JPS6016983A - 3-methylene-4-chromanone derivative - Google Patents
3-methylene-4-chromanone derivativeInfo
- Publication number
- JPS6016983A JPS6016983A JP12347183A JP12347183A JPS6016983A JP S6016983 A JPS6016983 A JP S6016983A JP 12347183 A JP12347183 A JP 12347183A JP 12347183 A JP12347183 A JP 12347183A JP S6016983 A JPS6016983 A JP S6016983A
- Authority
- JP
- Japan
- Prior art keywords
- methylene
- chromanone
- formula
- group
- methyl
- 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.)
- Pending
Links
- GPZSMCFSXYVSAL-UHFFFAOYSA-N 3-methylidenechromen-4-one Chemical class C1=CC=C2C(=O)C(=C)COC2=C1 GPZSMCFSXYVSAL-UHFFFAOYSA-N 0.000 title claims description 7
- 125000001424 substituent group Chemical group 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims abstract description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 21
- 150000001875 compounds Chemical class 0.000 abstract description 14
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 4
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 abstract description 3
- 230000008635 plant growth Effects 0.000 abstract description 3
- 230000002363 herbicidal effect Effects 0.000 abstract description 2
- 239000004009 herbicide Substances 0.000 abstract description 2
- 239000012442 inert solvent Substances 0.000 abstract description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 125000005843 halogen group Chemical group 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 abstract 1
- 239000005648 plant growth regulator Substances 0.000 abstract 1
- 238000007363 ring formation reaction Methods 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 6
- 150000002081 enamines Chemical class 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 230000009036 growth inhibition Effects 0.000 description 3
- 238000004809 thin layer chromatography Methods 0.000 description 3
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- XJPMZUHWKQNEBL-UHFFFAOYSA-N 2-[(3-chlorophenoxy)methyl]prop-2-enoic acid Chemical compound OC(=O)C(=C)COC1=CC=CC(Cl)=C1 XJPMZUHWKQNEBL-UHFFFAOYSA-N 0.000 description 2
- MSTDXOZUKAQDRL-UHFFFAOYSA-N 4-Chromanone Chemical group C1=CC=C2C(=O)CCOC2=C1 MSTDXOZUKAQDRL-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000005822 methylenation reaction Methods 0.000 description 2
- VGIVLIHKENZQHQ-UHFFFAOYSA-N n,n,n',n'-tetramethylmethanediamine Chemical compound CN(C)CN(C)C VGIVLIHKENZQHQ-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000002373 plant growth inhibitor Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- -1 substituted Chemical class 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- NUMXHEUHHRTBQT-AATRIKPKSA-N 2,4-dimethoxy-1-[(e)-2-nitroethenyl]benzene Chemical group COC1=CC=C(\C=C\[N+]([O-])=O)C(OC)=C1 NUMXHEUHHRTBQT-AATRIKPKSA-N 0.000 description 1
- VXQIXPHPKHRMDI-UHFFFAOYSA-N 5-chloro-3-methylidenechromen-4-one Chemical compound O1CC(=C)C(=O)C2=C1C=CC=C2Cl VXQIXPHPKHRMDI-UHFFFAOYSA-N 0.000 description 1
- SIEVXPRXIUIDLD-UHFFFAOYSA-N 6-methyl-3-methylidenechromen-4-one Chemical compound O1CC(=C)C(=O)C2=CC(C)=CC=C21 SIEVXPRXIUIDLD-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 244000058871 Echinochloa crus-galli Species 0.000 description 1
- 235000008247 Echinochloa frumentacea Nutrition 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 244000088415 Raphanus sativus Species 0.000 description 1
- 235000006140 Raphanus sativus var sativus Nutrition 0.000 description 1
- ZONYXWQDUYMKFB-UHFFFAOYSA-N SJ000286395 Natural products O1C2=CC=CC=C2C(=O)CC1C1=CC=CC=C1 ZONYXWQDUYMKFB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 125000004429 atom Chemical group 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
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229930003949 flavanone Natural products 0.000 description 1
- 150000002207 flavanone derivatives Chemical class 0.000 description 1
- 235000011981 flavanones Nutrition 0.000 description 1
- 229930003935 flavonoid Natural products 0.000 description 1
- 150000002215 flavonoids Chemical class 0.000 description 1
- 235000017173 flavonoids Nutrition 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
本発明は、新規な３−メチレン−４−クロマノンに関す
るものであり、この化合物は植物生長抑制剤として有用
である。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel 3-methylene-4-chromanone, which compound is useful as a plant growth inhibitor.
従来、知られていた３−メチレン−４−クロマノン誘導
体の多くは２位にフェニル基あるいけ置換フェニル基を
有し、これらはフラボノイドと呼ばれる黄色天然色素の
一種で、フラバノン系化合物として知９）れている（、
Ｗａｒｄ 、 Ｆ 、 Ｅ 、 ｅｉ ａＩＪ、Ｍｅ
ｄ 、 Ｃｈｅｍ、 １９８１ 、２４ （９） １０
７３〜１０７７及びＢｕｃｌ（Ｉｅｒ］−１＋ 、 Ｔ
、 ｅｔ ａｌ Ｕ、 Ｓ 、Ｐ。Many of the conventionally known 3-methylene-4-chromanone derivatives have a phenyl group or a substituted phenyl group at the 2-position, and these are a type of yellow natural pigment called flavonoid, and are known as flavanone compounds9) (,
Ward, F., E., ei aIJ, Me.
d, Chem, 1981, 24 (9) 10
73-1077 and Bucl(Ier)-1+, T
, et al U, S, P.
４．２４１，０６９等）。２位にフェニル基あるいは置
換フェニル基を有しない３−メチレン−４−クロマノン
としてはわずかに数例が知られているにすぎず（文献同
上）、しかもいずれも、縮合べ／ゼン環上に置換基を持
っていない。又、それら３−メチレ／−４−クロマノン
は主に薬理学的研究の対象（例えばダラム陽性菌に対す
る作用、抗ウイルス性）として記載さねでいるのみで植
物に対する作用は記されていない。4.241,069 etc.). There are only a few known examples of 3-methylene-4-chromanone that does not have a phenyl group or a substituted phenyl group at the 2-position (ibid.), and all of them have a substituent on the fused be/zene ring. It has no basis. Furthermore, 3-methylene/-4-chromanone has only been described as a subject of pharmacological research (for example, action against Durum-positive bacteria, antiviral properties), and no action on plants has been described.
本発明者は有用な対植物活性をもつ化合物を見出スヘく
研究し、３−メチレン−４−クロマノン誘導体に属する
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１〜だ。The present inventor discovered and conducted extensive research on compounds with useful activity against plants, synthesized a group of new compounds belonging to 3-methylene-4-chromanone derivatives, confirmed their effects on plants, and completed the present invention. It's 1~.
即ち本発明は対植物活性という有用な性質をもつ化合物
を新たに創り出すことを目的どするものである。That is, the purpose of the present invention is to create a new compound that has the useful property of being active against plants.
で表わされる置換−３−メチレ／−４−クロマノンであ
る。ここでＸげ塩素、臭素、フッ素などのハロケ″′／
原子、メチル基、メトギン基からなる群より選ばれる置
換基で、ｎは０〜２の整数である。It is a substituted-3-methylene/-4-chromanone represented by Here, chlorine, bromine, fluorine, etc.
A substituent selected from the group consisting of an atom, a methyl group, and a metgyne group, and n is an integer of 0 to 2.
即ちＸｎげ上記置換基Ｘが２個以内存在していてもよい
ことを意味している。Ｉ（，１，、Ｒ２はそれぞれ水素
原子若しくは低級アルキル基（炭素数１〜４）であるが
、両者で環を形成しテトラメチレン基となってもよい。That is, it means that up to two of the above substituents X may be present. I(, 1, and R2 are each a hydrogen atom or a lower alkyl group (having 1 to 4 carbon atoms), but both may form a ring to form a tetramethylene group.
本発明の化合物ｆｉＸ 、 Ｒ１、Ｒ，２のうち少なく
とも１個の置換基をもっている。即ちｎ−０゜Ｒ１＝
Ｒ２＝ Ｉ−Ｔの場合を含捷ない。The compound fiX of the present invention has at least one substituent among R1, R, and 2. That is, n-0°R1=
The case where R2=IT is not included.
本発明の化合物（（次のような方法により容易に合成す
ることができる。式中Ｘｎは前記と同じ意味である。The compound of the present invention can be easily synthesized by the following method. In the formula, Xn has the same meaning as above.
〈合成法−Ａ〉
ビスジメチルアミノ
合成法−人は、対応するカル′＋″／酸より常法例よっ
て容易に得られる酸クロライド■をベンゼンのような不
活性溶媒中一般に１’ｒｉｅｄｅｌ−Ｃｒａｆｔｓ触媒
と呼ばわる触媒（例えば塩化アルミニウム、塩化亜鉛）
の少過剰量存在下、０°〜３０°Ｃの温度に ３ −
て分子内環化させ目的とする置換−３メチレ／−４−ク
ロマノンＩを得る方法である。一方合成法−Ｂは０−ヒ
ドロキシアセトフェノンｍをで表わされるエナミンと常
温乃至１００℃の温度にて反応させ２−位が置換された
４−クロマノン■とした後、ビスジメチルアミノメタン
■と、無水酢酸により３位をメチレン化することによっ
て目的とする３−メチレン−４−クロマノンＩを得る方
法である。この際４−クロマノン■の３位メチレン化は
、一般に他のケトンのα−メチレン化に用いられる手法
を応用することももちろん可能である。<Synthetic Method A> Bisdimethylamino Synthetic Method - One can synthesize acid chloride ■, which is easily obtained from the corresponding car'+''/acid by a conventional method, in an inert solvent such as benzene, generally using a 1'riedel-Crafts catalyst. catalysts (e.g. aluminum chloride, zinc chloride)
In this method, the desired substituted -3methylene/-4-chromanone I is obtained by intramolecular cyclization at a temperature of 0° to 30°C in the presence of a small excess of 3-. On the other hand, in synthesis method B, 0-hydroxyacetophenone m is reacted with the enamine represented by at room temperature to 100°C to form 4-chromanone substituted at the 2-position, and then bisdimethylaminomethane This is a method to obtain the desired 3-methylene-4-chromanone I by methyleneating the 3-position with acetic acid. In this case, for the 3-position methylenation of 4-chromanone (1), it is of course possible to apply the method generally used for α-methylenation of other ketones.
な勘エナミン■は、メタノール等の不活性極性情 ４−
媒中で、対応するケト／と＆ｏリジンとより常法によっ
て容易に得ることができる。The enamine (2) can be easily obtained from the corresponding keto/&o lysine in an inert polar medium such as methanol by a conventional method.
合成法の更に詳細な説明は製造例によって具体的に示し
、それによって得られた各物質の代表的な物性値を第１
表に示した。A more detailed explanation of the synthesis method will be concretely shown using production examples, and typical physical property values of each substance obtained will be shown in the first section.
Shown in the table.
本発明の化合物の植物に対する作用を使用例に示した。The effects of the compounds of the present invention on plants are shown in usage examples.
このように植物生長抑制剤として有用な化合物が本発明
により提供された。Thus, the present invention provides a compound useful as a plant growth inhibitor.
−７
製造例１（合成法人）
６−メチル−３−メチレン−４−クロマノン（化合物扁
１）の合成
２−（４−メチルフェノキシ）メチルアクリル酸と塩化
チオニルより常法に従って調製した２−（４−メチルフ
ェノキシ）メチルアクリル酸クロライド（１］、、 ２
グ）の無水ベンゼン溶液（１００コ）を塩化アルミニウ
ム（７，４２）の無水ベンゼン溶液（２００ｍｌりに水
浴上で徐々に滴下する。-7 Production Example 1 (Synthesis Corporation) Synthesis of 6-methyl-3-methylene-4-chromanone (Compound 1) 2-(2-(4-methylphenoxy)methylacrylic acid and thionyl chloride were prepared according to a conventional method. 4-methylphenoxy) methylacrylic acid chloride (1),, 2
Anhydrous benzene solution (100 ml) of aluminum chloride (7,42) was gradually added dropwise to 200 ml of anhydrous benzene solution of aluminum chloride (7,42) on a water bath.
同温度で１時間攪拌を続けた後、反応溶液を冷却した２
００ ｍｌの６Ｎ塩酸に静かに注ぎ込む。ジエチルエ
ーテルで有機層を抽出し、エーテル溶液は水、重炭酸す
） ＩＪウム溶液、そして水で順次洗浄したのち、砒酸
マグネシウムで一夜乾燥する。溶媒を留去することによ
り、９．３７の黄色油状物が得られた。この件生成物は
一部（ｏ、４ｙ）を薄層クロマトグラフィー（ワコーゲ
ル■Ｂ−５Ｆ、ヘキサン：酢酸エチル−７：３展開）で
精製し淡黄色油状物（０，１６９収率１７．３係）を得
、これらのスペクトルデータよりその構造を確認した。After continuing stirring at the same temperature for 1 hour, the reaction solution was cooled.
Pour gently into 00 ml of 6N hydrochloric acid. The organic layer was extracted with diethyl ether, and the ether solution was washed successively with water, bicarbonate solution, and water, and then dried over magnesium arsenate overnight. By distilling off the solvent, a yellow oil of 9.37 was obtained. A part of the product (o, 4y) was purified by thin layer chromatography (Wakogel ■B-5F, developed with hexane:ethyl acetate-7:3) to give a pale yellow oil (0.169 yield 17.3). ), and its structure was confirmed from these spectral data.
製造例２（合成法Ａ）
５−クロロ−３−メチレン−４−クロマノン（化合物慕
５）の合成
２−（３−クロロフェノキシ）メチルアクリル酸より調
製した２−（３−クロロフェノキシ）メチルアクリル酸
クロライド（１０，５ｇ＞から製造例］と同様にして５
．６ ｇの黄色の粗生成物か得られた。薄層クロマトグ
ラフィ＝（ワコーケゞル■Ｂ−５Ｆ、ヘキサン：酢エチ
ー７＝３展開）で一部（０，４ｇ）を精製し、白色結晶
である５−クロロ−３−メチレ／−４−クロマノｙ （
０，１１ｇ収率１２２％を得た。この場合塩素原子が７
位に置換した異性体は得られなかった。同様にして第１
表の化合物朋２〜４，６〜８を合成した。Production Example 2 (Synthesis Method A) Synthesis of 5-chloro-3-methylene-4-chromanone (Compound 5) 2-(3-chlorophenoxy)methylacrylic acid prepared from 2-(3-chlorophenoxy)methylacrylic acid 5 in the same manner as in the example of production from acid chloride (10.5 g)
．． 6 g of yellow crude product were obtained. A portion (0.4 g) was purified by thin layer chromatography (Wako Kel B-5F, hexane:acetic acid ethyl 7=3 development) to obtain white crystals of 5-chloro-3-methylene/-4-chromano. y (
0.11g yield 122% was obtained. In this case, the chlorine atom is 7
No isomer substituted in this position was obtained. Similarly, the first
Compounds 2-4 and 6-8 shown in the table were synthesized.
製造例３（合成法Ｂ）
２−ブチル−２−メチル−３−メチレ／−４−クロマノ
／（化合物茄９）の合成
２−ヘキサノンとピロリジンから調製されたエナミン（
６，４，９）と０−ヒドロキシアセトフェノン（５４ｇ
）を無水メタノール６０ｍ１中で３時間半加熱還流する
。冷却後、溶媒を濃縮１〜希塩酸５０ｍ１を加え有機物
をベンヤ゛／で抽出する。ベンゼン層は水洗し、硫酸マ
グネシウムで乾燥する。溶媒を留去して７．７．９の褐
色油状物を得た。得られた粗生成物にシリカケゞルカラ
ムクロマトグラフイー（ワコーケゞル■ｃ−１ｏｏ、ベ
ンゼン：へキザン＝８＝２溶出）で精製して黄色油状物
である２−プチルー２−メチル−４−クロマノン（３０
ｇ収率３４４％）を得た。Production Example 3 (Synthesis Method B) Synthesis of 2-butyl-2-methyl-3-methylene/-4-chromano/(Compound 9) Enamine (prepared from 2-hexanone and pyrrolidine)
6,4,9) and 0-hydroxyacetophenone (54g
) is heated under reflux for 3.5 hours in 60 ml of anhydrous methanol. After cooling, the solvent was concentrated and 50 ml of diluted hydrochloric acid was added, and the organic matter was extracted with a solvent. The benzene layer is washed with water and dried with magnesium sulfate. The solvent was evaporated to give a brown oil of 7.7.9. The obtained crude product was purified by silica gel column chromatography (Wako Kele ■c-1oo, elution with benzene:hexane = 8 = 2) to obtain 2-butyl-2-methyl-4 as a yellow oil. -Chromanone (30
g yield 344%) was obtained.
次Ｋ、２−７’チル−２−メチル−４−クロマノン（０
，３、！９ ）とビスジメチルアミノメタン（４５ｍｌ
）を室温で攪拌１７、そこへ無水酢酸（４，５ｍｌ）
を徐々に滴下する。滴下終了后、１時間半加熱還流し、
冷後、氷水３Ｑｍｌ！に反応溶液を注ぎ込む。K, 2-7' thyl-2-methyl-4-chromanone (0
,3,! 9) and bisdimethylaminomethane (45ml)
) was stirred at room temperature, and acetic anhydride (4.5 ml) was added thereto.
Gradually drip. After dropping, heat under reflux for 1.5 hours.
After cooling, add 3Qml of ice water! Pour the reaction solution into.
有機層をジエチルエーテルで抽出し、エーテル溶液は希
アルカリ水溶液、水、飽和食塩水で順次洗浄し、硫酸マ
グネシウムで一夜乾燥する。溶媒を留去し得られた油状
の粗生成物を薄層クロマトグラフィー（ワコーケ゛ル■
Ｂ−５Ｆ、ベンゼン展開）で精製し、無色の油状物であ
る２−ブチル−２−メチル−２−メチレン−４−クロマ
ノン（０，１５ｇ収率４７５％）を得た。The organic layer is extracted with diethyl ether, and the ether solution is washed successively with a dilute aqueous alkaline solution, water, and saturated brine, and dried over magnesium sulfate overnight. The oily crude product obtained by distilling off the solvent was subjected to thin layer chromatography (Wako Cell).
B-5F (developed with benzene) to obtain 2-butyl-2-methyl-2-methylene-4-chromanone (0.15 g, yield 475%) as a colorless oil.
同様の方法により第１表の化合物朋１０を又、シクロペ
ンタノンとピロリジンより調製すれたエナミンを用いて
第１表の化合物Ａ ］ Ｉ 、 １２を合成した。In a similar manner, Compound 10 in Table 1 was synthesized, and Compounds A] I and 12 in Table 1 were synthesized using an enamine prepared from cyclopentanone and pyrrolidine.
使用例（植物生長抑制作用の試験）
タルク５０部、ベントナイト２５部、ソルボ−ルー９０
４７（東邦化学工業株式会社製界面活性剤）２部、ソル
ボ−ルー５０３９（同上）３部を良く混合し、キャリヤ
ーと（７た。被験化合物をそれぞれ５０部と前記キャリ
ヤー２００部を混合１〜．２０％水利剤を作った。この
水和剤を純水に分散させ所定濃度どじだ。別のシャーレ
で催芽させたイネ、タイノビエ、二十日ダイコン種子を
上記水和剤分散液に投入し、２５°Ｇの照明伺定温庫で
７日間育苗して生長程度を観察した。Usage example (test of plant growth inhibitory effect) Talc 50 parts, Bentonite 25 parts, Sorbo-roux 90
47 (surfactant manufactured by Toho Chemical Co., Ltd.) and 3 parts of Sorbo-Rue 5039 (same as above) were mixed well, and 50 parts of each of the test compounds and 200 parts of the carrier were mixed with carrier (7). .20% water conservancy was made. This water dispersant was dispersed in pure water and adjusted to a specified concentration. Seeds of rice, Japanese millet, and 20-day radish germinated in a separate Petri dish were added to the above water dispersion liquid. Seedlings were grown for 7 days in a warm room with constant lighting at 25°G and their growth was observed.
結果を第２表に示す。The results are shown in Table 2.
表示法 無影響−１，２５％生長抑制−２゜５０％生長
抑制＝３．７５％生長
一１０＝
抑制−４，，１００％生長抑制＝５
第２表に示し７たよって、本発明に用いられた化合物は
植物の生長を顕著に抑制し７、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 = 3.75% growth - 10 = inhibition - 4, 100% growth inhibition = 5 As shown in Table 2, the present invention The compound used significantly inhibits plant growth 7 and is expected to be used as a herbicide.
＝１１− 第 ２ 表=11- Table 2
Claims (1)
ルキル基又けＲ１とＲ２とで環を形成したテトラメチレ
ン基を表わし、Ｘｎ Ｕ、ハロケゝン原子メチル基及び
メトキシ基からなる群より選ばれる２個以内（ｎ−０〜
２）の置換基が存在し得ることを意味する。）で表わさ
れ、少くとも１個の置換基をもつ３−メチレン−４−ク
ロマノン誘導体[Claims] ■t'- (In the formula, R1 and R2 each represent a hydrogen atom or a lower alkyl group and a tetramethylene group formed by R1 and R2 to form a ring, Xn U, a halokene atom methyl up to two selected from the group consisting of a group and a methoxy group (n-0 to
It means that the substituent of 2) may be present. 3-methylene-4-chromanone derivative represented by ) and having at least one substituent
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12347183A JPS6016983A (en) | 1983-07-08 | 1983-07-08 | 3-methylene-4-chromanone 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 |
|---|---|---|---|
| JP12347183A JPS6016983A (en) | 1983-07-08 | 1983-07-08 | 3-methylene-4-chromanone derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6016983A true JPS6016983A (en) | 1985-01-28 |
Family
ID=14861444
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12347183A Pending JPS6016983A (en) | 1983-01-18 | 1983-07-08 | 3-methylene-4-chromanone derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6016983A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01319481A (en) * | 1988-05-06 | 1989-12-25 | Merck Patent Gmbh | Cromane derivative |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4241069A (en) * | 1979-09-04 | 1980-12-23 | Miles Laboratories, Inc. | 3-Methylene flavanones and 3-methylene chromanones |
-
1983
- 1983-07-08 JP JP12347183A patent/JPS6016983A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4241069A (en) * | 1979-09-04 | 1980-12-23 | Miles Laboratories, Inc. | 3-Methylene flavanones and 3-methylene chromanones |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01319481A (en) * | 1988-05-06 | 1989-12-25 | Merck Patent Gmbh | Cromane derivative |
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