JPS59144731A - Beta-substituted phenoxy-alpha-methylenepropionic acid derivative - Google Patents
Beta-substituted phenoxy-alpha-methylenepropionic acid derivativeInfo
- Publication number
- JPS59144731A JPS59144731A JP58018600A JP1860083A JPS59144731A JP S59144731 A JPS59144731 A JP S59144731A JP 58018600 A JP58018600 A JP 58018600A JP 1860083 A JP1860083 A JP 1860083A JP S59144731 A JPS59144731 A JP S59144731A
- Authority
- JP
- Japan
- Prior art keywords
- beta
- acid
- phenoxy
- substituted
- methylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 Beta-substituted phenoxy-alpha-methylenepropionic acid Chemical class 0.000 title abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 claims abstract description 5
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 5
- 125000004076 pyridyl group Chemical group 0.000 claims abstract description 5
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 claims abstract description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 8
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 abstract description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 abstract description 4
- 230000008635 plant growth Effects 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 3
- 150000002989 phenols Chemical class 0.000 abstract description 3
- 125000000714 pyrimidinyl group Chemical group 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 230000002363 herbicidal effect Effects 0.000 abstract description 2
- 239000004009 herbicide Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 235000019260 propionic acid Nutrition 0.000 abstract description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- QQZJWQCLWOQDQV-UHFFFAOYSA-N 3-bromo-2-(bromomethyl)propanoic acid Chemical compound OC(=O)C(CBr)CBr QQZJWQCLWOQDQV-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000005648 plant growth regulator Substances 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 241000196324 Embryophyta Species 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000009036 growth inhibition Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZSBDGXGICLIJGD-UHFFFAOYSA-N 4-phenoxyphenol Chemical compound C1=CC(O)=CC=C1OC1=CC=CC=C1 ZSBDGXGICLIJGD-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000009422 growth inhibiting effect Effects 0.000 description 2
- 230000000887 hydrating effect Effects 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 239000002373 plant growth inhibitor Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 150000007970 thio esters Chemical class 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- UTKHLTRHMHQVGS-UHFFFAOYSA-N 3,4-dihydro-2h-thiochromene-3-carboxylic acid Chemical compound C1=CC=C2CC(C(=O)O)CSC2=C1 UTKHLTRHMHQVGS-UHFFFAOYSA-N 0.000 description 1
- VIIIJFZJKFXOGG-UHFFFAOYSA-N 3-methylchromen-2-one Chemical compound C1=CC=C2OC(=O)C(C)=CC2=C1 VIIIJFZJKFXOGG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 244000058871 Echinochloa crus-galli Species 0.000 description 1
- 235000008247 Echinochloa frumentacea Nutrition 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical class O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000005733 Raphanus sativus var niger Nutrition 0.000 description 1
- 235000006140 Raphanus sativus var sativus Nutrition 0.000 description 1
- 240000001970 Raphanus sativus var. sativus Species 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000035613 defoliation Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 239000003630 growth substance Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- AYOOGWWGECJQPI-NSHDSACASA-N n-[(1s)-1-(5-fluoropyrimidin-2-yl)ethyl]-3-(3-propan-2-yloxy-1h-pyrazol-5-yl)imidazo[4,5-b]pyridin-5-amine Chemical compound N1C(OC(C)C)=CC(N2C3=NC(N[C@@H](C)C=4N=CC(F)=CN=4)=CC=C3N=C2)=N1 AYOOGWWGECJQPI-NSHDSACASA-N 0.000 description 1
- DYFFAVRFJWYYQO-UHFFFAOYSA-N n-methyl-n-phenylaniline Chemical compound C=1C=CC=CC=1N(C)C1=CC=CC=C1 DYFFAVRFJWYYQO-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
Landscapes
- Quinoline Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Thiazole And Isothizaole Compounds (AREA)
- Pyridine Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【発明の詳細な説明】
この発明は、新規なβ−置換フエノキシ−α−メチレン
グロビオン酸誘導体に関するものであり、植物生長抑制
剤として有用な新規化合物に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel β-substituted phenoxy-α-methylene globionic acid derivatives, and relates to novel compounds useful as plant growth inhibitors.
β−フェノキシ−α−メチレンプμピオン識は、３−メ
チルクマリンを合成する中間体として報告されている。β-phenoxy-α-methylene propionate has been reported as an intermediate in the synthesis of 3-methylcoumarin.
またβ−フェニルチオ−α−メチレンプ３ピオン酸は、
チオクロマン−３−カルボン酸を合成するための中間体
として報告されている（ ８ｗａｍｉｎａｔｈａｎ等、
８ｙｎｔｈｅｓｉｉａＯｏｍｍｕｎｉｏａｔｉｏｎｓ、
８＠ｐｔ、 １９７５、ｐＢ９９゜同Ｊｕｎ・ １９
７６、ｐ４０？）。In addition, β-phenylthio-α-methylenep3pionic acid is
It has been reported as an intermediate for the synthesis of thiochroman-3-carboxylic acid (8waminathan et al.
8ynthesiia ommunioations,
8@pt, 1975, pB99゜Jun. 19
76, p40? ).
これらの文献には４−メチルなど、いくつかの核置換体
も記されている。しかし、β−ンエノキシ基に更にもう
ひとつの環式基をもつ置換基が連結されたα−メチレン
ゲｐピオン酸ないしそのエステルについては記載がなく
、植物に対する作用も記されていない。Several nuclear substituents, such as 4-methyl, are also described in these documents. However, there is no description of α-methylenegepionic acid or its ester in which a substituent having another cyclic group is linked to the β-enoxy group, nor is there any mention of its effects on plants.
また特公昭５２−１９７２号公報には、ＷＬ物生長調整
剤としである種のα−置換アクリル酸誘導体が記されて
いるが、これらの化合物はチオエステルや鎖式チオエー
テル型の構造をもつ物質であり、環式（チオ）エーテル
型の構造をもつ化合物は記されていない。In addition, Japanese Patent Publication No. 52-1972 describes certain α-substituted acrylic acid derivatives as WL growth regulators, but these compounds are substances with a thioester or chain thioether type structure. However, compounds with a cyclic (thio)ether type structure are not described.
本発明者らは対植物活性の如き有用な性質をもつ化合物
を見出すべく鋭意研究の結果、β−置換フエノキシ−α
−メチレンプロピオン酸誘導体に属する一群の新規化合
物を合成し、それらの植物に対する作用を確認し本発明
を完成するに到った。As a result of intensive research to find compounds with useful properties such as activity against plants, the present inventors found that β-substituted phenoxy-α
- We have synthesized a group of new compounds belonging to methylenepropionic acid derivatives, confirmed their effects on plants, and completed the present invention.
本発明の新規なβ−置換フエノキシ−α−メチレンプロ
ピオン酸誘導体は、一般式
Ｃ式中、ムは、フェニル、ベンジル、ピリジル、ナフチ
ル、キノリニル、ピリミジル、ベンゾチアゾリル又はキ
ノキサリニルから選ばれる環式基であり、ハロゲン、ニ
ドｏ１低級アルコキシ、低級アルキル及びトリフルオロ
メチルよりなる群から選ばれる環上の置換基をもってい
てもよい、ｘは一〇 −、−Ｓ −、−ＮＨ−、又は−
ＮＯＨ，−であり、Ｒは水素原子又は炭素数１〜４の低
級アルキル基である。〕で表わされるものである。The novel β-substituted phenoxy-α-methylenepropionic acid derivatives of the present invention have the general formula C, where M is a cyclic group selected from phenyl, benzyl, pyridyl, naphthyl, quinolinyl, pyrimidyl, benzothiazolyl, or quinoxalinyl. , halogen, lower alkoxy, lower alkyl, and trifluoromethyl, x may have a substituent on the ring selected from the group consisting of 10-, -S-, -NH-, or -
NOH,-, and R is a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms. ].
上記一般式より明らかな如く、ムはフェニル基で代表さ
れる特定の環式基であり、−Ｘ−を介してα−メチレン
ゲμピオン酸のβ−位にあるフェノキシ基に連結してい
る。As is clear from the above general formula, M is a specific cyclic group represented by a phenyl group, and is linked to the phenoxy group at the β-position of α-methylene gel μ pionic acid via -X-.
人としてはフェニルに代えてベンジル、ピリジル、ナフ
チル、キノリニル、ビリンジル、ベンゾチアゾリル若し
くはキノキサリニルから選ばれる炭素環式又は複嵩堀式
の基であってもよい。ムは上ｉｆｄの基本骨格のみのも
のでもよく、また核置換基をもつものであってもよい。For humans, phenyl may be replaced by a carbocyclic or compound group selected from benzyl, pyridyl, naphthyl, quinolinyl, biringyl, benzothiazolyl, and quinoxalinyl. The compound may have only the basic skeleton of the above ifd, or may have a nuclear substituent.
置換基はハロゲン、ニトロ、低級アルコキシ（炭素数１
〜４）、低級アルキル（炭素数１〜４）およびトリフル
オロメチルよりなる群から選ぶことができ、Ａの核水素
原子の２個までを置換できる。Substituents include halogen, nitro, lower alkoxy (1 carbon number)
~4), lower alkyl (having 1 to 4 carbon atoms), and trifluoromethyl, and up to two of the nuclear hydrogen atoms in A can be substituted.
こりような環式基Ａをもうひとつの環式部分であるフェ
ノキシと結合するＸは、−０＋。The X that connects such a cyclic group A to another cyclic moiety, phenoxy, is -0+.
−８＋、−ＮＨ−又は−ＮＯＨ，−であり、従って例え
ば人がフェニルの場合は、それぞれジ７工二ルエーテル
、ジフェニルチオエーテル、ジフェニルアミン及びジフ
ェニルメチルアミン型の構造をもつことになる。-8+, -NH- or -NOH,-, and therefore, for example, if a person is phenyl, they will have structures of the di7-denyl ether, diphenylthioether, diphenylamine, and diphenylmethylamine types, respectively.
本発明のβ−置換フエノキシ−α−メチレンプロピオン
酸誘導体は、主としてメチルエステル（Ｒ−ＯＨ，）と
して見出されたが炭素数４迄の低級アルキルエステル（
Ｒ−００低級ア−４
ルキル晶）及び遊離酸（Ｒ＋＝ｌ（）についても同様の
合成法により得ることができた。The β-substituted phenoxy-α-methylenepropionic acid derivatives of the present invention were mainly found as methyl esters (R-OH,), but lower alkyl esters having up to 4 carbon atoms (
R-00 lower alkyl crystal) and free acid (R+=l()) could also be obtained by the same synthetic method.
本発明の化食物の代弐例を表−１に示す。Table 1 shows two examples of chemical foods of the present invention.
特開Ｂ、’！５９−１４４７３１ （６）上記の一般式
で択一的に示された部分ｍ造をもつ本発明の化合物は、
表−１において以下に示すよ５な化合物査号により開示
されている。Tokukai B,'! 59-144731 (6) The compound of the present invention having the moiety m structure alternatively shown in the above general formula,
In Table 1, compounds are disclosed by the 5 compound numbers shown below.
Ａ＝フェニル：屓１〜７．１９、
Ａ−ベンジル：Ａｉｌ ８
Ａ；ビリジル：ム１０〜１２
Ａ＝ナフチル：Ａ２０，２１
ム＝キノリニル：４１４〜１６
人；ピリミジル：扁１６
人＝ベンゾチアゾリル：Ａ８．９．２２Ａ＝キノキサリ
ニル：Ａ１７
置換基なし：Ａ１％８〜１Ω、１５．１４Ｓ１６．１Ｂ
−２２置換基ハ日ゲン：Ａ２，４．１１．１７二トロ：
Ａ５．１２、アルコキシ：Ａ１５アルキル：Ａ５．１５
、 トリフルオ四メチル＝Ａ７゜Ｘ＝酸素：Ａ１〜８．
１０〜１８、Ｘ＝硫黄ｚ崖ＰＸ ” ＮＨｍ ４１９〜
２１ 、Ｘ±Ｎ０Ｈｓ： Ａ ２２本発明の化合物は、
次のような方法で合成することができる。式中Ａ、Ｘは
先に記したものと同じであり、Ｋは炭系数１〜４の低級
アルキル基である。A=phenyl: 1-7.19, A-benzyl: Ail 8 A; biridyl: 10-12 A=naphthyl: A20,21 Mu=quinolinyl: 414-16; pyrimidyl: 16=benzothiazolyl: A8 .9.22A=quinoxalinyl: A17 No substituent: A1% 8-1Ω, 15.14S16.1B
-22 substituent: A2, 4.11.17 Nitro:
A5.12, alkoxy: A15 alkyl: A5.15
, trifluorotetramethyl=A7°X=oxygen: A1-8.
10~18, X=sulfur z cliff PX ” NHm 419~
21, X±N0Hs: A 22 The compound of the present invention is
It can be synthesized by the following method. In the formula, A and X are the same as those described above, and K is a lower alkyl group having 1 to 4 carbon atoms.
〔合成法−１〕
（１） （２） （３）°”・（４）
ＯＨ２
〔合成法−２〕
（１） 十 （ＢｒＯＨ２） ２０Ｈ−０００Ｋ −＋
（４）（５）
〔合成法−６〕
Ｂｒ０Ｈ２００００１１（６）＋＋１） −＋ （４）
ＯＨ２
換フェノール（１）を例えばエタノールのような溶媒及
びアルカリ（例えばＮａＯＨ、５倍モル）の存在下にβ
、β′−ジブロモイソ酪酸（２）と反応させることによ
ってβ−位が置換されたα−メチレンプ京ピオンＲ（３
）を得、さらにこの（３）をエステル化することによっ
て目的とするβ−置換フェノキシα−メチレンプロピオ
ン酸誘導体（４）を得る方法である。[Synthesis method-1] (1) (2) (3)°”・(4)
OH2 [Synthesis method-2] (1) 10 (BrOH2) 20H-000K −+
(4) (5) [Synthesis method-6] Br0H2000011 (6)++1) −+ (4)
OH2-converted phenol (1) is oxidized to β in the presence of a solvent such as ethanol and an alkali (e.g. NaOH, 5 times the molar amount).
, α-methylenepkyopion R (3) substituted at the β-position by reacting with β′-dibromoisobutyric acid (2)
) and further esterifies this (3) to obtain the desired β-substituted phenoxy α-methylenepropionic acid derivative (4).
合成法−２は前記と同様の置換フェノール（１）をエー
テル、 ＴＨＦのような不活性溶媒中トリエチルアミン
のような塩基（２倍モル）の存在下β、β′−ジブロモ
酪酸のエステル（５）と反応させ、目的物（４）を得る
方法である。Synthesis method 2 involves converting the same substituted phenol (1) as described above into ether and β,β'-dibromobutyric acid ester (5) in the presence of a base (2 times the mole) such as triethylamine in an inert solvent such as THF. This is a method to obtain the target product (4) by reacting with
合成法−３は同様の置換フェノール（１）ラニーチル、
ＴＨＦのような不活性溶媒中、トリエチルアミンのよ
プな塩基（尋モル）の存在下、α−プ目モモメチルアク
リル酸エステル６）と反応させることで目的物（４）を
得る方法である。Synthesis method-3 is a similar substituted phenol (1) ranithil,
This is a method for obtaining the desired product (4) by reacting with α-peach methyl acrylic acid ester 6) in the presence of a base such as triethylamine (fathomolar) in an inert solvent such as THF.
合成法の更に詳細な具体例は以下の製造例により示し、
またそれにより得られた各物質の代表的な物性値は表−
１に示した。A more detailed example of the synthesis method is shown in the following production example,
In addition, the typical physical properties of each substance obtained are shown in Table-
Shown in 1.
製造例−１〔合成法−１〕
２〜メチレン−５−（４−（２−す７チルアミノ）フェ
ノキシ）プロピオン酸の合成ｏ、９４１ （４！ｌ ｖ
ｒｏｌ ）の４−（２−ナフチルアξ））フェノールを
無水エタノール２０―に溶解する。次に粉末の水酸化ナ
トリウム（０，４８１／ １２ ｒｎ ｍｏＩりを加え
、しばらく加熱還流する。Production Example-1 [Synthesis Method-1] Synthesis of 2-methylene-5-(4-(2-s7tylamino)phenoxy)propionic acid o, 941 (4!l v
4-(2-naphthyl ξ))phenol of rol ) is dissolved in absolute ethanol 20-. Next, add powdered sodium hydroxide (0,481/12 rn moI) and heat under reflux for a while.
反応系が均一となったのち、 １．０１ （４ｍｍｏ
７）のβ、β′−ジブｑモイソ酪酸の無水エタノール溶
液（１ｏｄ）を滴下し、還流条件で６時間牛反応を行な
う。反応終ｒｆｉｋ室温まで冷却し、次にエタノールを
減圧留去する。得られた残液に水を加え１０％塩酸で酸
性化（Ｐ）（２〜５）し、ジエチルエーテルで抽出する
。エーテル層を飽和Ａｉｌ水で抽出し、アルカリ抽出層
を再び濃塩酸で酸性化すると灰白色法でんが析出する。After the reaction system became homogeneous, 1.01 (4 mmo
Anhydrous ethanol solution (1 od) of β, β'-dibuqmoisobutyric acid (7) was added dropwise, and the cow reaction was carried out under reflux conditions for 6 hours. At the end of the reaction, the reaction mixture is cooled to room temperature, and then the ethanol is distilled off under reduced pressure. Water is added to the resulting residual liquid, acidified (P) (2-5) with 10% hydrochloric acid, and extracted with diethyl ether. The ether layer is extracted with saturated Ail water, and the alkaline extracted layer is acidified again with concentrated hydrochloric acid to precipitate a gray-white powder.
吸引ろ過により析出物を分離し、水洗後渡圧下乾燥する
と０．６５ ＆の粗生成物が得られる。得られた粗生成
物は精製することなく次の反応に用いることができるが
粗生成物を薄層りμマドグラフィー（ワコーゲル■Ｂ−
５Ｆ、ヘキサン：酢酸エチル（以下Ｈ：ｌＣと略す）−
５：５で展間とさらに再結晶（ベンゼン）することによ
り灰白色結晶の２−メチレン−５−（４−Ｃ２−す７チ
ルアミノ）フェノキシ）−グロビオン酸（化合物Ａ２１
）が得られた。The precipitate is separated by suction filtration, washed with water, and then dried under passing pressure to obtain a crude product of 0.65… The obtained crude product can be used in the next reaction without purification, but the crude product can be used as a thin layer by μMadography (Wakogel ■B-
5F, hexane:ethyl acetate (hereinafter abbreviated as H:LC)-
Further recrystallization (benzene) at a ratio of 5:5 gave off-white crystals of 2-methylene-5-(4-C2-s7thylamino)phenoxy)-globionic acid (compound A21).
)was gotten.
製造例−２
２−メチレン−３−（４−（２−ナフチルアミノ）フェ
ノキシ）プロピオン酸メチルの合成
実施例−１で得られた粗２−メチレン−６−（４−（２
−す７チルアミノ）フェノキシ）プルピオン酸（ｏ、ｓ
７ ｍ ｍｏｊ純分）を無水メタノール３０１に溶解
し、触媒量の濃硫酸を加えて７時間加熱還流する。反応
終了後溶媒を減圧下留去し、残渣に水を加えジエチルエ
ーテルで抽出する。エーテル層を水洗、飽和食塩水洗し
て、無水硫酸マグネシウムで乾燥する。乾燥剤をＰ別し
エーテルを減圧留去すると褐色の残渣が得られる。薄層
クロマドグ２フイー（製造例１と同条件、但しＨ：ｇ＝
７：５で展開）で精製し、０．１２ 、Ｆ （９７％）
の２−メチレン−３−（４−（２−ナフチルアミノ）フ
ェノキシ）プロピオン酸メチル（化合物屋２０）が得ら
れた。Ａ−Ｘ−を変えた出発物（１）を用い、＃造例１
．２と同様の方法により化合物Ａ８．１０．１１が得ら
れた。Production Example-2 Synthesis of methyl 2-methylene-3-(4-(2-naphthylamino)phenoxy)propionate Crude 2-methylene-6-(4-(2-
-su7thylamino)phenoxy)purpionic acid (o, s
7 m moj purity) was dissolved in anhydrous methanol 301, added with a catalytic amount of concentrated sulfuric acid, and heated under reflux for 7 hours. After the reaction was completed, the solvent was distilled off under reduced pressure, water was added to the residue, and the mixture was extracted with diethyl ether. The ether layer is washed with water and saturated brine, and dried over anhydrous magnesium sulfate. The desiccant is removed by P and the ether is distilled off under reduced pressure to obtain a brown residue. Thin layer chroma dog 2 fee (same conditions as production example 1, but H:g=
7:5 development) and purified with 0.12, F (97%)
Methyl 2-methylene-3-(4-(2-naphthylamino)phenoxy)propionate (Compound Shop 20) was obtained. #Preparation Example 1 using the starting material (1) with different A-X-
．． Compound A8.10.11 was obtained in the same manner as in Example 2.
製造例−６〔合成法−２〕
２−メチレン−３−（４−フェノキシ）プロピオン酸メ
チルの合成
β２β’−シフロモ酪酸メチルエステル０．５９１（１
，５ｍ ｒｌＩｏｔ ）を無水ＴＨＦ１０ｄに８％する
。Production Example-6 [Synthesis Method-2] Synthesis of methyl 2-methylene-3-(4-phenoxy)propionate β2β'-cifuromobutyric acid methyl ester 0.591 (1
, 5 m rlIot ) to 8% in 10 d of anhydrous THF.
水冷下アルゴン気流下でトリエチルアミン０．５０１
（３，０ｍ ｍｏｌ ）を滴下し室温で３０分攪拌を続
ける。次に再び水冷下にして、４−ヒドロキシジフェニ
ルエーテルｏ、１９１ （１，Ｏｒｒｒｒｒｒｏｌ）の
無水Ｎ、に一ジメチルホルムアンド（５−）の溶液を滴
下する。滴下終了後、室温にて１時間牛攪拌する。生じ
た沈でんをろ別し、飽和重曹水、水、飽和食塩水で順次
洗ったのち無水硫酸マグネシウムで乾燥する。乾燥剤を
除去した後溶媒を減圧留去すると黄色油状物が得られる
。Triethylamine 0.501 under water cooling and argon flow
(3.0 mmol) was added dropwise and stirring was continued for 30 minutes at room temperature. Next, under water cooling again, a solution of dimethyl formand (5-) was added dropwise to anhydrous N of 4-hydroxydiphenyl ether o, 191 (1, Orrrrrol). After the addition is complete, the mixture is stirred at room temperature for 1 hour. The resulting precipitate is filtered off, washed successively with saturated aqueous sodium bicarbonate, water, and saturated brine, and then dried over anhydrous magnesium sulfate. After removing the drying agent, the solvent is distilled off under reduced pressure to obtain a yellow oil.
この油状物を薄層クロマトグラフィー（＃造例２と同条
件）で精製して０．１９ Ｉｉ（６７％）の２−メチレ
ン−３−（４−７二ノキシフエノキシ）プロピオン酸メ
チル（化合物ＡＩ）を得た。This oil was purified by thin-layer chromatography (same conditions as in Example 2) to obtain 0.19 Ii (67%) of methyl 2-methylene-3-(4-7 dynoxyphenoxy)propionate (compound AI). I got it.
ム−Ｘを変えた種々の出発物（１）を用い、上記と同様
にして化合物屋２〜７．９．１２〜１９．２２が得られ
た。Compounds 2-7.9.12-19.22 were obtained in the same manner as above using various starting materials (1) with different Mu-X.
本発明の新規化合物は植物に対して生長抑制作用を有す
る。この植物に対する作用効果を以下の使用例に示した
。従来知られているチオエステルや鎖式チオエーテル構
造をもつα−置換アクリル酸誘導体が比較的低濃度にお
いて植物の生長促進、高濃度において落葉促進作用をも
つものであったのと異なり、本発明の新規化合物は植物
の生長抑制作用をもつのである。このように、植物生長
抑制剤として有用な新規化合物が本発明により提供され
た。The novel compound of the present invention has a growth inhibiting effect on plants. The effects on this plant are shown in the usage examples below. Unlike conventionally known α-substituted acrylic acid derivatives with thioester or chain thioether structures, which had the effect of promoting plant growth at relatively low concentrations and promoting defoliation at high concentrations, the novel effects of the present invention The compound has a growth inhibitory effect on plants. Thus, the present invention provides a novel compound useful as a plant growth inhibitor.
使用例（植物生長抑制作用の試験）
メルク５０ ％ （重量基準、以下同じ）、ベントナイ
ト２５部、ソルボ−ルー９０４７（東邦化学工業株式会
社製界面活性剤）２部、ソルボ−ルー５ｏｓｐ （同上
）３部を良く混合し、キャリヤーとした。被験化合物を
それぞれ５０部と前記キャリヤー２００都を混合し、２
０％水相剤を作った。この水和剤を純水に分散させ所定
濃度とした。別のシャーレで催芽させたイネ、タイヌビ
エ、二十日ダイコン種子を上記水和剤分散液に投入し、
２５℃の照明付定温庫で７日間育苗して生長程度を観察
した。結果を表−２に示す。Usage example (test for plant growth inhibitory effect) Merck 50% (by weight, same below), 25 parts of bentonite, 2 parts of Sorbo-Rue 9047 (surfactant manufactured by Toho Chemical Co., Ltd.), Sorbo-Rue 5 osp (same as above) Three parts were mixed well and used as a carrier. Mix 50 parts of each of the test compounds and 200 parts of the above carrier,
A 0% aqueous phase agent was made. This hydrating agent was dispersed in pure water to a predetermined concentration. Rice, Japanese millet, and Japanese radish seeds germinated in a separate petri dish are added to the above-mentioned hydrating agent dispersion,
Seedlings were grown for 7 days in a constant temperature warehouse with lighting at 25°C, and the growth level was observed. The results are shown in Table-2.
表示法 無影響−１，２５％止長抑制＝２゜５０％生長
抑＊ＩＪ−ｘ、７ｓ％生長抑制＝４，１００％生長抑制
−５
弐−２に示したように、本発明の化合物は植物の生長を
顕著に抑制し、除草剤への利用が期待される。Indication method: No effect - 1,25% growth inhibition = 2° 50% growth inhibition *IJ-x, 7s% growth inhibition = 4,100% growth inhibition -5 As shown in 2-2, the compound of the present invention It significantly inhibits plant growth and is expected to be used as a herbicide.
／／ＡＯＩＮ ３７１０６
７４１９−４Ｈ３９１０２７４１９−４Ｈ
４３／３４ ７２１５−４
Ｈ４３１５４７２１５−４Ｈ
４３／６０ １０１ ７２１５−４Ｈ
４３／７８ １０１ ７２１５−４Ｈ
＠発 明 者 平子慶之
姫路市余部区上余部５００
０発 明 者 森島端雄
姫路市余部区上余部５００
０発 明 者 正本和久
姫路市網干区新在家１２３９
２４４−//AOIN 37106
7419-4H391027419-4H 43/34 7215-4
H431547215-4H 43/60 101 7215-4H
43/78 101 7215-4H
@ Inventor Yoshiyuki Hirako 500 Kamiyobe, Abobe-ku, Himeji City 0 Inventor Morishima Hanao 500 Kamiyobe, Abobe-ku, Himeji City 0 Inventor Masamoto Waku 1239-244 Shinzaike, Aboshi-ku, Himeji City
Claims (1)
ル、キノリニル、ビリ叱ジル、ベンゾチアゾリル又はキ
ノキサリニルから選ばれる環式基であり、ハロゲン、ニ
トロ、低級アルコキシ、低級アルキル及びトリフルオμ
メチルよりなる群から選ばれる環上の置換基をもってい
てもよい、Ｘは一〇−、−Ｓ＋。 −ＮＨ＋、又は−ＮＧＨ，−であり、Ｒは水素原子又は
炭素数１〜４の低級アルキル基である。〕で表わされる
β−置換フエノキシ−α−メチレンプ目ピオン酸誘導体[Scope of Claims] t General formula [wherein, human is a cyclic group selected from phenyl, benzyl, pyridyl, naphthyl, quinolinyl, pyridyl, benzothiazolyl, or quinoxalinyl; halogen, nitro, lower alkoxy, lower Alkyl and trifluoroμ
It may have a substituent on the ring selected from the group consisting of methyl, and X is 10-, -S+. -NH+ or -NGH,-, and R is a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms. ] β-substituted phenoxy-α-methylene pionic acid derivative
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58018600A JPS59144731A (en) | 1983-02-07 | 1983-02-07 | Beta-substituted phenoxy-alpha-methylenepropionic acid derivative |
| EP84100497A EP0117412A1 (en) | 1983-01-18 | 1984-01-18 | Propene derivatives and their use as plant growth inhibitors |
| EP84100585A EP0118685A1 (en) | 1983-02-07 | 1984-01-20 | Propene derivatives and their use as plant growth inhibitors |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58018600A JPS59144731A (en) | 1983-02-07 | 1983-02-07 | Beta-substituted phenoxy-alpha-methylenepropionic acid derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59144731A true JPS59144731A (en) | 1984-08-18 |
| JPH0259818B2 JPH0259818B2 (en) | 1990-12-13 |
Family
ID=11976131
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58018600A Granted JPS59144731A (en) | 1983-01-18 | 1983-02-07 | Beta-substituted phenoxy-alpha-methylenepropionic acid derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59144731A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59157051A (en) * | 1983-02-25 | 1984-09-06 | Daicel Chem Ind Ltd | Beta-oxy-alpha-methylenepropionic acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5753438A (en) * | 1980-07-29 | 1982-03-30 | Basf Ag | Manufacture of 2-aryloxy-acrylic acid compound |
| JPS57140771A (en) * | 1981-01-12 | 1982-08-31 | Ici Australia Ltd | Herbicidal compounds and composition and use |
-
1983
- 1983-02-07 JP JP58018600A patent/JPS59144731A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5753438A (en) * | 1980-07-29 | 1982-03-30 | Basf Ag | Manufacture of 2-aryloxy-acrylic acid compound |
| JPS57140771A (en) * | 1981-01-12 | 1982-08-31 | Ici Australia Ltd | Herbicidal compounds and composition and use |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59157051A (en) * | 1983-02-25 | 1984-09-06 | Daicel Chem Ind Ltd | Beta-oxy-alpha-methylenepropionic acid |
| JPH0261929B2 (en) * | 1983-02-25 | 1990-12-21 | Daicel Chem |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0259818B2 (en) | 1990-12-13 |
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