KR100250958B1 - Silylalkylbenzoamides, process for preparing the same and agricultural fungicide - Google Patents
Silylalkylbenzoamides, process for preparing the same and agricultural fungicide Download PDFInfo
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- KR100250958B1 KR100250958B1 KR1019980011273A KR19980011273A KR100250958B1 KR 100250958 B1 KR100250958 B1 KR 100250958B1 KR 1019980011273 A KR1019980011273 A KR 1019980011273A KR 19980011273 A KR19980011273 A KR 19980011273A KR 100250958 B1 KR100250958 B1 KR 100250958B1
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- formula
- methyl
- reaction
- methylethyl
- trimethylsilyl
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- 239000000417 fungicide Substances 0.000 title claims abstract description 7
- 230000000855 fungicidal effect Effects 0.000 title claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 title claims abstract 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 C 1 -C 6 cycloalkyl Chemical group 0.000 claims abstract description 8
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical class ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 5
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 claims abstract description 5
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 4
- 150000002431 hydrogen Chemical group 0.000 claims abstract description 4
- 150000003335 secondary amines Chemical class 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims abstract 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 63
- 238000006243 chemical reaction Methods 0.000 claims description 60
- 235000007164 Oryza sativa Nutrition 0.000 claims description 13
- 235000009566 rice Nutrition 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 240000008067 Cucumis sativus Species 0.000 claims description 7
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 claims description 7
- 235000007340 Hordeum vulgare Nutrition 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 241000209140 Triticum Species 0.000 claims description 7
- 235000021307 Triticum Nutrition 0.000 claims description 7
- 235000007688 Lycopersicon esculentum Nutrition 0.000 claims description 5
- 240000003768 Solanum lycopersicum Species 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 206010037660 Pyrexia Diseases 0.000 claims description 2
- 235000013312 flour Nutrition 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 2
- 240000005979 Hordeum vulgare Species 0.000 claims 1
- 239000007810 chemical reaction solvent Substances 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 150000003141 primary amines Chemical class 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 51
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 51
- 239000002904 solvent Substances 0.000 description 36
- 238000001816 cooling Methods 0.000 description 26
- LLLAHCKXRGDNQE-UHFFFAOYSA-N 4-methyl-3-(1-trimethylsilylpropan-2-yl)benzoyl chloride Chemical compound CC1=C(C=C(C(=O)Cl)C=C1)C(C[Si](C)(C)C)C LLLAHCKXRGDNQE-UHFFFAOYSA-N 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 18
- 238000004440 column chromatography Methods 0.000 description 18
- 238000004817 gas chromatography Methods 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 238000001035 drying Methods 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 17
- 239000012044 organic layer Substances 0.000 description 17
- 239000011541 reaction mixture Substances 0.000 description 17
- 239000000741 silica gel Substances 0.000 description 17
- 229910002027 silica gel Inorganic materials 0.000 description 17
- RBHJBMIOOPYDBQ-UHFFFAOYSA-N carbon dioxide;propan-2-one Chemical compound O=C=O.CC(C)=O RBHJBMIOOPYDBQ-UHFFFAOYSA-N 0.000 description 13
- 239000012230 colorless oil Substances 0.000 description 13
- 239000002689 soil Substances 0.000 description 12
- 241000209094 Oryza Species 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000003814 drug Substances 0.000 description 10
- 241000209219 Hordeum Species 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229940079593 drug Drugs 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 241000221785 Erysiphales Species 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical group NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000003898 horticulture Methods 0.000 description 4
- 230000003902 lesion Effects 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- 241000227653 Lycopersicon Species 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 3
- 125000000068 chlorophenyl group Chemical group 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000001727 in vivo Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229910052760 oxygen Chemical group 0.000 description 3
- 239000001301 oxygen Chemical group 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 150000003613 toluenes Chemical class 0.000 description 3
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- 229920001213 Polysorbate 20 Polymers 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000011081 inoculation Methods 0.000 description 2
- 244000000003 plant pathogen Species 0.000 description 2
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 2
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910052710 silicon Chemical group 0.000 description 2
- 239000010703 silicon Chemical group 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229910052717 sulfur Chemical group 0.000 description 2
- 239000011593 sulfur Chemical group 0.000 description 2
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- HAGTZEZXHQEPGL-UHFFFAOYSA-N 2-phenylethylsilane Chemical class [SiH3]CCC1=CC=CC=C1 HAGTZEZXHQEPGL-UHFFFAOYSA-N 0.000 description 1
- PNPCRKVUWYDDST-UHFFFAOYSA-N 3-chloroaniline Chemical compound NC1=CC=CC(Cl)=C1 PNPCRKVUWYDDST-UHFFFAOYSA-N 0.000 description 1
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 1
- 239000005047 Allyltrichlorosilane Substances 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 241001480061 Blumeria graminis Species 0.000 description 1
- 241000123650 Botrytis cinerea Species 0.000 description 1
- HTJDQJBWANPRPF-UHFFFAOYSA-N Cyclopropylamine Chemical compound NC1CC1 HTJDQJBWANPRPF-UHFFFAOYSA-N 0.000 description 1
- 241001149475 Gaeumannomyces graminis Species 0.000 description 1
- 241000233622 Phytophthora infestans Species 0.000 description 1
- 241001123569 Puccinia recondita Species 0.000 description 1
- 241000231139 Pyricularia Species 0.000 description 1
- 241000813090 Rhizoctonia solani Species 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- BGPCFXZWLWDDDU-UHFFFAOYSA-N chloro(propyl)silane Chemical compound CCC[SiH2]Cl BGPCFXZWLWDDDU-UHFFFAOYSA-N 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000006877 oatmeal agar Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002786 root growth Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- OOXSLJBUMMHDKW-UHFFFAOYSA-N trichloro(3-chloropropyl)silane Chemical compound ClCCC[Si](Cl)(Cl)Cl OOXSLJBUMMHDKW-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- HKFSBKQQYCMCKO-UHFFFAOYSA-N trichloro(prop-2-enyl)silane Chemical compound Cl[Si](Cl)(Cl)CC=C HKFSBKQQYCMCKO-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
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- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
Abstract
화학식 1을 갖는 실릴알킬벤조아미드, 그의 제조방법 및 그를 유효성분으로 하는 농원예용 살진균제가 제공된다. 본 발명의 실릴알킬벤조아미드는, 화학식 2의 실릴알킬벤조산 유도체들을 티오닐클로라이드로 처리하여 벤조일클로라이드 유도체들을 합성한후, 이를 화학식 3의 1차 또는 2차 아민과 반응시킴으로써 제조한다.There is provided a silylalkylbenzoamide having the formula (1), a method for producing the same, and an agricultural and horticultural fungicide using the same. The silylalkylbenzoamides of the present invention are prepared by treating the silylalkylbenzoic acid derivatives of formula (2) with thionyl chloride to synthesize benzoyl chloride derivatives and then reacting them with the primary or secondary amines of formula (3).
[화학식 1][Formula 1]
[화학식 2][Formula 2]
[화학식 3][Formula 3]
(식 중, R1은 수소 또는 C1-C4의 직쇄 또는 가지달린 알킬이고, R2는, C1-C4의 직쇄 또는 가지달린 알킬, C1-C6의 시클로알킬, 알릴, 페닐, 오르토-, 메타-, 또는 파라-클로로페닐기이고, R3는 수소 또는 메틸기이며, X는 수소, 메타- 또는 파라-플루오(Wherein R 1 is hydrogen or C 1 -C 4 straight or branched alkyl, R 2 is C 1 -C 4 straight or branched alkyl, C 1 -C 6 cycloalkyl, allyl, phenyl , Ortho-, meta-, or para-chlorophenyl group, R 3 is hydrogen or methyl group, X is hydrogen, meta- or para-fluoro
로, 클로로, 또는 메틸기이고, Me는 메틸기, n은 1 또는 2임)Chloro, or a methyl group, Me is a methyl group, n is 1 or 2)
Description
본 발명은 다음 화학식 1을 갖는 실릴알킬벤조아미드 유도체, 그의 제조방법 및 그를 유효성분으로 하는 농원예용 살진균제에 관한 것이다.The present invention relates to a silylalkylbenzoamide derivative having the following formula (1), a preparation method thereof, and an agricultural and horticultural fungicide using the same.
[화학식 1][Formula 1]
(식 중, R1은 수소 또는 C1-C4의 직쇄 또는 가지달린 알킬이고, R2는, C1-C4의 직쇄 또는 가지달린 알킬, C1-C6의 시클로알킬, 알릴, 페닐, 오르토-, 메타-, 또는 파라-클로로페닐기이고, R3는 수소 또는 메틸기이며, X는 수소, 메타- 또는 파라-플루오로, 클로로, 또는 메틸기이고, Me는 메틸기, n은 1 또는 2임)(Wherein R 1 is hydrogen or C 1 -C 4 straight or branched alkyl, R 2 is C 1 -C 4 straight or branched alkyl, C 1 -C 6 cycloalkyl, allyl, phenyl , Ortho-, meta-, or para-chlorophenyl group, R 3 is hydrogen or methyl group, X is hydrogen, meta- or para-fluoro, chloro, or methyl group, Me is methyl group, n is 1 or 2 )
EP 0619 297 A1에 의하면 다음과 같은 a) ∼ g)의 벤조아미드계 유기규소 화합물이 우수한 살균성을 보이는 것으로 보고되었는데, 이들은 특히 뿌리성장을 방해하는 Gg균 (Gaeumannomyces graminis)에 대해 뛰어난 살균효과를 보인 것으로 기재되어 있다.According to EP 0619 297 A1, the following benzoamide-based organosilicon compounds of a) to g) showed excellent bactericidal properties, which showed an excellent bactericidal effect against Gg bacteria ( Gaeumannomyces graminis ) which inhibited root growth. It is described as.
(상기 식 중, A는 -C(X)-아민, B는 -Wm-Q(R2)3이고, A는 B가 될 수 있다. Q는 탄소 또는 규소, W는 아민, 메틸아민 혹은 산소이며, X는 산소 혹은 황이고, m은 0 또는 1인데, Q가 규소인 경우 m은 0이다. n은 0-3, p는 0-2의 정수이며, n과 p의 합은 3 이하이다. Y는 산소, 황 혹은 아민(NR1)이고 R1은 알킬기이다)(Wherein A is -C (X) -amine, B is -W m -Q (R 2 ) 3 and A can be B. Q is carbon or silicon, W is amine, methylamine or Oxygen, X is oxygen or sulfur, m is 0 or 1, and Q is silicon, m is 0. n is 0-3, p is an integer from 0-2, and the sum of n and p is 3 or less Y is oxygen, sulfur or amine (NR 1 ) and R 1 is an alkyl group)
또한, 1992년 몬산토사는 아미드계 유기규소 화합물이 뿌리식물에 대하여 뛰어난 살균활성을 나타낸다고 보고하고 있다 (WO 93/07751). 현재 상품화가 추진되고 있는 이계열 화합물들의 특징은 방향족 고리에 아미드기와 입체장애가 큰 치환기를 갖고 있다.In 1992, Monsanto also reported that amide organosilicon compounds showed excellent bactericidal activity against root plants (WO 93/07751). Currently, the commercialization of two series compounds is characterized by having an amide group in the aromatic ring and a substituent having a high steric hindrance.
(식 중, Z1과 Z2는 방향족 고리의 탄소 또는 질소이고, A는 -C(X)NR1R2, C(O)SR3, -NH-C(X)R4(X = 0, S, NR)이다. B는 -C(R5)pH(2-p)M(M = CR6, SiR6, GeR6, SnR6, p = 0-2)이고, R 또는 R1-6는 알킬기, 알케닐기, 알키닐기, 아릴기, 알콕시기, 아미드기, 할로겐기 등을 나타내며, Rn은 알킬, 알릴, 아민등이며, n은 0-3의 정수이다)(Wherein Z 1 and Z 2 are carbon or nitrogen of an aromatic ring, A is —C (X) NR 1 R 2 , C (O) SR 3 , —NH—C (X) R 4 (X = 0) , S, NR) B is -C (R 5 ) p H (2-p) M (M = CR 6 , SiR 6 , GeR 6 , SnR 6 , p = 0-2) and R or R 1 -6 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an amide group, a halogen group, etc., R n is alkyl, allyl, an amine, etc., n is an integer of 0-3.)
본 발명의 목적은 신규한 실릴알킬벤조아미드 유도체를 제공하는 데 있다.It is an object of the present invention to provide novel silylalkylbenzoamide derivatives.
본 발명의 또 다른 목적은 상기 실릴알킬벤조아미드 유도체의 제조방법을 제공하는 것이다.Still another object of the present invention is to provide a method for preparing the silylalkylbenzoamide derivative.
본 발명의 또 다른 목적은 상기 실릴알킬벤조아미드 유도체를 유효성분으로 하는 농원예용 살진균제를 제공하는 데 있다.Still another object of the present invention is to provide an agricultural and horticultural fungicide using the silylalkylbenzoamide derivative as an active ingredient.
본 발명에 따른 화학식 1의 실릴알킬화된 벤조아미드 유도체는 다음 반응식 1에 표시된 바와 같이 화학식 2의 실릴알킬화된 벤조산과 티오닐클로라이드를 반응시켜 벤조일클로라이드 유도체를 합성한뒤, 이를 화학식 3의 1차 또는 2차 아민과 반응시킴으로써 제조할 수 있다.The silylalkylated benzoamide derivative of Formula 1 according to the present invention synthesizes a benzoyl chloride derivative by reacting the silylalkylated benzoic acid of Formula 2 with thionyl chloride as shown in the following Scheme 1, and then converts the primary or It can be prepared by reacting with a secondary amine.
(식 중, R1은 수소 또는 C1-C4의 직쇄 또는 가지달린 알킬이고, R2는, C1-C4의 직쇄 또는 가지달린 알킬, C1-C6의 시클로알킬, 알릴, 페닐, 오르토-, 메타-, 또는 파라-클로로페닐기이고, R3는 수소 또는 메틸기이며, X는 수소, 메타- 또는 파라-플루오로, 클로로, 또는 메틸기이고, Me는 메틸기, n은 1 또는 2임)(Wherein R 1 is hydrogen or C 1 -C 4 straight or branched alkyl, R 2 is C 1 -C 4 straight or branched alkyl, C 1 -C 6 cycloalkyl, allyl, phenyl , Ortho-, meta-, or para-chlorophenyl group, R 3 is hydrogen or methyl group, X is hydrogen, meta- or para-fluoro, chloro, or methyl group, Me is methyl group, n is 1 or 2 )
본 발명자들은 다음 반응식 2에 나타낸 바와 같이 트리메틸실릴알킬벤젠 유도체들에서 벤젠고리의 메틸기를 초산코발트로 산화시킴으로써 화학식 2와 같은 실릴알킬화된 벤조산 유도체를 합성할 수 있음을 발견하였다.The inventors have discovered that silylalkylated benzoic acid derivatives such as formula (2) can be synthesized by oxidizing the methyl group of the benzene ring to cobalt acetate in trimethylsilylalkylbenzene derivatives as shown in Scheme 2 below.
본 발명에서 출발물질로 사용된 상기 화학식 2의 화합물 중 n이 1이고 R3가 메틸기인 2-(아릴)프로필클로로실란은 본 발명자들의 한국특허출원 제 12996/1992호와 유사한 방법으로 알릴트리클로로실란을 알루미늄 클로라이드와 같은 루이스산 촉매 하에서 톨루엔 유도체에 프리델-크라프트 반응으로 부가시켜 합성할 수 있다.2- (aryl) propylchlorosilane in which n is 1 and R 3 is a methyl group among the compounds of Formula 2 used as a starting material in the present invention is allyltrichloro in a manner similar to that of Korean Patent Application No. 12996/1992. Silane can be synthesized by addition of the silane acid catalyst such as aluminum chloride to the toluene derivative by Friedel-Crafts reaction.
또한, 본 발명에서 사용되는 톨루엔 유도체와 알릴트리클로로실란은 시약을 구입하여 사용하였다.In addition, the toluene derivative and allyl trichlorosilane used by this invention purchased the reagent and used.
또한, 본 발명에서 출발물질로 사용된 화학식 2의 화합물 중 n이 1, 2이고 R3가 수소인 실릴에틸벤젠 유도체는 1959년 (Chem. Abstr. 53, 9110c) 비소트로바 등이 보고한 방법에 따라 2-클로로에틸 또는 3-클로로프로필트리클로로실란을 알루미늄 클로라이드와 같은 루이스산 촉매 하에 톨루엔 유도체에 프리델-크라프트 반응으로 부가시켜 합성하였다. 또한 화학식 2에서 n이 1이고 R3가 수소인 실릴알킬벤젠 유도체의 경우는 출발물질을 비닐트리클로로실란으로 하여 위와 유사한 방법 (안드리아노브 등, 1961년,Zh. Obshch. Khim. 1961,31, 4033)으로 합성하였다.In addition, the silylethylbenzene derivative wherein n is 1, 2 and R 3 is hydrogen among the compounds of formula 2 used as starting materials in the present invention is reported by Bisotrova et al. In 1959 (Chem. Abstr. 53, 9110c). 2-chloroethyl or 3-chloropropyltrichlorosilane was synthesized according to a Friedel-Craft reaction to a toluene derivative under a Lewis acid catalyst such as aluminum chloride. In the case of the silylalkylbenzene derivative in which n is 1 and R 3 is hydrogen in the formula (2), the starting material is vinyltrichlorosilane and similar method to that described above (Andrianov et al., 1961, Zh. Obshch. Khim . 1961, 31). , 4033).
전형적인 합성과정은 건조된 질소대기하에서 반응식 1에서와 같이 벤조산유도체와 티오닐클로라이드를 톨루엔 용액중에서 반응시켜 합성하고 진공증류하여 벤조일클로라이드 유도체들을 분리하는 것이다. 이 반응에서 반응촉진제로 DMF(디메틸포름아미드) 2-3방울을 사용하였다. 건조된 질소대기하에서 반응기에 아민과 용매로서 톨루엔을 넣고 얼음조에서 벤조일클로라이드유도체를 천천히 적가한 뒤 온도를 상온으로 올려 1시간동안 교반시키고, 컬럼 크로마토그래피를 이용하여 순수한 실릴알킬벤조아미드 유도체들을 분리하였다. 이 반응에서 아민류는 벤조일클로라이드에 대해 몰 비로 3배를 사용하고, 낮은 끓은점을 갖은 아민류를 반응시킬때는 아세톤-드라이아이스 냉각기를 사용하여 아민이 기화되어 이탈되는 것을 방지하였다.A typical synthesis process is to react benzoic acid derivatives and thionyl chloride in a toluene solution under dry nitrogen atmosphere to synthesize benzoyl chloride derivatives by distillation under vacuum. In this reaction, 2-3 drops of DMF (dimethylformamide) were used as a reaction accelerator. Toluene was added to the reactor as an amine and a solvent in a dried nitrogen atmosphere. The benzoyl chloride derivative was slowly added dropwise in an ice bath, the temperature was raised to room temperature, stirred for 1 hour, and pure silylalkylbenzoamide derivatives were separated using column chromatography. It was. In this reaction, amines were used three times in molar ratio relative to benzoyl chloride, and when reacting low boiling amines, an acetone-dry ice cooler was used to prevent amines from vaporizing and leaving.
다음에 실시예를 들어 본 발명을 더욱 상세히 설명하나 본 발명의 범위가 이들 실시예로 한정되는 것은 아니다.The present invention will be described in more detail with reference to the following Examples, but the scope of the present invention is not limited to these Examples.
실시예 1. N-메틸-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드의 합성Example 1.Synthesis of N-methyl-4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide
건조된 질소분위기하에서 100 ml들이 삼구 플라스크에 4-메틸-3-(2-트리메틸실릴)-1-메틸에틸)벤조산 2.5 g (10.0 mmol)과 티오닐클로라이드 3.6 g (30.2 mmol) 및 용매로 톨루엔 50 ml을 넣고 반응 촉진제로 DMF 2-3방울을 적가하여 실온에서 4시간동안 반응시켰다. 기체 크로마토그래피로 반응의 완결을 확인한 뒤 과량의 티오닐클로라이드를 상압에서 증류하여 제거한 후 진공증류하여 4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조일클로라이드 2.58 g(수율; 95.0%)을 얻었다.In a 100 ml three-necked flask under dried nitrogen atmosphere, 2.5 g (10.0 mmol) of 4-methyl-3- (2-trimethylsilyl) -1-methylethyl) benzoic acid, 3.6 g (30.2 mmol) of thionyl chloride and toluene as solvent 50 ml was added and 2-3 drops of DMF were added dropwise as a reaction accelerator, and the reaction was carried out at room temperature for 4 hours. After completion of the reaction by gas chromatography, excess thionyl chloride was removed by distillation at atmospheric pressure, followed by vacuum distillation to give 2.58 g of 4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoyl chloride (yield). 95.0%).
건조된 100 ml들이 삼구플라스크를 아세톤-드라이아이스 냉각조로 냉각시킨 뒤 건조된 진공하의 냉각조건에서 메틸아민 0.54 g (17.4 mmol)을 반응플라스크로 옮긴 뒤 아세톤-드라이아이스 냉각기와 건조관을 장치하고 반응기에 용매인 톨루엔 25 ml을 넣고 아세톤-드라이아이스 냉각조로 반응플라스크를 냉각시킨 상태에서 4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조일클로라이드 1.42 g (5.28 mmol)을 적가하였다. 아세톤-드라이아이스 냉각조를 제거하여 서서히 반응조의 온도를 실온으로 올려주면서 상온에서 1시간동안 교반시켜준 뒤 기체 크로마토그래피로 반응의 완결을 확인하였다. 반응혼합물을 희석된 시트릭산으로 처리하고 분액 깔때기로 유기층만 모은 뒤 회전증발기로 용매를 제거하고 칼럼 크로마토그래피 (실리카겔, 부피비 6:1 헥산:에틸아세테이트)로 분리하여 무색결정의 N-메틸-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드 1.34 g(수율; 96.3%, 녹는점; 79 ∼ 80℃)을 합성하였다.The dried 100 ml three-necked flask was cooled with an acetone-dry ice cooling bath, and then 0.54 g (17.4 mmol) of methylamine was transferred to the reaction flask under cooling conditions under dry vacuum, followed by an acetone-dry ice cooler and a drying tube. 25 ml of toluene, a solvent, was added dropwise to 1.42 g (5.28 mmol) of 4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoyl chloride while the reaction flask was cooled with an acetone-dry ice cooling bath. It was. After removing the acetone-dry ice cooling bath and slowly raising the temperature of the reactor to room temperature, the mixture was stirred at room temperature for 1 hour, and then confirmed by gas chromatography. The reaction mixture was treated with diluted citric acid, the organic layer was collected with a separatory funnel, the solvent was removed with a rotary evaporator, and separated by column chromatography (silica gel, volume ratio 6: 1 hexane: ethyl acetate) to give N-methyl-4 as a colorless crystal. 1.34 g (yield; 96.3%, melting point; 79-80 ° C) of -methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide were synthesized.
실시예 2. N-에틸-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드의 합성Example 2. Synthesis of N-ethyl-4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide
건조된 100 ml들이 삼구플라스크를 아세톤-드라이아이스 냉각조로 냉각시킨 뒤 건조된 진공하의 냉각조건에서 에틸아민 0.71 g (15.8 mmol)을 반응플라스크로 옮긴 뒤 아세톤-드라이아이스 냉각기와 건조관을 장치하고 반응기에 용매인 톨루엔 25 ml을 넣고 아세톤-드라이아이스 냉각조로 반응플라스크를 냉각시킨 상태에서 4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조일클로라이드 1.42 g (5.28 mmol)을 적가하였다. 아세톤-드라이아이스 냉각조를 제거하여 서서히 반응조의 온도를 실온으로 올려주면서 상온에서 1시간동안 교반시켜준 뒤 기체 크로마토그래피로 반응의 완결을 확인하였다. 반응혼합물을 희석된 시트릭산으로 처리하고 분액 깔때기로 유기층만 모은 뒤 회전증발기로 용매를 제거하고 컬럼 크로마토그래피 (실리카겔, 부피비 6:1 헥산:에틸아세테이트)로 분리하여 무색결정의 N-메틸-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드 1.34 g(수율; 92.8%, 녹는점; 95 ∼ 96.5℃)을 합성하였다.The dried 100 ml three-necked flask was cooled with an acetone-dry ice cooling bath, and then 0.71 g (15.8 mmol) of ethylamine was transferred to the reaction flask under cooling conditions under a dry vacuum, followed by an acetone-dry ice cooler and a drying tube. 25 ml of toluene, a solvent, was added dropwise to 1.42 g (5.28 mmol) of 4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoyl chloride while the reaction flask was cooled with an acetone-dry ice cooling bath. It was. After removing the acetone-dry ice cooling bath and slowly raising the temperature of the reactor to room temperature, the mixture was stirred at room temperature for 1 hour, and then confirmed by gas chromatography. The reaction mixture was treated with diluted citric acid, the organic layer was collected with a separatory funnel, the solvent was removed with a rotary evaporator, and separated by column chromatography (silica gel, volume ratio 6: 1 hexane: ethyl acetate) to give N-methyl-4 as a colorless crystal. 1.34 g (yield; 92.8%, melting point; 95-96.5 ° C.) of -methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide were synthesized.
실시예 3. N-프로필-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드의 합성Example 3. Synthesis of N-propyl-4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide
건조된 100 ml들이 삼구플라스크를 냉각기와 건조관을 장치하고 반응기에 용매인 톨루엔 25 ml을 넣었다. 얼음조로 반응 플라스크를 냉각시킨 뒤 프로필아민 0.94 g (15.9 mmol)을 반응플라스크에 넣고 주사기를 이용하여 4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조일클로라이드 1.42 g (5.28 mmol)을 적가하였다. 반응기의 온도를 실온으로 올려주면서 상온에서 1시간동안 교반시켜준 뒤 기체크로마트그래피로 반응의 완결을 확인하였다. 반응혼합물을 희석된 시트릭산으로 처리하고 분액 깔때기로 유기층만 모은 뒤 회전증발기로 용매를 제거하고 컬럼 크로마토그래피 (실리카겔, 부피비 6:1 헥산:에틸아세테이트)로 분리하여 무색오일상의 N-프로필-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드 1.38 g(수율; 89.6%)을 합성하였다.The dried 100 ml three-necked flask was equipped with a cooler and a drying tube, and 25 ml of solvent toluene was added to the reactor. After cooling the reaction flask with an ice bath, 0.94 g (15.9 mmol) of propylamine was added to the reaction flask, and 1.42 g (5.28) of 4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoyl chloride was added using a syringe. mmol) was added dropwise. After raising the temperature of the reactor to room temperature, the mixture was stirred for 1 hour at room temperature, and gas chromatography was confirmed to complete the reaction. The reaction mixture was treated with diluted citric acid, the organic layer was collected with a separatory funnel, the solvent was removed with a rotary evaporator and separated by column chromatography (silica gel, volume ratio 6: 1 hexane: ethyl acetate) to give N-propyl-4 as a colorless oil. 1.38 g (yield; 89.6%) of -methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide were synthesized.
실시예 4. N-부틸-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드의 합성Example 4 Synthesis of N-Butyl-4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide
건조된 100 ml들이 삼구플라스크를 냉각기와 건조관을 장치하고 반응기에 용매인 톨루엔 25 ml을 넣었다. 얼음조로 반응플라스크를 냉각시킨 뒤 부틸아민 1.16 g (15.9 mmol)을 반응플라스크에 넣고 주사기를 이용하여 4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조일클로라이드 1.42 g (5.28 mmol)을 적가하였다. 반응기의 온도를 실온으로 올려주면서 상온에서 1시간 동안 교반시켜준 뒤 기체크로마트그래피로 반응의 완결을 확인하였다. 반응혼합물을 희석된 시트릭산으로 처리하고 분액 깔때기로 유기층만 모은 뒤 회전증발기로 용매를 제거하고 컬럼 크로마토그래피 (실리카겔, 부피비 6:1 헥산:에틸아세테이트)로 분리하여 무색결정상의 N-부틸-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드 1.43 g (수율; 88.6%, 녹는점; 102.5 ∼ 103.5℃)을 합성하였다.The dried 100 ml three-necked flask was equipped with a cooler and a drying tube, and 25 ml of solvent toluene was added to the reactor. After cooling the reaction flask with an ice bath, 1.16 g (15.9 mmol) of butylamine was added to the reaction flask, and then 1.42 g (5.28) of 4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoyl chloride was added using a syringe. mmol) was added dropwise. After raising the temperature of the reactor to room temperature, the mixture was stirred for 1 hour at room temperature, and gas chromatography was confirmed to complete the reaction. The reaction mixture was treated with diluted citric acid, the organic layer was collected with a separatory funnel, the solvent was removed with a rotary evaporator, separated by column chromatography (silica gel, volume ratio 6: 1 hexane: ethyl acetate), and colorless crystalline N-butyl-4. 1.43 g (yield; 88.6%, melting point; 102.5 to 103.5 ° C) of -methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide were synthesized.
실시예 5. N-이소프로필-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드의 합성Example 5. Synthesis of N-isopropyl-4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide
건조된 100 ml들이 삼구플라스크를 냉각기와 건조관을 장치하고 반응기에 용매인 톨루엔 25 ml을 넣었다. 얼음조로 반응플라스크를 냉각시킨 뒤 이소프로필아민 0.94 g (15.9 mmol)을 반응플라스크에 넣고 주사기를 이용하여 4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조일클로라이드 1.42 g (5.28 mmol)을 적가하였다. 반응기의 온도를 실온으로 올려주면서 상온에서 1시간동안 교반시켜준 뒤 기체크로마트그래피로 반응의 완결을 확인하였다. 반응혼합물을 희석된 시트릭산으로 처리하고 분액 깔때기로 유기층만 모은 뒤 회전증발기로 용매를 제거하고 컬럼 크로마토그래피(실리카겔, 부피비 6:1 헥산:에틸아세테이트)로 분리하여 무색결정상의 N-이소프로필-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드 1.40 g (수율; 90.9%, 녹는점; 102.5 ∼ 103.5℃)을 합성하였다.The dried 100 ml three-necked flask was equipped with a cooler and a drying tube, and 25 ml of solvent toluene was added to the reactor. After cooling the reaction flask with an ice bath, 0.94 g (15.9 mmol) of isopropylamine was added to the reaction flask, and then 1.42 g of 4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoyl chloride was added using a syringe. 5.28 mmol) was added dropwise. After raising the temperature of the reactor to room temperature, the mixture was stirred for 1 hour at room temperature, and gas chromatography was confirmed to complete the reaction. The reaction mixture was treated with diluted citric acid, the organic layer was collected with a separatory funnel, the solvent was removed with a rotary evaporator, separated by column chromatography (silica gel, volume ratio 6: 1 hexane: ethyl acetate), and colorless crystalline N-isopropyl-. 1.40 g (yield; 90.9%, melting point; 102.5 to 103.5 ° C) of 4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide were synthesized.
실시예 6. N-시클로프로필-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드의 합성Example 6 Synthesis of N-cyclopropyl-4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide
건조된 100 ml들이 삼구플라스크를 냉각기와 건조관을 장치하고 반응기에 용매인 톨루엔 25 ml을 넣었다. 얼음조로 반응플라스크를 냉각시킨 뒤 시클로프로필아민 0.95 g (16.6 mmol)을 반응플라스크에 넣고 주사기를 이용하여 4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조일클로라이드 1.42 g (5.28 mmol)을 적가하였다. 반응기의 온도를 실온으로 올려주면서 상온에서 1시간동안 교반시켜준 뒤 기체크로마트그래피로 반응의 완결을 확인하였다. 반응혼합물을 희석된 시트릭산으로 처리하고 분액 깔때기로 유기층만 모은 뒤 회전증발기로 용매를 제거하고 컬럼 크로마토그래피(실리카겔, 부피비 6:1 헥산:에틸아세테이트)로 분리하여 무색오일상의 N-시클로프로필-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드 1.40 g (수율; 91.3%)을 합성하였다.The dried 100 ml three-necked flask was equipped with a cooler and a drying tube, and 25 ml of solvent toluene was added to the reactor. After cooling the reaction flask with an ice bath, 0.95 g (16.6 mmol) of cyclopropylamine was added to the reaction flask, and then 1.42 g of 4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoyl chloride was added using a syringe. 5.28 mmol) was added dropwise. After raising the temperature of the reactor to room temperature, the mixture was stirred for 1 hour at room temperature, and gas chromatography was confirmed to complete the reaction. The reaction mixture was treated with diluted citric acid, the organic layer was collected with a separatory funnel, the solvent was removed with a rotary evaporator, and separated by column chromatography (silica gel, volume ratio 6: 1 hexane: ethyl acetate) to give N-cyclopropyl- as a colorless oil. 1.40 g (yield; 91.3%) of 4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide were synthesized.
실시예 7. N-시클로헥실-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드의 합성Example 7 Synthesis of N-cyclohexyl-4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide
건조된 100 ml들이 삼구플라스크를 냉각기와 건조관을 장치하고 반응기에 용매인 톨루엔 25 ml을 넣었다. 얼음조로 반응플라스크를 냉각시킨 뒤 시클로헥실아민 1.58 g (16.0 mmol)을 반응플라스크에 넣고 주사기를 이용하여 4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조일클로라이드 1.42 g (5.28 mmol)을 적가하였다. 반응기의 온도를 실온으로 올려주면서 상온에서 1시간 동안 교반시켜준 뒤 기체크로마트그래피로 반응의 완결을 확인하였다. 반응혼합물을 희석된 시트릭산으로 처리하고 분액 깔때기로 유기층만 모은 뒤 회전증발기로 용매를 제거하고 컬럼 크로마토그래피 (실리카겔, 부피비 6:1 헥산:에틸아세테이트)로 분리하여 무색오일상의 N-시클로헥실-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드 1.48 g (수율; 84.5%)을 합성하였다.The dried 100 ml three-necked flask was equipped with a cooler and a drying tube, and 25 ml of solvent toluene was added to the reactor. After cooling the reaction flask with an ice bath, 1.58 g (16.0 mmol) of cyclohexylamine was added to the reaction flask, and 1.42 g of 4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoyl chloride was added using a syringe. 5.28 mmol) was added dropwise. After raising the temperature of the reactor to room temperature, the mixture was stirred for 1 hour at room temperature, and gas chromatography was confirmed to complete the reaction. The reaction mixture was treated with diluted citric acid, the organic layer was collected with a separatory funnel, the solvent was removed with a rotary evaporator, and separated by column chromatography (silica gel, volume ratio 6: 1 hexane: ethyl acetate) to give N-cyclohexyl- as a colorless oil. 1.48 g (yield; 84.5%) of 4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide were synthesized.
실시예 8. N-알릴-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드의 합성Example 8. Synthesis of N-allyl-4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide
건조된 100ml 들이 삼구 플라스크를 냉각기와 건조관을 장치하고 반응기에 용매인 톨루엔 25 ml을 넣었다. 얼음조로 반응플라스크를 냉각시킨 뒤 알릴아민 0.91 g (15.9 mmol)을 반응플라스크에 넣고 주사기를 이용하여 4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조일클로라이드 1.42 g (5.28 mmol)을 적가하였다. 반응기의 온도를 실온으로 올려주면서 상온에서 1시간동안 교반시켜준 뒤 기체크로마트그래피로 반응의 완결을 확인하였다. 반응혼합물을 희석된 시트릭산으로 처리하고 분액 깔때기로 유기층만 모은 뒤 회전증발기로 용매를 제거하고 컬럼 크로마토그래피(실리카겔, 부피비 6:1 헥산:에틸아세테이트)로 분리하여 무색오일상의 N-알릴-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드 1.40g(수율; 91.6%)을 합성하였다.The dried 100 ml three-necked flask was equipped with a cooler and a drying tube, and 25 ml of solvent toluene was added to the reactor. After cooling the reaction flask with an ice bath, 0.91 g (15.9 mmol) of allylamine was added to the reaction flask, and 1.42 g (5.28) of 4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoyl chloride was added using a syringe. mmol) was added dropwise. After raising the temperature of the reactor to room temperature, the mixture was stirred for 1 hour at room temperature, and gas chromatography was confirmed to complete the reaction. The reaction mixture was treated with diluted citric acid, the organic layer was collected with a separatory funnel, the solvent was removed with a rotary evaporator and separated by column chromatography (silica gel, volume ratio 6: 1 hexane: ethyl acetate) to give N-allyl-4 as a colorless oil. 1.40 g (yield; 91.6%) of -methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide were synthesized.
실시예 9. N-페닐-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드의 합성Example 9 Synthesis of N-phenyl-4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide
건조된 100 ml들이 삼구플라스크를 냉각기와 건조관을 장치하고 반응기에 용매인 톨루엔 25 ml을 넣었다. 얼음조로 반응플라스크를 냉각시킨 뒤 아닐린 1.48 g (15.9 mmol)을 반응플라스크에 넣고 주사기를 이용하여 4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조일클로라이드 1.42 g (5.28 mmol)을 적가하였다. 반응기의 온도를 실온으로 올려주면서 상온에서 1시간동안 교반시켜준 뒤 기체크로마트그래피로 반응의 완결을 확인하였다. 반응혼합물을 희석된 시트릭산으로 처리하고 분액 깔때기로 유기층만 모은 뒤 회전증발기로 용매를 제거하고 컬럼 크로마토그래피(실리카겔, 부피비 6:1 헥산:에틸아세테이트)로 분리하여 무색오일상의 N-페닐-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드 1.52g (수율; 88.4%)을 합성하였다.The dried 100 ml three-necked flask was equipped with a cooler and a drying tube, and 25 ml of solvent toluene was added to the reactor. After cooling the reaction flask with an ice bath, 1.48 g (15.9 mmol) of aniline was added to the reaction flask, and 1.42 g (5.28 mmol) of 4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoyl chloride was added to the reaction flask. ) Was added dropwise. After raising the temperature of the reactor to room temperature, the mixture was stirred for 1 hour at room temperature, and gas chromatography was confirmed to complete the reaction. The reaction mixture was treated with diluted citric acid, the organic layer was collected with a separatory funnel, the solvent was removed with a rotary evaporator, and separated by column chromatography (silica gel, volume ratio 6: 1 hexane: ethyl acetate) to give N-phenyl-4 as a colorless oil. 1.52 g (yield; 88.4%) of -methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide was synthesized.
실시예 10. N-(2-클로로페닐)-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드의 합성Example 10. Synthesis of N- (2-chlorophenyl) -4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide
건조된 100 ml들이 삼구플라스크를 냉각기와 건조관을 장치하고 반응기에 용매인 톨루엔 25 ml을 넣었다. 얼음조로 반응플라스크를 냉각시킨 뒤 2-클로로아닐린 2.03g (15.9 mmol)을 반응플라스크에 넣고 주사기를 이용하여 4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조일클로라이드 1.42 g (5.28 mmol)을 적가하였다. 반응기의 온도를 실온으로 올려주면서 상온에서 1시간동안 교반시켜준 뒤 기체크로마트그래피로 반응의 완결을 확인하였다. 반응혼합물을 희석된 시트릭산으로 처리하고 분액 깔때기로 유기층만 모은 뒤 회전증발기로 용매를 제거하고 컬럼 크로마토그래피(실리카겔, 부피비 6:1 헥산:에틸아세테이트)로 분리하여 무색오일상의 N-(2-클로로페닐)-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드 1.74g (수율; 91.6%)을 합성하였다.The dried 100 ml three-necked flask was equipped with a cooler and a drying tube, and 25 ml of solvent toluene was added to the reactor. After cooling the reaction flask with an ice bath, 2.03 g (15.9 mmol) of 2-chloroaniline was added to the reaction flask, and then 1.42 g of 4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoyl chloride was added using a syringe. (5.28 mmol) was added dropwise. After raising the temperature of the reactor to room temperature, the mixture was stirred for 1 hour at room temperature, and gas chromatography was confirmed to complete the reaction. The reaction mixture was treated with diluted citric acid, the organic layer was collected with a separatory funnel, the solvent was removed with a rotary evaporator, and separated by column chromatography (silica gel, volume ratio 6: 1 hexane: ethyl acetate) to give N- (2- as a colorless oil. 1.74 g (yield; 91.6%) of chlorophenyl) -4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide were synthesized.
실시예 11. N-(3-클로로페닐)-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드의 합성Example 11.Synthesis of N- (3-chlorophenyl) -4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide
건조된 100 ml들이 삼구플라스크를 냉각기와 건조관을 장치하고 반응기에 용매인 톨루엔 25ml을 넣었다. 얼음조로 반응플라스크를 냉각시킨 뒤 3-클로로아닐린 2.02 g (15.8 mmol)을 반응플라스크에 넣고 주사기를 이용하여 4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조일클로라이드 1.42 g (5.28 mmol)을 적가하였다. 반응기의 온도를 실온으로 올려주면서 상온에서 1시간동안 교반시켜준 뒤 기체크로마트그래피로 반응의 완결을 확인하였다. 반응혼합물을 희석된 시트릭산으로 처리하고 분액 깔때기로 유기층만 모은 뒤 회전증발기로 용매를 제거하고 컬럼 크로마토그래피 (실리카겔, 부피비 6:1 헥산:에틸아세테이트)로 분리하여 무색오일상의 N-(3-클로로페닐)-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드 1.75 g (수율; 92.1%)을 합성하였다.The dried 100 ml three-necked flask was equipped with a cooler and a drying tube, and 25 ml of solvent toluene was added to the reactor. After cooling the reaction flask with an ice bath, 2.02 g (15.8 mmol) of 3-chloroaniline was added to the reaction flask, and then 1.42 g of 4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoyl chloride was added using a syringe. (5.28 mmol) was added dropwise. After raising the temperature of the reactor to room temperature, the mixture was stirred for 1 hour at room temperature, and gas chromatography was confirmed to complete the reaction. The reaction mixture was treated with diluted citric acid, the organic layer was collected with a separatory funnel, the solvent was removed with a rotary evaporator and separated by column chromatography (silica gel, volume ratio 6: 1 hexane: ethyl acetate) to give N- (3- colorless oil). 1.75 g (yield; 92.1%) of chlorophenyl) -4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide were synthesized.
실시예 12. N-(4-클로로페닐)-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드의 합성Example 12.Synthesis of N- (4-chlorophenyl) -4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide
건조된 100 ml들이 삼구플라스크를 냉각기와 건조관을 장치하고 반응기에 용매인 톨루엔 25 ml을 넣었다. 얼음조로 반응플라스크를 냉각시킨 뒤 4-클로로아닐린 2.03 g (15.9 mmol)을 반응플라스크에 넣고 주사기를 이용하여 4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조일클로라이드 1.42 g (5.28 mmol)을 적가하였다. 반응기의 온도를 실온으로 올려주면서 상온에서 1시간동안 교반시켜준 뒤 기체크로마트그래피로 반응의 완결을 확인하였다. 반응혼합물을 희석된 시트릭산으로 처리하고 분액 깔때기로 유기층만 모은 뒤 회전증발기로 용매를 제거하고 컬럼 크로마토그래피(실리카겔, 부피비 6:1 헥산:에틸아세테이트)로 분리하여 무색오일상의 N-(4-클로로페닐)-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드 1.76 g (수율; 92.6%)을 합성하였다.The dried 100 ml three-necked flask was equipped with a cooler and a drying tube, and 25 ml of solvent toluene was added to the reactor. After cooling the reaction flask with an ice bath, 2.03 g (15.9 mmol) of 4-chloroaniline was added to the reaction flask, and then 1.42 g of 4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoyl chloride was added using a syringe. (5.28 mmol) was added dropwise. After raising the temperature of the reactor to room temperature, the mixture was stirred for 1 hour at room temperature, and gas chromatography was confirmed to complete the reaction. The reaction mixture was treated with diluted citric acid, the organic layer was collected with a separatory funnel, the solvent was removed with a rotary evaporator, and separated by column chromatography (silica gel, volume ratio 6: 1 hexane: ethyl acetate) to give N- (4- as a colorless oil. 1.76 g (yield; 92.6%) of chlorophenyl) -4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide were synthesized.
실시예 13. N,N-디메틸-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드의 합성Example 13. Synthesis of N, N-dimethyl-4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide
건조된 100ml들이 삼구플라스크를 아세톤-드라이아이스 냉각조로 냉각시킨 뒤 건조된 진공하의 냉각조건에서 디메틸아민 0.72g (16.0 mmol)을 반응플라스크로 옮긴 뒤 아세톤-드라이아이스 냉각기와 건조관을 장치하고 반응기에 용매인 톨루엔 25 ml을 넣고 아세톤-드라이아이스 냉각조로 반응플라스크를 냉각시킨 상태에서 4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조일클로라이드 1.42 g (5.28 mmol)을 적가하였다. 아세톤-드라이아이스 냉각조를 제거하여 서서히 반응조의 온도를 실온으로 올려주면서 상온에서 1시간동안 교반시켜준 뒤 기체크로마트그래피로 반응의 완결을 확인하였다. 반응혼합물을 희석된 시트릭산으로 처리하고 분액 깔때기로 유기층만 모은 뒤 회전증발기로 용매를 제거하고 컬럼 크로마토그래피(실리카겔, 부피비 6:1 헥산:에틸아세테이트)로 분리하여 무색오일의 N,N-디메틸-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드 1.36 g (수율; 92.8%)을 합성하였다.The dried 100 ml three-necked flask was cooled with an acetone-dry ice cooling bath, and then 0.72 g (16.0 mmol) of dimethylamine was transferred to the reaction flask under a dry vacuum cooling condition, followed by an acetone-dry ice cooler and a drying tube. 25 ml of toluene as a solvent was added thereto, and 1.42 g (5.28 mmol) of 4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoyl chloride was added dropwise while the reaction flask was cooled with an acetone-dry ice cooling bath. . After removing the acetone-dry ice cooling bath and slowly raising the temperature of the reactor to room temperature, the mixture was stirred at room temperature for 1 hour, and gas chromatography was confirmed to complete the reaction. The reaction mixture was treated with diluted citric acid, the organic layer was collected with a separatory funnel, the solvent was removed with a rotary evaporator, separated by column chromatography (silica gel, volume ratio 6: 1 hexane: ethyl acetate), and colorless oil N, N-dimethyl. 1.36 g (yield; 92.8%) of 4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide were synthesized.
실시예 14. N,N-디에틸-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드의 합성Example 14 Synthesis of N, N-diethyl-4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide
건조된 100 ml들이 삼구플라스크를 냉각기와 건조관을 장치하고 반응기에 용매인 톨루엔 25 ml을 넣었다. 얼음조로 반응플라스크를 냉각시킨 뒤 디에틸아민 1.16 g (15.9 mmol)을 반응플라스크에 넣고 주사기를 이용하여 4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조일클로라이드 1.42 g (5.28 mmol)을 적가하였다. 반응기의 온도를 실온으로 올려주면서 상온에서 1시간동안 교반시켜준 뒤 기체크로마트그래피로 반응의 완결을 확인하였다. 반응혼합물을 희석된 시트릭산으로 처리하고 분액 깔때기로 유기층만 모은 뒤 회전증발기로 용매를 제거하고 컬럼 크로마토그래피(실리카겔, 부피비 6:1 헥산:에틸아세테이트)로 분리하여 무색오일상의 N,N-디에틸-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드 1.51 g (수율; 93.6%)을 합성하였다.The dried 100 ml three-necked flask was equipped with a cooler and a drying tube, and 25 ml of solvent toluene was added to the reactor. After cooling the reaction flask with an ice bath, 1.16 g (15.9 mmol) of diethylamine was added to the reaction flask, and 1.42 g of 4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoyl chloride was added using a syringe. 5.28 mmol) was added dropwise. After raising the temperature of the reactor to room temperature, the mixture was stirred for 1 hour at room temperature, and gas chromatography was confirmed to complete the reaction. The reaction mixture was treated with diluted citric acid, the organic layer was collected with a separatory funnel, the solvent was removed with a rotary evaporator, and separated by column chromatography (silica gel, volume ratio 6: 1 hexane: ethyl acetate) to give N, N-di as a colorless oil. 1.51 g (yield; 93.6%) of ethyl-4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide were synthesized.
실시예 15. N,N-디프로필-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드의 합성Example 15 Synthesis of N, N-dipropyl-4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide
건조된 100 ml들이 삼구플라스크를 냉각기와 건조관을 장치하고 반응기에 용매인 톨루엔 25 ml을 넣었다. 얼음조로 반응플라스크를 냉각시킨 뒤 디프로필아민 1.61 g (15.9 mmol)을 반응플라스크에 넣고 주사기를 이용하여 4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조일클로라이드 1.42 g (5.28 mmol)을 적가하였다. 반응기의 온도를 실온으로 올려주면서 상온에서 1 시간동안 교반시켜준 뒤 기체크로마트그래피로 반응의 완결을 확인하였다. 반응혼합물을 희석된 시트릭산으로 처리하고 분액 깔때기로 유기층만 모은 뒤 회전증발기로 용매를 제거하고 컬럼 크로마토그래피(실리카겔, 부피비 6:1 헥산:에틸아세테이트)로 분리하여 무색오일상의 N,N-디프로필-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드 1.63 g (수율; 92.5%)을 합성하였다.The dried 100 ml three-necked flask was equipped with a cooler and a drying tube, and 25 ml of solvent toluene was added to the reactor. After cooling the reaction flask with an ice bath, 1.61 g (15.9 mmol) of dipropylamine was added to the reaction flask, and then 1.42 g of 4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoyl chloride was added using a syringe. 5.28 mmol) was added dropwise. After raising the temperature of the reactor to room temperature, the mixture was stirred at room temperature for 1 hour, and gas chromatography was confirmed to complete the reaction. The reaction mixture was treated with diluted citric acid, the organic layer was collected with a separatory funnel, the solvent was removed with a rotary evaporator, and separated by column chromatography (silica gel, volume ratio 6: 1 hexane: ethyl acetate) to give N, N-di as a colorless oil. 1.63 g (yield; 92.5%) of propyl-4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide were synthesized.
실시예 16. N,N-디이소프로필-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드의 합성Example 16 Synthesis of N, N-diisopropyl-4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide
건조된 100 ml들이 삼구플라스크를 냉각기와 건조관을 장치하고 반응기에 용매인 톨루엔 25 ml을 넣었다. 얼음조로 반응플라스크를 냉각시킨 뒤 디이소프로필아민 1.61 g (15.9 mmol)을 반응플라스크에 넣고 주사기를 이용하여 4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조일클로라이드 1.42 g (5.28 mmol)을 적가하였다. 반응기의 온도를 실온으로 올려주면서 상온에서 1시간동안 교반시켜준 뒤 기체크로마트그래피로 반응의 완결을 확인하였다. 반응혼합물을 희석된 시트릭산으로 처리하고 분액 깔때기로 유기층만 모은 뒤 회전증발기로 용매를 제거하고 컬럼 크로마토그래피(실리카겔, 부피비 6:1 헥산:에틸아세테이트)로 분리하여 무색오일상의 N,N-디이소프로필-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드 1.62 g (수율; 92.0%)을 합성하였다.The dried 100 ml three-necked flask was equipped with a cooler and a drying tube, and 25 ml of solvent toluene was added to the reactor. After cooling the reaction flask with an ice bath, 1.61 g (15.9 mmol) of diisopropylamine was added to the reaction flask, and 1.42 g of 4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoyl chloride was added using a syringe. (5.28 mmol) was added dropwise. After raising the temperature of the reactor to room temperature, the mixture was stirred for 1 hour at room temperature, and gas chromatography was confirmed to complete the reaction. The reaction mixture was treated with diluted citric acid, the organic layer was collected with a separatory funnel, the solvent was removed with a rotary evaporator, and separated by column chromatography (silica gel, volume ratio 6: 1 hexane: ethyl acetate) to give N, N-di as a colorless oil. 1.62 g (yield; 92.0%) of isopropyl-4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide were synthesized.
실시예 17. N,N-디부틸-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드의 합성Example 17 Synthesis of N, N-dibutyl-4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide
건조된 100 ml들이 삼구플라스크를 냉각기와 건조관을 장치하고 반응기에 용매인 톨루엔 25 ml을 넣었다. 얼음조로 반응플라스크를 냉각시킨 뒤 디부틸아민 2.06 g (15.9 mmol)을 반응플라스크에 넣고 주사기를 이용하여 4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조일클로라이드 1.42 g (5.28 mmol)을 적가하였다. 반응기의 온도를 실온으로 올려주면서 상온에서 1 시간동안 교반시켜준 뒤 기체크로마트그래피로 반응의 완결을 확인하였다. 반응혼합물을 희석된 시트릭산으로 처리하고 분액 깔때기로 유기층만 모은 뒤 회전증발기로 용매를 제거하고 컬럼 크로마토그래피(실리카겔, 부피비 6:1 헥산:에틸아세테이트)로 분리하여 무색오일상의 N,N-디부틸-4-메틸-3-(2-(트리메틸실릴)-1-메틸에틸)벤조아미드 1.72 g (수율; 90.1%)을 합성하였다.The dried 100 ml three-necked flask was equipped with a cooler and a drying tube, and 25 ml of solvent toluene was added to the reactor. After cooling the reaction flask with an ice bath, 2.06 g (15.9 mmol) of dibutylamine was added to the reaction flask, and then 1.42 g of 4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoyl chloride was added using a syringe. 5.28 mmol) was added dropwise. After raising the temperature of the reactor to room temperature, the mixture was stirred at room temperature for 1 hour, and gas chromatography was confirmed to complete the reaction. The reaction mixture was treated with diluted citric acid, the organic layer was collected with a separatory funnel, the solvent was removed with a rotary evaporator, and separated by column chromatography (silica gel, volume ratio 6: 1 hexane: ethyl acetate) to give N, N-di as a colorless oil. 1.72 g (yield; 90.1%) of butyl-4-methyl-3- (2- (trimethylsilyl) -1-methylethyl) benzoamide were synthesized.
그 밖의 실시예들은 실시예 1 또는 3의 방법에 따라 합성하였다. 녹는점은 ℃로 기록되었다.Other examples were synthesized according to the method of Example 1 or 3. Melting point was recorded in ℃.
이와 같은 방법으로 합성한 실시예 1 내지 17 및 그 외의 본 발명에 따른 신규한 화합물들의 NMR 데이타를 다음 표 1에 나타내었다.Examples 1 to 17 synthesized in this manner and other NMR data of the novel compounds according to the present invention are shown in Table 1 below.
본 발명 화합물의 생물활성 시험Bioactivity Test of Compounds of the Invention
한국화학연구소 스크리닝센터 농약활성연구실에 의뢰하여 본 발명에 따른 실릴알킬벤조아미드 유도체들의 생물활성을 다음 표 2에 제시한 6가지 주요한 식물 병원균에 대해 in vivo 방법으로 시험하였으며 그 결과를 표 3에 나타내었다.The bioactivity of the silylalkylbenzoamide derivatives according to the present invention was tested by the in vivo method for six major plant pathogens shown in the following Table 2, which was commissioned by the Pesticide Activity Laboratory, Korea Research Institute of Chemical Technology. It was.
본 발명의 화학식 1의 실릴알킬벤조아미드 유도체들의 생물활성은 다음과 같이 in vivo로 시험하였다.Bioactivity of the silylalkylbenzoamide derivatives of formula 1 of the present invention was tested in vivo as follows.
In vivo 시험In vivo test
약제를 아세톤에 녹인 후 계면활성제 tween 20을 포함한 수용액을 가하여 희석 (250 ppm)시켰다. 이 때 아세톤의 최종농도는 10% 미만으로 하였다.The drug was dissolved in acetone and diluted (250 ppm) by adding an aqueous solution containing the surfactant tween 20. At this time, the final concentration of acetone was less than 10%.
1) 벼도열병 (Rice Blast, RCB)1) Rice Blast (Rice Blast, RCB)
원형 포트 (토양: 수도용 부농상토)에 볍씨 (낙동벼) 3립을 파종한 후 14일 간 육묘 (2,3엽기)하고, 준비된 약제를 벼에 분무 처리하였다. 오트밀 한천 배지 상에서 포자를 형성시킨 후 수확한 포자현탁액 (106포자/mL 농도)을 약제처리 1일 후에 분무 접종하였다. 암상태 실습상 (온도: 25℃)에서 1일 동안 정치시킨 후 온실 (온도 25 - 27℃, 상대습도 90% 이상)에 옮겨 3일 동안 발병시켰다.After seeding three rice seeds (Nakdong rice) into a round pot (soil: water-based subcontracted soil), seedlings (two and three leaves) were carried out for 14 days, and the prepared medicine was sprayed on rice. Spores were formed on oatmeal agar medium and spore suspensions harvested (10 6 spores / mL concentration) were spray inoculated 1 day after drug treatment. After standing for 1 day in the practice of the dark state (temperature: 25 ℃) and transferred to a greenhouse (temperature 25-27 ℃, relative humidity 90% or more) and developed for 3 days.
2) 벼 잎집무니마름병 (Rice Sheath Blight, RSB)2) Rice Sheath Blight (RSB)
온실에서 원형포트 (토양: 수도용 부농상토)에 볍씨 (낙동벼) 3립을 파종한 후 21일간 육묘하고, 준비된 약제를 벼에 분무 처리하였다. 약제처리 1일 후에 벼 잎집무니마름병균 (0.6 g/mL)을 분무한 후 암상태 실습상 (온도: 25℃)에서 4일 동안 정치시킨 후 온실 (온도 25℃, 상대습도 90% 이상)에 옮겨 발병시켰다. 약효는 잎에 형성된 병반 면적을 조사하여 평가하였다.In the greenhouse, three seeds of Dab seed (Nakdong rice) were seeded in a circular pot (soil: sub-farm soil) for 21 days, and the prepared medicines were sprayed on the rice. After 1 day of chemical treatment, rice leaf blight bacteria (0.6 g / mL) was sprayed and then left for 4 days in a dark state (temperature: 25 ℃) and then placed in a greenhouse (temperature 25 ℃, relative humidity of 90% or higher). Moved on. Drug efficacy was evaluated by examining the lesion area formed on the leaves.
3) 오이 잿빛곰팡이병 (Cucumber Gray Mold, CGM)3) Cucumber Gray Mold (CGM)
원형포트 (토양: 원예용 상토 2호)에 오이 종자 (한농 하우스 다다기) 1립을 파종한 후 14일간 육묘 (본엽 1엽기)하고, 준비된 약제를 오이의 옆면에 분무 처리하였다. 약제처리 1일 후에 오이 흰가루병균 (106포자/mL 농도의 유자낭 현탁액)을 분무 접종하였다. 실습상 (온도: 20℃)에서 3일 동안 발병시켰다. 약효는 균접종 5일 후 잎에 형성된 병반 면적을 조사하여 평가하였다.After seeding one seed of cucumber (Hanong House Tadagi) in a round pot (soil: horticulture soil No. 2), seedlings were seeded (one leafy season) for 14 days, and the prepared medicine was sprayed on the side of the cucumber. One day after the treatment, cucumber powdery mildew (oil sac suspension at a concentration of 10 6 spores / mL) was sprayed. Onset for 3 days in practice (temperature: 20 ° C). The efficacy was evaluated by examining the lesion area formed on the leaves 5 days after the inoculation.
4) 토마토 역병 (Tomato Late Blight, TLB)4) Tomato Late Blight (TLB)
원형포트 (토양: 원예용 상토 2호)에 토마토 종자 (홍농 서광) 2립을 파종한 후 14일간 육묘 (본엽 2엽기)하고, 준비된 약제를 토마토의 옆면에 분무 처리하였다. 약제처리 1일 후에 토마토 역병균 (106포자/mL 농도의 유자낭 현탁액)을 분무 접종하였다. 실습상 (온도: 20℃)에서 4일 동안 발병시켰다. 약효는 본엽 1,2엽에 형성된 병반 면적을 조사하여 평가하였다.After seeding two tomato seeds (Hongong Seokwang) in a round pot (soil: horticulture soil No. 2), seedlings (two leafy leaves) were carried out for 14 days, and the prepared agent was sprayed on the side of the tomato. One day after the inoculation, the tomato blight was spray inoculated with a sachet of 10 6 spores / mL concentration. Onset for 4 days in practice (temperature: 20 ° C). The efficacy was evaluated by examining the lesion area formed on the first and second leaf.
5) 밀 붉은녹병 (Wheat Leaf Rust, WLR)5) Wheat Leaf Rust (WLR)
원형포트 (토양: 원예용 상토 2호)에 밀 종자 (조광) 20-25립을 파종한 후 8일간 육묘 (본엽 1엽기)하고, 준비된 약제를 밀의 옆면에 분무 처리하였다. 약제처리 1일 후에 밀 붉은녹병균 (0.67 g/mL 농도의 포자 현탁액, tween 20 250 μg/mL)을 분무 접종하였다. 실습상 (온도: 20℃)에서 1일 동안 정치시킨 후 온실 (온도; 20℃, 상대습도 > 70%)에 옮겨 발병시켰다. 약효는 본엽 1엽에 형성된 병반 면적을 조사하여 평가하였다.After seeding 20-25 grains of wheat seeds (lighting) in a circular pot (soil: horticulture soil No. 2), seedlings (one leafy season) were applied for 8 days, and the prepared medicine was sprayed on the side of the wheat. One day after the treatment, wheat red rust bacteria (spore suspension at 0.67 g / mL concentration, tween 20 250 μg / mL) were spray-inoculated. In practice (temperature: 20 ℃) was allowed to stand for 1 day and then transferred to a greenhouse (temperature; 20 ℃, relative humidity> 70%) to develop. Drug efficacy was evaluated by examining the lesion area formed on the first leaf of the main leaf.
6) 보리 흰가루병 (Barley Powdery Mildew, BPM)6) Barley Powdery Mildew (BPM)
원형포트 (토양: 원예용 상토 2호)에 보리 종자 (등 보리) 5립씩을 파종한 후 8일간 육묘 (본엽 1,2엽기)하고, 준비된 약제를 보리의 옆면에 분무 처리하였다. 약제처리 1일 후에 보리 흰가루병균 (포자가 형성된 기주식물)을 털어서 접종하였다. 생육실 (온도: 20℃, 일광 하)에서 7일 동안 발병시켰다.Five seeds of barley seeds (back barley) were sown in a circular pot (soil: horticulture soil No. 2), and seedlings (1 and 2 leaf plants) were applied for 8 days, and the prepared medicine was sprayed on the side of barley. After 1 day of drug treatment, barley powdery mildew (spore-forming host plant) was shaken and inoculated. Onset for 7 days in the growth room (temperature: 20 ° C., daylight).
각 시험군의 약효는 다음 방제가 산출 방식에 따라 평가하였다.The efficacy of each test group was evaluated according to the following control calculation method.
이상의 실험결과를 표 3에 나타내었다. 표 3에서 100%에 가까울수록 균주 저지율이 우수함을 나타낸다. 표 3의 결과로부터 알 수 있는 바와 같이, 화학식 1의 화합물에서 R1이 H, R2가 메틸 또는 에틸과 같이 적은 치환기일 때 특히 방제 효과가 우수하였다.The above experimental results are shown in Table 3. In Table 3, the closer to 100%, the better the strain inhibition rate. As can be seen from the results of Table 3, in the compound of Formula 1, R 1 is particularly excellent when H, R 2 is a small substituent such as methyl or ethyl.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019980011273A KR100250958B1 (en) | 1998-03-31 | 1998-03-31 | Silylalkylbenzoamides, process for preparing the same and agricultural fungicide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019980011273A KR100250958B1 (en) | 1998-03-31 | 1998-03-31 | Silylalkylbenzoamides, process for preparing the same and agricultural fungicide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR19990076363A KR19990076363A (en) | 1999-10-15 |
| KR100250958B1 true KR100250958B1 (en) | 2000-04-15 |
Family
ID=19535644
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019980011273A KR100250958B1 (en) | 1998-03-31 | 1998-03-31 | Silylalkylbenzoamides, process for preparing the same and agricultural fungicide |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR100250958B1 (en) |
-
1998
- 1998-03-31 KR KR1019980011273A patent/KR100250958B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR19990076363A (en) | 1999-10-15 |
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