JPS6021985B2 - Method for producing 2-amino-1,3-oxazin-4-one derivative - Google Patents
Method for producing 2-amino-1,3-oxazin-4-one derivativeInfo
- Publication number
- JPS6021985B2 JPS6021985B2 JP4676583A JP4676583A JPS6021985B2 JP S6021985 B2 JPS6021985 B2 JP S6021985B2 JP 4676583 A JP4676583 A JP 4676583A JP 4676583 A JP4676583 A JP 4676583A JP S6021985 B2 JPS6021985 B2 JP S6021985B2
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- group
- oxazin
- substituted
- aryl
- 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.)
- Expired
Links
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Description
【発明の詳細な説明】
本発明は２一置換ァミノ−４・５一檀湊−１・３ーオキ
サジンー４ーオン誘導体（一般式瓜、式中Ｒ，，Ｒ２は
水素、アルキル、アリール、又はアラルキル基を、Ｘは
アルキル（又はアリール）アミノ基を意味する）の製造
法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to 2-substituted amino-4,5-danminato-1,3-oxazin-4-one derivatives (general formula: R, , R2 are hydrogen, alkyl, aryl, or aralkyl groups). , X means an alkyl (or aryl) amino group).
しかしてその意図するところは、医薬品、農薬又はそれ
らの中間体として価値ある題記化合物を経済的に有利に
製造することにある。２−アミノー１・３ーオキサジン
ー４ーオン謎導体の製造に関しては「ジケテンとカルボ
ジィミドの反応（Ｒ．Ｎ．Ｌａｃｅｙ、ｅｔａｌ．、Ｊ
．Ｃｈｅｍ．ＳＣｏ．、１９５〆 ２１払）、ジケテン
とシアナミドとの反応（Ｒ．■ｍｐｅｒｅｔａｌ．、Ｔ
ｅひａｈｅｄｒｏｎＬｅＵ．、１９７３、２斑；Ｔ．Ｋ
ａｔｏ ｅｔ ａｌ、Ｃｈｅｍ．Ｐｈａｒｍ．Ｂｕｌｌ
．、２９、８６２（１鯛１））、またジケテンーアセト
ン付加体とシァナミドとの反応（Ｇ．Ｊａ鉾ｒｅｔａｌ
．、飢ｎＣｈｅｍ．、１９７０１６８９）による方法が
報告されている。The intention is to economically advantageously produce the title compound, which is valuable as a pharmaceutical, agrochemical, or an intermediate thereof. Regarding the production of the 2-amino-1,3-oxazine-4-one mysterious conductor, see ``Reaction of diketene and carbodimide (RN. Lacey, et al., J.
．． Chem. SCo. , 195〆 21 pay), Reaction of diketene with cyanamide (R.■mperetal., T
ehiahedronLeU. , 1973, 2 spots; T. K
ato et al., Chem. Pharm. Bull
．． , 29, 862 (1)), and the reaction of diketene-acetone adduct with cyanamide (G. Jahoko retal.
．． , StarvationChem. , 19701689) has been reported.
さらに富田らは、４・５−置換−３ーヒドロキシーィソ
キサゾールとホルムアミドより誘導されるビルスマィャ
ー試薬とを反応せしめ５・６一位にメチル、フェニル、
ハロゲンなどの導入された２ーアミノ−１・３−オキサ
ジン誘導体（ｍ）を製造している（富田他、特許公報
昭５２一２０５０４（１９７９））。これらの中、前三
法は収率、操作の面で有利なものではあるが、オキサジ
ン骨核形成にジケテンが関与するために、製造される１
・３ーオキサジンの５、６位直換基が制限される（一般
的ｍ中Ｒ，はメチル基、Ｒ２は水素）。Furthermore, Tomita et al. reacted 4,5-substituted-3-hydroxyisoxazole with a Vilsmeyer reagent derived from formamide to create methyl, phenyl,
We manufacture 2-amino-1,3-oxazine derivatives (m) into which halogen etc. are introduced (Tomita et al., patent publication
Showa 52-20504 (1979)). Among these, the first three methods are advantageous in terms of yield and operation, but because diketene is involved in oxazine bone nucleation, the production of 1
- Direct substituents at the 5 and 6 positions of 3-oxazine are restricted (generally R in m is a methyl group and R2 is hydrogen).
また冨田らの方法はＲ，、Ｒ２の選択は可能であり、一
般製造法となり得るが、原料インキサゾールの製造は必
ずしも客易とは言い得ない。これに対し、本発明は任意
の８ーケト酸（又はェステル）を出発原料とする、５・
６−置換一２・２−ジメチルー１・３ージオキシンー４
ーオン（一般式１、式中Ｒ，、Ｒ２は水素、アルキル、
アリール、又はアラルキル基を意味する）を用いるため
、５、６位により自由に任意の置換基を導入することが
出来、技も優れた方法と言える。Further, although the method of Tomita et al. allows selection of R, R2 and can be a general production method, the production of the raw material inxazole cannot necessarily be said to be easy. On the other hand, the present invention uses any 8-keto acid (or ester) as a starting material.
6-substituted-2,2-dimethyl-1,3-dioxin-4
-one (general formula 1, in which R, R2 is hydrogen, alkyl,
Since this method uses an aryl or aralkyl group, it is possible to freely introduce any substituents at the 5th and 6th positions, and the technique can be said to be excellent.
本発明に用いる１・３−ジオキシンー４−オン（一般式
１）は前述のように、任意８−ケト酸又はそのェステル
をアセトンと反応させ容易に縛られるが、置換シアナミ
ド（一般式０）も市販品、あるいは臭化シアンと第一ア
ミン又は第二アミンとより容易に製造される。さらに反
応操作は容易であり、収率も良好である。すなわち１・
３ージオキシン（１）に対してシアナミド（Ｖ）を１．
２５当量混じ、１３び乃至１６５０に加熱すればよい。
加熱時間は３０分乃至１時間で充分であり、また溶媒で
充分であり、また溶媒を用いる必要もない。一般にモノ
置換一１・３−ジオキサン（１）の場合、低温、短時間
で反応が進行する。後処理も常法の処理でよい。たとえ
ば、反応後、結晶性のものは再結晶により容易に純品が
得られる。結晶し難いものはカラムクロマトグラフィー
により、納品を得ることが出来る。以上本発明は題記化
合物の製造法として、製造の一般性、原料入手の容易さ
、操作の簡易な点、従来法に比し最も優れたものと言え
よう。As mentioned above, 1,3-dioxin-4-one (general formula 1) used in the present invention can be easily bound by reacting any 8-keto acid or its ester with acetone, but substituted cyanamide (general formula 0) can also be bound. It is commercially available or more easily prepared with cyanogen bromide and primary or secondary amines. Furthermore, the reaction operation is easy and the yield is good. That is, 1.
1. Cyanamide (V) was added to 3-dioxin (1).
It is sufficient to mix 25 equivalents and heat to 13 to 1650 ℃.
A heating time of 30 minutes to 1 hour is sufficient, and a solvent is sufficient, and there is no need to use a solvent. Generally, in the case of monosubstituted 1,3-dioxane (1), the reaction proceeds at low temperature and in a short time. Post-processing may also be carried out by conventional methods. For example, after the reaction, a crystalline product can be easily obtained as a pure product by recrystallization. Products that are difficult to crystallize can be obtained by column chromatography. As described above, the present invention can be said to be the most superior method for producing the title compound compared to conventional methods in terms of generality of production, ease of obtaining raw materials, and simple operation.
次に実施例を挙げて本発明を詳細に説明する。Next, the present invention will be explained in detail with reference to Examples.
実施例 １２−ジエチルアミノー６−エチル−１・３ー
オキサジンー４−オン（ｍｍ：一般式ｍ、式中Ｒ，はエ
チル基、Ｒ２は水素、×はジェチルアミノ基を意味する
）２・２ージメチル−６ーエチルー１・３ージオキシン
ー４ーオソ（一般式１、式中Ｒ，はエチル基、Ｒ２は水
素を意味する）（０．６３夕、４ミリモル）とＮ・Ｎ−
ジェチルシアナミド（一般式ロ、式中Ｘはジェチルアミ
ノ基を意味する）（０．５夕、５ミリモル）を１３０ｏ
で３０分加熱する。Example 12-diethylamino-6-ethyl-1,3-oxazin-4-one (mm: general formula m, where R is an ethyl group, R2 is hydrogen, and x means a dietylamino group) 2,2-dimethyl-6 -ethyl-1,3-dioxin-4-otho (general formula 1, in which R means ethyl group, R2 means hydrogen) (0.63 mmol, 4 mmol) and N.N-
Diethyl cyanamide (general formula 2, in which X means a diethylamino group) (0.5 mmol, 5 mmol) at 130°C
Heat for 30 minutes.
冷後反応物をアルミナ（２２夕）力ラムクロマトグラフ
ィ−に付す。エーテル−酢酸エチル（３：２）溶出部分
より油状物質を得る。収量０．６５夕（８３％）。元素
分析値 計算値（Ｃ，虹．６Ｎ２０２）：Ｃ、６１．２
０；日、８２２：Ｎ、１４．２８実測値；Ｃ、６０．班
：日、８．５１；Ｎ、１３．９９．赤外吸収スペクトル
（ＣＨＣ１３）仇‐１：１６７２、１６５７：（ｓｈ）
、１５６０、１５４２（ｓｈ）．ＮＭＲ（ＣＤＣ１３）
跡：１．２３（班、ｔ、Ｊ＝７，４ＨＺ）、２．４６（
が、ｑ、Ｊ＝７，４ＨＺ）、３．５３（』日、ｑ、Ｊ＝
７．４ＨＺ）、５．７３（ＩＨ、ｓ）．実施例 ２
２ージエチルアミノー５ーメチル−６−フエニルー１・
３ーオキサジン−４ーオン（ｍｐ、一般式ｍ、式中Ｒ，
はフェニル、Ｒ２はメチル基、Ｘはジェチルアミノ基を
意味する）２・２・５ートリメチルー６ーフエニルー１
．３ージオキシンー４−オン（一般式１、式中Ｒ，はフ
ェニル基を、Ｒ２はメチル基を意味する）（０．４４夕
、２ミリモル）とＮ・Ｎージエチルシアナミド（０、式
中×はジェチルアミノ基を意味する）（０．２５夕、２
．５ミリモル）の混合物を１６５０で１時間加熱する。After cooling, the reaction product was subjected to column chromatography on alumina (22mm). An oily substance was obtained from the ether-ethyl acetate (3:2) eluate. Yield: 0.65 yen (83%). Elemental analysis value Calculated value (C, Rainbow.6N202): C, 61.2
0: day, 822: N, 14.28 actual value; C, 60. Group: Sun, 8.51; N, 13.99. Infrared absorption spectrum (CHC13) -1:1672, 1657: (sh)
, 1560, 1542 (sh). NMR (CDC13)
Trace: 1.23 (group, t, J = 7,4HZ), 2.46 (
is, q, J=7,4HZ), 3.53('' day, q, J=
7.4HZ), 5.73 (IH, s). Example 2 2-diethylamino-5-methyl-6-phenyl-1.
3-oxazin-4-one (mp, general formula m, in the formula R,
means phenyl, R2 means methyl group, and X means jetylamino group) 2,2,5-trimethyl-6-phenyl-1
．． 3-dioxin-4-one (general formula 1, where R means a phenyl group and R2 means a methyl group) (0.44 mmol, 2 mmol) and N.N-diethyl cyanamide (0, where x means a methyl group) (means jethylamino group) (0.25 min, 2
．． 5 mmol) is heated at 1650 for 1 hour.
冷後反応物をシリカゲル（１２夕）カラムクロマトグラ
フイーに付す。エーテル−酢酸エチル（２：１）溶出分
より油状物を得る。ｂｐｏ．００５肌Ｈｇ１７００、０
．３６夕（７０％）。元素分析値計算値（Ｃ，迅，８Ｎ
２０２）：Ｃ、６９．７４；日、７．０２；Ｎ、１０．
８５．実測値：Ｃ、７０．２４：日、７．２１：Ｎ、１
０．７７．赤外吸収スペクトル（ＣＨＣ１３）弧‐１：
１６４６、１５６１．ＮＭＲ（ＣＤＣ１３）胸：１．２
６（細、ｔ）、２．０９（祖、ｓ）、３．５７（４日、
ｑ）、７．５２（斑、ｓ）．以上の実施例に従い、５・
６一置換−２・２ージメチルー１・３ージオキシン−４
ーオン（１）とジメチルおよびジェチルシアナミド（ロ
、式中Ｘはジメチルアミノおよびジチルアミノ基を意味
する）とを反応させ得られたオキサジンｍの収率、融点
を表に示す。なお、これらの元素分析、赤外および核磁
気共鳴スペクトルは構造を支持している。またｍａ、ｄ
および１以外は新規の化合物である。夫（文献融点）冨
田他 特許公報
昭３２一２０５０４（１９７９）After cooling, the reaction product was subjected to silica gel (12 days) column chromatography. An oily substance was obtained from the ether-ethyl acetate (2:1) eluate. bpo. 005 Skin Hg1700,0
．． 36th evening (70%). Elemental analysis value calculation value (C, speed, 8N
202): C, 69.74; Sun, 7.02; N, 10.
85. Actual value: C, 70.24: day, 7.21: N, 1
0.77. Infrared absorption spectrum (CHC13) arc-1:
1646, 1561. NMR (CDC13) Chest: 1.2
6 (thin, t), 2.09 (so, s), 3.57 (4th,
q), 7.52 (spots, s). According to the above example, 5.
6-monosubstituted-2,2-dimethyl-1,3-dioxin-4
The yield and melting point of oxazine m obtained by reacting -one (1) with dimethyl and diethyl cyanamide (in the formula, X means dimethylamino and dithylamino groups) are shown in the table. Furthermore, these elemental analyzes and infrared and nuclear magnetic resonance spectra support the structure. Also ma, d
The compounds other than 1 and 1 are new compounds. Husband (Reference Melting Point) Tomita et al. Patent Publication 1979-20504 (1979)
Claims (1)
シン−４−オン（下記一般式I、式号Ｒ＿１およびＲ＿
２は水素、アルキル、アリール、またはアラルキル基を
意味する）と置換シアナミド（下記一般式II、式中Ｘは
アルキル又はアリール置換アミノ基を意味する）とを反
応せしめることを特徴とする２−アミノ−５・６−置換
−１・３−オキサジン−４−オン誘導体（下記一般式I
II、式中Ｒ＿１、Ｒ＿２は水素、アルキル、アリール、
またはアラルキル基を、Ｘはアルキル又はアリール置換
アミノ基を意味する）の製造法。 ▲数式、化学式、表等があります▼[Scope of Claims] 1 5,6-substituted-2,2-dimethyl-1,3-dioxin-4-one (the following general formula I, formulas R_1 and R_
2 means a hydrogen, alkyl, aryl, or aralkyl group) and a substituted cyanamide (the following general formula II, in which X means an alkyl or aryl substituted amino group) are reacted. -5,6-substituted-1,3-oxazin-4-one derivatives (general formula I below)
II, where R_1 and R_2 are hydrogen, alkyl, aryl,
or an aralkyl group, X means an alkyl- or aryl-substituted amino group). ▲Contains mathematical formulas, chemical formulas, tables, etc.▼
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4676583A JPS6021985B2 (en) | 1983-03-18 | 1983-03-18 | Method for producing 2-amino-1,3-oxazin-4-one derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4676583A JPS6021985B2 (en) | 1983-03-18 | 1983-03-18 | Method for producing 2-amino-1,3-oxazin-4-one derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59172482A JPS59172482A (en) | 1984-09-29 |
| JPS6021985B2 true JPS6021985B2 (en) | 1985-05-30 |
Family
ID=12756421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4676583A Expired JPS6021985B2 (en) | 1983-03-18 | 1983-03-18 | Method for producing 2-amino-1,3-oxazin-4-one derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6021985B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2144455T3 (en) * | 1992-01-30 | 2000-06-16 | Mitsubishi Chem Corp | DERIVED FROM 1,3-OXAZIN-4-ONA, HERBICIDE CONTAINING IT, AND NEW INTERMEDIATE TO PRODUCE IT. |
-
1983
- 1983-03-18 JP JP4676583A patent/JPS6021985B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59172482A (en) | 1984-09-29 |
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