• The Korean Journal of Pesticide Science
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• v.10 no.2
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• pp.69-75
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• 2006

For the development of new agrochemical fungicide 3-amino-2-phenylimino-1,3-thiazolines 2 were designed through the molecular modification based on isostere concept of 3-methyl-2-phenylimino-1,3-thiazolines 1 which showed antifungal activity against rice blast. All the compounds 2 were fit Lipinski rule and they had higher solubility in water than that of 1 by virtual calculation. We constructed 195 kinds of focused library of 3-amino-2-phenylimino-1,3-thiazolines through 6H-[1,3,4]thiadiazines (195 compounds) which synthesized from the reaction of thiourea 4 with $\gamma$-chloroacetoacetanilides 5.

• The Korean Journal of Pesticide Science
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• v.10 no.3
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• pp.165-171
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• 2006

A new 3-amino-1,3-thiazoline chemical library was synthesized through parallel synthetic technology and in vivo antifungal activity of the compounds were investigated against the typical 6 plant diseases (100 ppm). The characteristic feature of these derivatives was that both a benzyl moiety in C-2 imino and an amino group in C-3 of 2-imino-1,3-thiazoline scaffold were substituted in the molecule respectively. Some compounds showed antifungal activity with selectivity against tomato late blight and rice blast. The fungitoxicity would be attributed to 3,4-dichlorophenyl moiety of the benzyl group.

• Applied Biological Chemistry
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• v.45 no.3
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• pp.157-161
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• 2002

New 2-benzoylimino-1,3-oxathile derivatives 3 were synthesized and tested their fungicidal activities for the development of new agrochemical fungicide. Reaction of ${\gamma}-chloro-{\beta}-keto$ anilide derivative 5 with potassium thiocyanate followed by the treatment of acid catalyst gave cyclyzed 2-imino-1,3-oxathiole 3. New compound 3 reacted with benzoyl· chlorides to afford the corresponding 2-benzoylimino-1,3-oxathiole derivatives 7. Antifungal screening (in vivo) of the synthesized compounds against typical plant diseases, which include rice blast, rice sheath blight, cucumber gray mold, tomato late blight, wheat leaf rust, and barley powdery mildew, was carried out. No significant fungicidal activities were shown of the synthesized compounds at 100 mg/l.

• Journal of the Korean Chemical Society
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• v.47 no.1
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• pp.38-42
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• 2003

For the purpose of developing new agrochemical fungicides, compound 2 possessing 1,3-thiazole scaffold as well as urea moiety in the structure was designed through molecular modification of lead compound, 2-imino-1,3-thiazoline based on isosterism. The reaction of N-methylthiouea 5 and bromoacetonitrile in ethanol gave 2,4-diimino-1,3-thiazole 4 regioselectively, which was treated with phenyl isocyanates to give the corresponding 7 which is tautomer of 2. The structural assignment of 7 was confirmed by various spectra($^1H$ NMR, $^{13}C$ NMR, FT-IR, HRMS), and X-ray crystallographic data. Compound 8 which is a structural isomer of 7 was formed through thermodynamically unstable intermediate 2,4-diimino-1,3-thiazole 6.

• The Korean Journal of Pesticide Science
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• v.7 no.2
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• pp.155-158
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• 2003

2-Imino-1,3-thiazolines 1 show selective antifungal activity against pyricularia oryzae by new mode of action. A synthesis of novel 2-cyano-l,3-thiazolines 2 in which cyano moiety is substituted in imino group at C-2 of 1 is described. The lone pair electrons of sulfur and nitrogen as well as strong electron withdrawing cyano substituent in 1,3-thiazoline scaffold would effect the biological activity of 2-imino-1,3-thiazoline series. Regiospecific nucleophilic attack of thiourea 4 for $\gamma$-chloro-$\beta$-ketoacetoacetanilide 3 followed by acid catalyzed dehydration gave 2.

• The Korean Journal of Pesticide Science
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• v.5 no.2
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• pp.13-17
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• 2001

A synthesis of new 2-phenylimino-1,3-thiazolines 2 for the purpose of development of new agrochemical fuugicide was described. Reaction of chlorine with diketene followed by treatment of benzylamine without isolation of intermediate 8a gave ${\gamma}-chloro-{\beta}-keto$ benzylamide 10a. Thioureas 4 obtained from the reaction of methyl isothiocyanate with aniline derivatives were subjected to 10a in acetone solution to afford the corresponding 2-phenylimino-1,3-thiazoline hydrochloric acid salts 2 through unisolable inltermediates 11 and 12. The plausible reaction mechanism including nucleophilic attack of sulfur assisted neighboring nitrogen lone pair electron on phenyl of thiourea 4 was discussed.

• The Korean Journal of Pesticide Science
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• v.8 no.3
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• pp.168-174
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• 2004

In a course of the process for a lead optimization of 2-imino-l,3-thiazolines 1 which show a selective in vivo antifungal activity against rice blast, new compounds 2 in which C-5 was substituted by methyl group of the lead compound were synthesized and tested for the biological activity. Bromination of $\beta$-keto ester 7 followed by the reaction with thiourea and hydrolysis gave 2-imino-5-methyl-l,3-thiazoline carboxylic acid 3. Coupling reactions of 3 with aniline derivatives afforded 17 kinds of the corresponding 2-imino-5-methyl-l,3-thiazoline carboxanilides 2. Their in vivo antifungal activity against rice blast was weaker than that of 1, indicating that the in vivo antifungal activity of 2-imino-l,3-thiazolines was affected by the substituent at C-5. These results would be an important data for the molecular design in the lead optimization process of this series.

• Applied Biological Chemistry
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• v.42 no.4
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• pp.356-360
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• 1999

Growth-inhibitory effects of citrus oils and agricultural fungicides, which were on the market, on several molds isolated from putrefied citrus fruits were investigated. When fungicidal activities of 11 kinds of synthetic agrochemicals against 6 species of molds, Alternaria alternata, Rhizopus sp., Botrytis cinerea, Monilia candida, Penicillium italicum and Penicillium digitatum, were investigated, agrochemicals containing mancozeb or fluazinam as an effective component had the broadest fungicidal spectrum. Agrochemicals containing iprodione, benomyl, azoxystrobin or thiophanate were less effective on the molds and those containing conazole derivative were intermediately effective. Resistance of the molds to the agrochemicals were species- and agrochemical-dependent. Among those molds tested, Penicillium italicum and Alternaria alternata showed relatively higher level of survival in the presence of synthetic fungicides. On the other hand, when the molds were exposed to citrus oils by direct contact, no cell could survive regardless of the species. The fungicidal activity of citrus oils was also confirmed by paper disk method and microscopic observation. These results suggested that citrus oils had broad killing activity against molds. Therefore, it would be necessary to design method for the application of citrus oils in order to improve post-harvest storage of citrus fruits.