.42(d，1H，J＝8.2Hz， Pyridine-H)，7.81(dd，1H，J＝2.3Hz，J＝8.2Hz，Pyridine-H)，8.42(d，1H，J＝1.9Hz，Pyridine-H)，10.07(br，1H， CH 2NH). |
| 46 | 1.26(t，3H，J＝7.6Hz，CH 3CH 2C＝C)，2.64(q，2H，J＝7.6Hz，CH 3CH 2C＝C)，3.26(t，2H，J＝6.3Hz， CH 2SO 2CH 2CH 2NH)，3.38(s，3H，OCH 3)，3.63(t，2H，J＝4.7Hz，CH 2O)，3.90(q，2H，J＝6.2Hz， CH 2SO 2CH 2CH 2NH)，4.29-4.31(m，4H，CH 2SO 2CH 2CH 2NH?OCH 2)，7.42(d，1H，J＝8.2Hz，Pyridine-H)，7.81(dd， 1H，J＝2.0Hz，J＝8.2Hz，Pyridine-H)，8.42(s，1H，Pyridine-H)，10.06(br，1H，CH 2NH). |
| 47 | 1.19(t，3H，J＝7.0Hz，OCH 2CH 3)，1.41(d，6H，J＝7.2Hz，CH(CH 3) 2)，3.07-3.19(m，1H，CH(CH 3) 2)，3.22(t，2H，J＝ 6.5Hz，SO 2CH 2CH 2NH)，3.56(q，2H，J＝7.0Hz，OCH 2CH 3)，3.68(t，2H，J＝5.0Hz，CH 2O)，3.95(q，2H，J＝6.4Hz， CH 2SO 2CH 2CH 2NH)，4.27-4.30(m，4H，CH 2SO 2CH 2CH 2NH，OCH 2)，7.43(d，1H，J＝8.3Hz，Pyridine-H)，7.80(dd， 1H，J＝2.4Hz，J＝8.3Hz，Pyridine-H)，8.41(d，1H，J＝2.3Hz，Pyridine-H)，10.41(br，1H，CH 2NH). |
| 48 | 1.41(d，6H，J＝7.2Hz，CH(CH 3) 2)，3.10-3.20(m，1H，CH(CH 3) 2)，3.26(t，2H，J＝6.5Hz，CH 2SO 2CH 2CH 2NH)， 3.38(s，3H，OCH 3)，3.64(t，2H，J＝4.7Hz，CH 2O)，3.95(q，2H，J＝6.3Hz，CH 2SO 2CH 2CH 2NH)，4.28-4.31(m，4H， CH 2SO 2CH 2CH 2NH?OCH 2)，7.43(d，1H，J＝8.2Hz，Pyridine-H)，7.81(dd，1H，J＝2.3Hz，J＝8.3Hz，Pyridine-H)， 8.42(d，1H，J＝1.8Hz，Pyridine-H)，10.41(br，1H，CH 2NH). |
The primary dcreening operation of embodiment 13 weeding activity is measured
Pot-culture method (cauline leaf processing): in the dixie cup of 8 centimetres of diameters, put into a certain amount of soil, add a certain amount of water, after planting cover certain thickness soil, in greenhouse, cultivate, cover with plastic film before coming up.After emerging, every day in addition quantitative clear water to keep normal growth.Carrying out the cauline leaf spraying when seedling length to the certain period handles.Treatment dosage is 100 gram/mus.Handle 20 days " Invest, Then Investigate " results, measure fresh weight on the ground, suppress percentage ratio with fresh weight and represent drug effect.
Pot-culture method (soil treatment): in the dixie cup of 8 centimetres of diameters, put into a certain amount of soil, add a certain amount of water, after planting cover certain thickness soil, and, in greenhouse, cultivate then, cover with plastic film before coming up in dispenser on the same day.After emerging, every day in addition quantitative clear water to keep normal growth.Carrying out the cauline leaf spraying when seedling length to the certain period handles.Treatment dosage is 100 gram/mus.Handle 20 days " Invest, Then Investigate " results, measure fresh weight on the ground, suppress percentage ratio with fresh weight and represent drug effect.
Measure part of compounds (I) live body weeding activity: with rape, barnyard grass grass, Amaranthus retroflexus and Ma Tang is the examination material
The results are shown in Table 3.
The weeding activity inhibiting rate of table 3 part of compounds (I) (dosage 100 gram/mus, inhibiting rate %)
| 3 | 51.8 | 39.7 | 0 | 0 | 100 | 41.1 | 15.0 | 34.7 |
| 4 | 10.0 | 0 | 0 | 0 | 95.0 | 32.6 | 0 | 5.0 |
| 5 | 44.6 | 0 | 0 | 0 | 100 | 90.0 | 57.6 | 76.2 |
| 6 | 79.3 | 17.5 | 10.0 | 0 | 100 | 85.3 | 57.1 | 68.3 |
| 7 | 74.0 | 14.3 | 0 | 51.1 | 100 | 100 | 80.0 | 100 |
| 8 | 15.0 | 72.3 | 0 | 0 | 100 | 100 | 98.0 | 98.6 |
| 9 | 0 | 0 | 0 | 0 | 10.0 | 0 | 0 | 14.0 |
| 10 | 0 | 0 | 0 | 0 | 0 | 0 | 5.0 | 0 |
| 11 | 8.5 | 0 | 0 | 0 | 90.0 | 41.1 | 5.0 | 0 |
| 12 | 0 | 0 | 10.0 | 0 | 85.0 | 5.0 | 0 | 0 |
| 13 | 0 | 0 | 0 | 0 | 96.0 | 74.7 | 5.0 | 0 |
| 14 | 0 | 5.0 | 0 | 0 | 100 | 95.6 | 57.5 | 0 |
| 15 | 4.0 | 0 | 0 | 15.0 | 100 | 100 | 47.1 | 46.5 |
| 16 | 0 | 15.0 | 0 | 0 | 100 | 100 | 85.5 | 74.6 |
| 17 | 5.0 | 27.0 | 0 | 0 | 15.0 | 0 | 10.0 | 10 |
| 18 | 4.6 | 0 | 0 | 0 | 0 | 17.9 | 0 | 10 |
| 19 | 10.0 | 0 | 0 | 10.0 | 80.0 | 0 | 0 | 0 |
| 10 | 5.0 | 15.0 | 0 | 0 | 15.0 | 40.7 | 28.3 | 18.3 |
| 21 | 0 | 0 | 0 | 0 | 98.0 | 0 | 0 | 0 |
| 22 | 10.0 | 10.0 | 0 | 0 | 68.0 | 45.1 | 32.3 | 32.4 |
| 23 | 60.1 | 5.0 | 5.0 | 0 | 100 | 60.0 | 55.9 | 32.7 |
| 24 | 0 | 0 | 10.0 | 0 | 100 | 98.9 | 60.0 | 46.5 |
| 25 | 0 | 10.0 | 0 | 0 | 100 | 18.7 | 20.0 | 81.2 |
| 26 | 0 | 10.0 | 0 | 0 | 100 | 0 | 10.0 | 75.0 |
| 27 | 5.0 | 10.0 | 0 | 0 | 100 | 37.3 | 10.0 | 95.8 |
| 28 | 5.0 | 20.0 | 0 | 0 | 86.3 | 72.9 | 15.0 | 70.8 |
| 29 | 0 | 5.0 | 10.0 | 0 | 100 | 98.3 | 0 | 91.7 |
| 30 | 5.0 | 5.0 | 0 | 0 | 100 | 86.4 | 64.0 | 91.7 |
| 31 | 38.1 | 10.0 | 23.8 | 0.0 | 100 | 100 | 71.5 | 98.8 |
| 32 | 0 | 0 | 0 | 0 | 100 | 100 | 92.5 | 100 |
| 33 | 5.0 | 0 | 0 | 10.0 | 63.4 | 1.7 | 15.0 | 89.6 |
| 34 | 0 | 0 | 0 | 5.0 | 33.5 | 0 | 5.0 | 0 |
| 35 | 0 | 10.0 | 0 | 0 | 31.0 | 0 | 0 | 0 |
| 36 | 0 | 0 | 0 | 0 | 100 | 22.0 | 15.0 | 62.5 |
| 37 | 0 | 15.0 | 0 | 0 | 83.2 | 8.5 | 10.0 | 79.2 |
| 38 | 10.0 | 10.0 | 0 | 10.0 | 86.9 | 72.9 | 0 | 89.6 |
| 39 | 5.0 | 0 | 0 | 0 | 100 | 88.1 | 0 | 93.8 |
| 40 | 0 | 0 | 0 | 0 | 100 | 100 | 20.0 | 79.2 |
| 41 | 0 | 0 | 0 | 0 | 29.8 | 0 | 0 | 70.8 |
| 42 | 5.0 | 5.0 | 0 | 20.0 | 32.5 | 8.5 | 0 | 0 |
| 43 | 0 | 0 | 0 | 0 | 71.4 | 5.1 | 0 | 0 |
| 44 | 0 | 10.0 | 0 | 0 | 44.7 | 0 | 0 | 25.0 |
| 45 | 5.0 | 10.0 | 0 | 0 | 42.8 | 18.6 | 0 | 75.0 |
| 46 | 0 | 15.0 | 0 | 0 | 93.8 | 0 | 0 | 0 |
| 47 | 5.0 | 5.0 | 0 | 0 | 100 | 52.5 | 0 | 71.2 |
| 48 | 15.0 | 0 | 0 | 30.0 | 100 | 100 | 10.0 | 97.9 |
The result shows: part of compounds shows weeding activity preferably, and its pharmacodynamic properties is: handle the back weed growth and obviously be suppressed, and not regrowth of young leaves, vein and leaf margin begin flavescence, and be withered, death.Long action time, consistent with other photosynthesis weedicide symptoms; Cauline leaf is handled active in soil treatment; Activity to the broad-leaved rape is higher than Gramineae barnyard grass grass.
Claims (8)
1. one kind contains heterocycle long-chain amido replacement cyanoacrylate compound, it is characterized in that it is that general formula is the compound of (I)
Wherein, R
1: alkyl, alkoxyalkyl, aryloxyalkyl group, alcoxyl alkoxyalkyl, fragrant oxygen aryloxyalkyl group; R
2: C
1-C
3Alkylthio, C
1-C
3Alkyl.Het: phenyl ring, pyridine ring, thiazole ring, pyrimidine ring, pyridazine ring, thiadiazoles ring, thiadiazine ring, furan nucleus, tetrahydrofuran (THF) Huan, oxazole ring, isoxazole ring, oxadiazole ring, pyrazoles ring, thiphene ring, pyrrole ring, Pyrrolidine ring, triazole ring, ferrocene, or above-mentioned heterocycle is by fluorine, chlorine, bromine, C
1-C
6Alkoxyl group or C
1-C
6Alkylamino radical replaces; X: oxygen, nitrogen, sulphur, sulfinyl, alkylsulfonyl; M:1-12; N:0-12.
2. replace cyanoacrylate compound according to the said heterocycle long-chain amido that contains of claim 1, it is characterized in that R
1Be C
1-C
6Alkyl, alkoxyalkyl, aryloxyalkyl group, alcoxyl alkoxyalkyl, fragrant oxygen aryloxyalkyl group.
3. replace cyanoacrylate compound according to the said heterocycle long-chain amido that contains of claim 1, it is characterized in that R
2Be C
1-C
3Alkylthio, C
1-C
3Alkyl.
4. replace cyanoacrylate compound according to the said heterocycle long-chain amido that contains of claim 1, it is characterized in that Het is phenyl ring, pyridine ring, thiazole ring, pyrimidine ring, pyridazine ring, thiadiazoles ring, thiadiazine ring, furan nucleus, tetrahydrofuran (THF) Huan, oxazole ring, isoxazole ring, oxadiazole ring, pyrazoles ring, thiphene ring, pyrrole ring, Pyrrolidine ring, triazole ring, ferrocene, or above-mentioned heterocycle is by fluorine, chlorine, bromine, C
1-C
6Alkoxyl group or C
1-C
6Alkylamino radical replaces.
5. according to the said cyanoacrylate compound that contains the thiadiazoles ring of claim 1, it is characterized in that X is X: oxygen, nitrogen, sulphur, sulfinyl, alkylsulfonyl.
6. according to the said cyanoacrylate compound that contains the thiadiazoles ring of claim 1, it is characterized in that m is 0-12.
7. according to the said cyanoacrylate compound that contains the thiadiazoles ring of claim 1, it is characterized in that n is 1-12.
8. according to the said application on agricultural chemicals that contains the cyanoacrylate compound of thiadiazoles ring of claim 1, it is characterized in that weedicide as broadleaf weedss such as the rape in the corn field, Amaranthus retroflexus.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110437174A (en) * | 2019-08-30 | 2019-11-12 | 南通大学 | The cyanoacrylate compound and its preparation method and application of the phenyl unit of methyl mercapto containing thiazole |
| CN110845436A (en) * | 2019-11-18 | 2020-02-28 | 合肥锦绣田园化工科技有限公司 | Thiazolesulfone compound and preparation and application thereof |
| CN111892546A (en) * | 2020-09-04 | 2020-11-06 | 南通大学 | Preparation and application of cyanoacrylate containing 1,2, 3-triazole biphenyl |
-
2010
- 2010-06-10 CN CN2010101967432A patent/CN102276551A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110437174A (en) * | 2019-08-30 | 2019-11-12 | 南通大学 | The cyanoacrylate compound and its preparation method and application of the phenyl unit of methyl mercapto containing thiazole |
| CN110437174B (en) * | 2019-08-30 | 2021-10-26 | 南通大学 | Cyanoacrylate compound containing thiazole methylthio phenyl unit and preparation method and application thereof |
| CN110845436A (en) * | 2019-11-18 | 2020-02-28 | 合肥锦绣田园化工科技有限公司 | Thiazolesulfone compound and preparation and application thereof |
| CN111892546A (en) * | 2020-09-04 | 2020-11-06 | 南通大学 | Preparation and application of cyanoacrylate containing 1,2, 3-triazole biphenyl |
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