JPS6067472A - Tetrahydro-3-methyl-5-isopropyl-4h-1,3,5-oxadiazin-4-one - Google Patents
Tetrahydro-3-methyl-5-isopropyl-4h-1,3,5-oxadiazin-4-oneInfo
- Publication number
- JPS6067472A JPS6067472A JP58175833A JP17583383A JPS6067472A JP S6067472 A JPS6067472 A JP S6067472A JP 58175833 A JP58175833 A JP 58175833A JP 17583383 A JP17583383 A JP 17583383A JP S6067472 A JPS6067472 A JP S6067472A
- Authority
- JP
- Japan
- Prior art keywords
- methyl
- reaction
- compound
- added
- tetrahydro
- 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
- Inks, Pencil-Leads, Or Crayons (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は新規なオキサジアジン誘導体およＯ・その製法
Ｏこ関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel oxadiazine derivatives and methods for their preparation.
従来オキサジアジン誘導体は染色助剤等に有用であり、
種々の化合物か知られているが、２個のＮ−置換基がそ
れぞれ異なったアルキル基を有し、かつそのＮ−置換ア
ルキル基の少なくとも一個が分岐鎖を有する化合物は知
られていない。Conventionally, oxadiazine derivatives are useful as dyeing aids, etc.
Various compounds are known, but no compound is known in which the two N-substituents have different alkyl groups and at least one of the N-substituted alkyl groups has a branched chain.
本発明者らは種々のオキサジアジン誘導体の製法および
生成物の物性を検討するうち、２個のＮ−置換基がそれ
ぞれ異なったアルキル基を有し、かつそのＮ−置換アル
キル基の少なくとも一個が分岐鎖を有する化合物、就中
、テトラヒドロ−３−メチル−５−インブチル−４ｔＩ
−１，３，５−オキサジアジン−４−オンが常温で液
状であり、高い誘電率を有することから有機電解質、高
速インキジェット用媒体および特定電圧下での残留分極
を示すのでその分野での用途等に有用であることを見出
した。The present inventors investigated the production methods of various oxadiazine derivatives and the physical properties of the products, and found that two N-substituents each have different alkyl groups, and at least one of the N-substituted alkyl groups is branched. compounds having a chain, especially tetrahydro-3-methyl-5-inbutyl-4tI
-1,3,5-Oxadiazin-4-one is liquid at room temperature and has a high dielectric constant, making it useful as an organic electrolyte, medium for high-speed inkjet, and because it exhibits residual polarization under a specific voltage, it is used in these fields. We have found that it is useful for
即ち、本発明は式：
で示される化合物、即ちテトラヒドロ−３−メチル−５
−イソブチル−４Ｈ−１，３，５−オキサジアジン−４
−オンおよびその製法を提供する。That is, the present invention provides a compound represented by the formula: Tetrahydro-3-methyl-5
-isobutyl-4H-1,3,5-oxadiazine-4
-on and its manufacturing method.
一般的なオキサジアジン類の製造方法はＪ、Ｏｒｇ。A general method for producing oxadiazines is described by J. Org.
Ｃｈｅｍ、２８．．１８７６〜？ （１９６３）、Ｂｕ
ｌｌ、 Ｃｌｘｅｍ、 Ｓｏｃ、 Ｊａｐａｎ １１．
２４８〜２６１（１９３６）、Ｊ、Ｏｒｇ、 Ｃｈｅ
ｍ、 ２９．２７７７〜８ （１９６４）等に記載され
ている。しかしながら従来のジアルキル尿素とバラホル
ムアルデヒドを脱水縮合する反応（Ｊ、 Ｏｒｇ、 Ｃ
ｈｅｍ、 ２９゜２７７７〜８ （１９６４）では未反
応のジアルキル尿素が残存したりジアルキル尿素のジノ
チロール化物が残存する。また反応が完全に行なわれな
かったために生ずる種々の副生物等が生成し、これは蒸
溜等の通常の精製手段で分離除去することは困難である
。また前述の有機電解質として使用するにはかなりの高
純度の化合物が要請される。Chem, 28. ．． 1876~? (1963), Bu
ll, Clxem, Soc, Japan 11.
248-261 (1936), J, Org, Che
M, 29.2777-8 (1964), etc. However, the conventional dehydration condensation reaction of dialkylurea and paraformaldehyde (J, Org, C
hem, 29°2777-8 (1964), unreacted dialkylurea or dinotyrolated dialkylurea remains. Furthermore, various by-products are generated due to incomplete reaction, and these are difficult to separate and remove by ordinary purification means such as distillation. Further, use as the above-mentioned organic electrolyte requires a compound of considerably high purity.
本発明者らは上記の問題を解決するためジアルキル尿素
（本発明では１−メチル−３−イソブチル尿素を用いた
）とパラホルムアルデヒドとを酸触媒の存在下に反応さ
せてジメチロール化を完結させ、次いでベンゼン等の溶
剤を用いて水分を共沸により除去し、その後、更に脱水
剤を加えて脱水し、ジメチロール化尿素を完全に脱水環
化させることにより、高純度のオキサジアジン銹導体を
得ることに成功した。In order to solve the above problem, the present inventors completed dimethylolation by reacting dialkylurea (1-methyl-3-isobutyl urea was used in the present invention) and paraformaldehyde in the presence of an acid catalyst. Next, water is removed azeotropically using a solvent such as benzene, and then a dehydrating agent is added for dehydration to completely dehydrate and cyclize the dimethylolated urea, thereby obtaining a highly pure oxadiazine rust conductor. Successful.
即ち、本発明は１−メチル−３−イソブチル尿素とホル
ムアルデヒドを反応させて、１−メチル−３−イソブチ
ル尿素のジメチロール化物を得、これを脱水環化させる
ことを特徴とする式：で示されるテトラヒドロ−３−メ
チル−５−インブチル−４Ｈ−１，３，５−オキサジア
ジン−４−オンの製法を提供する。That is, the present invention is characterized by reacting 1-methyl-3-isobutylurea with formaldehyde to obtain a dimethylolated product of 1-methyl-3-isobutylurea, and cyclizing this by dehydration. A method for preparing tetrahydro-3-methyl-5-ynbutyl-4H-1,3,5-oxadiazin-4-one is provided.
１−メチル−３−インブチル尿素とホルムアルデヒドの
反応は１−メチル−３−イソブチル尿素を通常ホルムア
ルデヒド水溶液、例えば３５％水溶液に溶解し、酸性触
媒、例えば、塩酸、硫酸、リン酸、パラトルエンスルホ
ン酸、及び／アルいはこれらの酸性塩等を加え、室温で
１〜３時間攪拌することにより行う。この反応により１
−メチル−３−イソブチル尿素のジメチロール化物が得
られる。ホルムアルデヒドは１−メチル−３−イソブチ
ル尿素１モルに対してモル以上、好ましくは２．０５〜
２．５モル用いる。酸性触媒は原料尿素化合物の０．５
重量％程度用いる。反応が完了した後、例えばベンゼン
、トルエン、キシレン等の共沸溶剤を反応生成物全量の
約１〜２倍加え、加熱共沸により、水分のほぼ全量を除
去する。最後に反応を完全にするためにジメチロール化
物の共沸溶剤溶液に適当な脱水剤、例えばＰ２Ｏ５、無
水硼酸等をジメチロール化物１００重量部に対し、５〜
１０重量部加え還流加熱する。脱水剤は適当な手段、例
えば一過、遠心分離等により除去し、共沸溶剤を溜去す
ることにより、本発明化合物を得ることができる。The reaction between 1-methyl-3-imbutyl urea and formaldehyde is carried out by dissolving 1-methyl-3-isobutyl urea in an aqueous formaldehyde solution, for example a 35% aqueous solution, and using an acidic catalyst such as hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid. , and/or an acid salt thereof, and stirred at room temperature for 1 to 3 hours. This reaction results in 1
- A dimethylolated product of methyl-3-isobutyl urea is obtained. Formaldehyde is at least mol per 1 mol of 1-methyl-3-isobutyl urea, preferably from 2.05 to 1 mol.
2.5 mol is used. The acidic catalyst is 0.5 of the raw material urea compound.
Approximately % by weight is used. After the reaction is completed, an azeotropic solvent such as benzene, toluene, xylene, etc. is added in an amount of about 1 to 2 times the total amount of the reaction product, and almost the entire amount of water is removed by heating azeotropically. Finally, in order to complete the reaction, a suitable dehydrating agent such as P2O5, boric anhydride, etc.
Add 10 parts by weight and heat under reflux. The compound of the present invention can be obtained by removing the dehydrating agent by an appropriate means such as filtration or centrifugation, and distilling off the azeotropic solvent.
本発明化合物は水に可溶性の液状化合物であり、九Ｅｑ
淀気佼ｎ）すい 株１市 ）−１て ズテへ省？仏７ノ
后テ １「：市 ノ ・ツキジェット用媒体、可溶化剤
、反応媒体、その他、機能流体として種々の分野に使用
できる。The compound of the present invention is a liquid compound soluble in water, and has a concentration of 9 Eq.
Yodokika n) Sui Kabu 1 City ) -1 Te Zutehe Ministry? It can be used in various fields as a jet medium, solubilizer, reaction medium, and other functional fluids.
また本発明方法によれば副反応が少なく、簡単な操作で
純度の高い化合物を高収率で得ることができる。Furthermore, according to the method of the present invention, there are few side reactions, and a highly pure compound can be obtained in high yield with simple operations.
以下、実施例をあげて説明する。Examples will be described below.
実施例
１−メチル−３−インブチル尿素１３０ｇ（１モル）を
３５％ホルマリン溶液１８８ｇ（２，２モル）に溶解し
、これに濃塩酸０．５−を添加し、室温で１時間攪拌す
る。原料尿素の消失をＴＬＣで確認後、これにベンゼン
２００ｒｎｌを加え、デイーンスタークの蒸溜器を付し
、生成水分および原料ホルマリン溶液の水分を共沸によ
り糸外に除去する。水分をほぼ除去した後、五酸化りん
約２０ｇを添加し、１時間還流加熱し、環化反応を完結
させる。ＧＬＣによりジメチロール化物の消失を確認後
、反応液を冷却し、次いで五酸化りんを一過により除き
、無水炭酸カリで中和する。更に硫酸マグネシウムで斂
怪］７−那過傍ベンゼンを溜去し−残溜物から９５℃（
０，８＋＋＋ｍＨｇ）溜分を採取した。Example 1 - 130 g (1 mol) of methyl-3-imbutyl urea is dissolved in 188 g (2.2 mol) of a 35% formalin solution, 0.5 g of concentrated hydrochloric acid is added thereto, and the mixture is stirred at room temperature for 1 hour. After confirming the disappearance of the raw material urea by TLC, 200 rnl of benzene was added thereto, and a Dean Stark distiller was attached to remove the produced water and the water of the raw material formalin solution to the outside of the thread by azeotropy. After almost all moisture has been removed, about 20 g of phosphorus pentoxide is added and heated under reflux for 1 hour to complete the cyclization reaction. After confirming the disappearance of the dimethylol compound by GLC, the reaction solution is cooled, and then phosphorus pentoxide is removed by passing and neutralized with anhydrous potassium carbonate. Furthermore, the benzene was distilled off with magnesium sulfate] and the residue was heated at 95°C (
0.8 +++ mHg) fraction was collected.
収量１６７ｇ（収率９７．１％）であった。The yield was 167 g (yield 97.1%).
生成物の物理特数を表−１に、ガスクロマトグラム、赤
外吸収スペクトルおよびＮ’ Ｍ Ｒのチャー１・（基
準ＴＭＳ、溶媒ＣＣＩ！４、濃度〜１５％）をそれぞれ
第１図、第２図および第３図に示す。The physical properties of the product are shown in Table 1, and the gas chromatogram, infrared absorption spectrum, and N'MR Char 1 (standard TMS, solvent CCI!4, concentration ~15%) are shown in Figures 1 and 2, respectively. As shown in FIG.
ガスクロマトグラフィーの測定条件は以下の通りである
。The measurement conditions for gas chromatography are as follows.
検出器： ＦＩＤ
カラム： ステンレス製、長さ１ｍ、充填剤Ｓ１亡−３
０
キャリヤーガス ： Ｎ２： ０．８に９／ｃｎインジ
工クンヨン温度：２２０°Ｃ
展１）口温度 ＝１６０°Ｃ
チャート送り速度 ＝５叫／分
表−１Detector: FID Column: Stainless steel, length 1m, packing material S1-3
0 Carrier gas: N2: 0.8 to 9/cn Injection temperature: 220°C 1) Mouth temperature = 160°C Chart feed rate = 5/min Table-1
第１図は本発明化合物のガスクロマトグラム、第２図は
本発明化合物の赤外分光分析チャー１・、第３図は本発
明化合物のＮＭＲチャート、をそれぞれ示す。
第１図FIG. 1 shows a gas chromatogram of the compound of the present invention, FIG. 2 shows an infrared spectroscopy chart 1 of the compound of the present invention, and FIG. 3 shows an NMR chart of the compound of the present invention. Figure 1
Claims (1)
−４Ｈ−１，３，５−オキサジアジン−４−オン。[Claims] 1. Tetrahydro-3-methyl-5-isobutyl-4H-1,3,5-oxadiazin-4-one represented by the formula 0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58175833A JPS6067472A (en) | 1983-09-22 | 1983-09-22 | Tetrahydro-3-methyl-5-isopropyl-4h-1,3,5-oxadiazin-4-one |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58175833A JPS6067472A (en) | 1983-09-22 | 1983-09-22 | Tetrahydro-3-methyl-5-isopropyl-4h-1,3,5-oxadiazin-4-one |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6067472A true JPS6067472A (en) | 1985-04-17 |
Family
ID=16003010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58175833A Pending JPS6067472A (en) | 1983-09-22 | 1983-09-22 | Tetrahydro-3-methyl-5-isopropyl-4h-1,3,5-oxadiazin-4-one |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6067472A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5792064A (en) * | 1980-11-28 | 1982-06-08 | Fuji Photo Film Co Ltd | Aqueous ink for ink jet print |
-
1983
- 1983-09-22 JP JP58175833A patent/JPS6067472A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5792064A (en) * | 1980-11-28 | 1982-06-08 | Fuji Photo Film Co Ltd | Aqueous ink for ink jet print |
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