JPS5921673A - Preparation of 4-allyl-6-phenyl-1,2,4-triazin-5(2h)-one-3- thione - Google Patents
Preparation of 4-allyl-6-phenyl-1,2,4-triazin-5(2h)-one-3- thioneInfo
- Publication number
- JPS5921673A JPS5921673A JP57132882A JP13288282A JPS5921673A JP S5921673 A JPS5921673 A JP S5921673A JP 57132882 A JP57132882 A JP 57132882A JP 13288282 A JP13288282 A JP 13288282A JP S5921673 A JPS5921673 A JP S5921673A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- formula
- palladium
- preparation
- phenyl
- 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
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は式
で示されるｑ−７リルーに一７エニルー／２．２ダート
リアジン−ｔ（、ＺＨ）−オン−３−チオンの製造法に
関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing q-7lylu-17enyl/2.2dartriazine-t(,ZH)-one-3-thione represented by the formula.
式（１）で示される化合物は南アフリカ特許第１ＪＯ４
ｔｌ１０９号明細書に記載されているが、除草剤として
有用な式（ＩＩ）および弐（■）で示される化合物の製
造上重要な中間体である。The compound represented by formula (1) is covered by South African Patent No. 1 JO4
It is described in TL 109, and is an important intermediate in the production of compounds represented by formula (II) and 2 (■), which are useful as herbicides.
（Ｕ） ＠）
式（ＩＴ）で示さすする化合物１寸例えば４素の存在下
ヨウ化メチルとの反応により、寸た式（１）で示される
化合物け０の存在下に加熱することにより容易に式（１
）で示される化合物から製造することができる。(U) @) A compound represented by the formula (IT) is reacted with methyl iodide in the presence of, for example, 4 elements, and a compound represented by the formula (1) is heated in the presence of 0. Equation (1
) can be produced from the compound shown.
式（Ｉ）で示されるグーアリルチオセミカルバジドとフ
ェニルグリオキシル酸との反応により製 を造すること
かで今るが、収率が良好でないこと、両伸料化合物とも
高価であるこｂ等の欠点を有している。Currently, the product is produced by the reaction of guarylthiosemicarbazide represented by formula (I) with phenylglyoxylic acid, but it has drawbacks such as poor yield and high price of both extender compounds. have.
式（ＩＩＩ）で示される化合物に畑地の発芽前および発
芽後処理において、ハコベ、シロザ、７オビユ、妥・、
ベリ１ニユ、イチビ、ダブ、アブｉ）：、ミゾハコベ、
゛１ゼナ、キカシグサ、ノハラガラシ等の広葉雑草、ヒ
エ、エノコログサ、メヒシバ、スズメノカタビラ、スズ
メノカタビラ等のイネ科雑草、カヤツリグサ、ホタルイ
、マツバイ等のカヤツリグサ科雑草に対して除草効力を
有し、トウ上０：Ｉシ、コムギ等の作物に対して、特に
問題となる薬害を示さない。尚、式（１１０で示される
化合物の除草効力については後の蕗考例に記載した○
次に本発明製造法について述べる。In pre- and post-emergence treatments of field fields, the compound represented by formula (III)
Berry 1 New, Ichibi, Dove, Abu I):, Mizo Chickweed,
゛1 It has a herbicidal effect on broad-leaved weeds such as Xena, japonica, and grasshopper, grass family weeds such as Japanese barnyard grass, foxtail grass, grass grass, cyperus japonica, and cyperus cyperus, and cyperus weeds such as cyperus cyperus, bulrush, and cyperus. It does not cause particularly problematic phytotoxicity to crops such as wheat and wheat. The herbicidal efficacy of the compound represented by the formula (110) is described in the Fushimi Example below.Next, the production method of the present invention will be described.
式（Ｔ）で示される化合物は前述の公知の方法でに、フ
ェニルグリオキシル酸と４ｔ−７リルーチオセミカルバ
ジドとの反応によって得られるがα−ケト酸が必須であ
ることおよびグーアリルチオセミカルバジドを別途製造
しなけれμならないという欠点を有している。The compound represented by formula (T) can be obtained by the reaction of phenylglyoxylic acid and 4t-7lyluthiosemicarbazide according to the above-mentioned known method, but α-keto acid is essential and guallylthiosemicarbazide must be added separately. It has the disadvantage that it must be manufactured.
一方、本発明製造法において式（１）で示される化合物
の前駆体である式（ＩＶ）
で示される３−アリルチオ−４−フェニル−／。On the other hand, in the production method of the present invention, 3-allylthio-4-phenyl-/ represented by formula (IV) is a precursor of the compound represented by formula (1).
２、ゲートリアジン−Ｊ（，２Ｈ）−オンは、フェニル
グリオキシル酸誘導体（酸、エステル、アミド）とセミ
カルバジドとの反応により容易に得られる６−フェニル
−／、２．’Ｉ−トリアジンーｔ（、ｚＨ，＜）ｒ）−
オン−３−チオンを塩基存在下アリルハライドと反応さ
せれば簡単にかつ収率よく得ることができる。続いて式
（間で示される化合物をパラジウム（ＩＩ）化合物の存
在下に転位反応を行なわせることによって式（１）で示
される化合物を高収率で得ることができる０この場合の
パラジウム（１１）化合物としては塩化ｌ＜ラジウム、
酢酸パラジウム等であり、またこれらをアセトニトリル
、ベンゾニトリル等との錯体にして用いることもでき、
使用量は触媒量で十分であり０．０／〜、２０モルチ、
好ま６〈は０．７〜１０モルチである。また反応溶媒と
してはジエチルエーテル、テトラヒドロフラン、ジオキ
サン等のエーテル類があげられ、Ｏ０〜ｔｓｏ Ｃで７
０分から７５時間の反応で式（１）で示される化合物を
製造することができる。2. Gatetriazin-J(,2H)-one is a 6-phenyl-/,2. 'I-triazine-t(,zH,<)r)-
It can be easily obtained in good yield by reacting one-3-thione with allyl halide in the presence of a base. Subsequently, the compound represented by the formula (1) can be obtained in high yield by rearranging the compound represented by the formula (1) in the presence of a palladium (II) compound. ) As a compound, l chloride < radium,
palladium acetate, etc., and these can also be used in complexes with acetonitrile, benzonitrile, etc.
The amount used is 0.0/~, 20 molti, which is sufficient as a catalytic amount.
Preferably 6 is 0.7 to 10 mol. Examples of reaction solvents include ethers such as diethyl ether, tetrahydrofuran, and dioxane.
The compound represented by formula (1) can be produced in a reaction time of 0 minutes to 75 hours.
次に実施例をもって本発明？更に詳細に説明する。Next, the present invention with examples? This will be explained in more detail.
実施例
３−７リルチオー２−７エニルー／、、２゜ダートリア
ジン−５（コＨ）−オン７．００ｇ。Example 3-7 7.00 g of lilthio-2-7enyl/, 2° triazin-5(coH)-one.
塩化パラジウムベンゾニトリル錯体／Ｊｌｌｐおよびテ
トラヒドロフランＩＩ Ｏｍｌ ｆ混合し、１時間加熱
還流した。室温まで冷却後、溶媒を減圧留去した後の残
渣′Ｊｋｎ−ヘキサンーアセトン溶媒にてシリカゲルの
短いカラムにてカラムクロマトグラフィーを行った０得
られた溶出液を濃縮すると白色結晶が得られ、これをｎ
−ヘキサン−アセトン溶媒にて再結晶を行い、純粋なグ
ーアリル−６−フェニル−／。Palladium chloride benzonitrile complex/Jllp and tetrahydrofuran II Oml were mixed and heated under reflux for 1 hour. After cooling to room temperature, the solvent was distilled off under reduced pressure and the residue was subjected to column chromatography on a short column of silica gel using a hexane-acetone solvent.The resulting eluate was concentrated to give white crystals. This is n
- Recrystallization from hexane-acetone solvent yields pure guaryl-6-phenyl/.
コ、ｌｌ−トリアジン−ｊ（’、！Ｈ）−オン−３−チ
オンθ、７７ノを得た。（収率７７チ）融 点
／ｇ乙、？℃ （文＃値／ｇ７℃ ）元素分析値 ｃ（
＠ Ｈ（％） Ｎ’（＠Ｓ（％）計算値 ！；ｇ
、７Ｋ ４ＬＪ、２ ／７．／３ ／３．（１７
実測値 ５ｇ、Ｗ グ、’１３ ／７．０７７３．
０２次に、式（１）で示される化合物から前述の如く容
易に製造できる式（至）で示される化合物の除草効スに
ついて記載する。, 11-triazine-j(',!H)-one-3-thione θ, 77 was obtained. (Yield 77cm) Melting point
/g otsu,? ℃ (Text# value/g7℃) Elemental analysis value c(
@H(%) N'(@S(%) calculated value!;g
, 7K 4LJ, 2/7. /3 /3. (17
Actual value 5g, W gu, '13 /7.0773.
02 Next, the herbicidal effect of the compound represented by the formula (to) which can be easily produced as described above from the compound represented by the formula (1) will be described.
作物に対する薬害と雑草に対する効力は、調査時点に枯
れ残った植物体の地上部の乾燥重量と無処理区のそれと
の比率（＠を求め下表の区分に従ってθから５までの数
字で評価し、その評価値で示した０
参考例 畑地発芽前土壌処理試験
直径７９ｍ１高さ１０．の円筒プラスチックビーカーに
畑地土壌を詰め、トウモロコシ、ヒエ、７オビユおよび
スベリヒエを播種した。Efficacy against chemical damage to crops and weeds is evaluated by calculating the ratio (@) of the dry weight of the above-ground parts of the plants remaining withered at the time of the survey to that of the untreated area, and using numbers from θ to 5 according to the categories in the table below. The evaluation value was 0.Reference Example Pre-germination Soil Treatment Test for Upland Field Field soil was packed into a cylindrical plastic beaker with a diameter of 79 m and a height of 10 mm, and corn, Japanese barnyard grass, 7-year-old Japanese millet, and purslane were sown.
覆土後、弐ｍで示される化合物７０部、ポリオキシエチ
レンアルキルアリールエーテル７部、アルキルアリール
スルホン酸塩３部およびシクロへキサノンに０部をよく
混合して得た乳剤の所定量をハンドスブレヤーにて土壌
処理した。その後、温室内にて育成し、処理後−〇Ｆ１
目に除草効力を調査した。その結果を第１表に示す。After covering with soil, a predetermined amount of an emulsion obtained by thoroughly mixing 70 parts of the compound represented by 2m, 7 parts of polyoxyethylene alkylaryl ether, 3 parts of alkylaryl sulfonate, and 0 parts with cyclohexanone was added using a hand shaker. Soil treated. After that, it was grown in a greenhouse and after treatment -〇F1
The herbicidal efficacy was visually investigated. The results are shown in Table 1.
なお、供試乳剤は所定量を水で希釈し、／アール当りＳ
ｔ散布の割合で試験を行った。The sample emulsion was diluted with water in a predetermined amount, and
Tests were conducted at a rate of t sparging.
餓 ／ 表Hunger / table
Claims (1)
（■）化合物の存在下に転位反応を行わせることを特徴
と→−る式 で示されるグーフリル−２−フェニル−／、Ｊ。 ｑ−トリアジン−ｈ（、ｚＨ）−オン−３−チオンの製
造法[Claims] Goufuryl represented by the formula →-, characterized in that a rearrangement reaction is carried out with the formula % formula % co, q-triazine-”j(J) ion in the presence of a palladium (■) compound -2-phenyl-/, J. Method for producing q-triazine-h(,zH)-one-3-thione
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57132882A JPS5921673A (en) | 1982-07-28 | 1982-07-28 | Preparation of 4-allyl-6-phenyl-1,2,4-triazin-5(2h)-one-3- thione |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57132882A JPS5921673A (en) | 1982-07-28 | 1982-07-28 | Preparation of 4-allyl-6-phenyl-1,2,4-triazin-5(2h)-one-3- thione |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS5921673A true JPS5921673A (en) | 1984-02-03 |
Family
ID=15091760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57132882A Pending JPS5921673A (en) | 1982-07-28 | 1982-07-28 | Preparation of 4-allyl-6-phenyl-1,2,4-triazin-5(2h)-one-3- thione |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5921673A (en) |
-
1982
- 1982-07-28 JP JP57132882A patent/JPS5921673A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS59163372A (en) | Pyrazole derivative, its preparation and herbicide | |
| JPS62153273A (en) | Pyrazole compound | |
| JPS62126178A (en) | Novel triazine derivative and herbicide containing said derivative | |
| JPS61293956A (en) | Chloroacetamide compound and production thereof | |
| JPS5879964A (en) | Optically active n-(1'-methyl-2'-methoxyethyl)- n-chloroacetyl-2-ethyl-6-methylaniline, manufacture and herbicidal composition | |
| WO1994008988A1 (en) | Cyclohexanedione derivative | |
| JPS5921673A (en) | Preparation of 4-allyl-6-phenyl-1,2,4-triazin-5(2h)-one-3- thione | |
| JPS62153283A (en) | Pyrazole compound | |
| JPS5921672A (en) | 4-allyl-1,2,4-triazin-5(2h)-one-3-thione derivative and its preparation | |
| JPS62138475A (en) | Pyrazole compound | |
| JPH064602B2 (en) | 5-thioxo-2-imidazolinylbenzoic acid, ester, salt and related compounds, and herbicidal composition comprising them | |
| JPS60109563A (en) | Herbicide | |
| JPS62123145A (en) | 1,3-cyclohexanedione derivative and herbicide for paddy field containing said derivative as active component | |
| JPH02119A (en) | Lithium aluminum hydride based asymmetric reducing agent | |
| JPH01250363A (en) | 4-benzylaminopyrimidine derivative and herbicide | |
| JPS6317833B2 (en) | ||
| JPS62292783A (en) | Imidazopyrrolinedione derivative, production thereof and herbicide containing same as active ingredient | |
| JPS6011482A (en) | Thiadiazinone derivative and herbicide | |
| RU2038351C1 (en) | Benzene derivatives containing heterocycle, methods of their synthesis, and herbicide agent | |
| KR820001279B1 (en) | Process for preparation of imidazole carboxylic acids derivatives | |
| KR890004130B1 (en) | Process of preparing 1,2,4-triatol-3-carboxyamide compound | |
| JPS625944A (en) | N-acylamino acid derivative, production and use thereof | |
| JPS5973554A (en) | Acetamide derivative, its preparation, and herbicide containing it as active ingredient | |
| JPS61106543A (en) | N-substituted amine | |
| JPS6263572A (en) | Production of trifluoromethylpyridoxyphenoxypropionic acid or its derivative |