JPS6230188B2 - - Google Patents
Info
- Publication number
- JPS6230188B2 JPS6230188B2 JP7511178A JP7511178A JPS6230188B2 JP S6230188 B2 JPS6230188 B2 JP S6230188B2 JP 7511178 A JP7511178 A JP 7511178A JP 7511178 A JP7511178 A JP 7511178A JP S6230188 B2 JPS6230188 B2 JP S6230188B2
- Authority
- JP
- Japan
- Prior art keywords
- methylbenzothiazolone
- tetra
- mol
- butylammonium
- formula
- 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
- OJKLTHIQRARJCE-UHFFFAOYSA-N 2-methoxy-1,3-benzothiazole Chemical class C1=CC=C2SC(OC)=NC2=C1 OJKLTHIQRARJCE-UHFFFAOYSA-N 0.000 claims description 5
- XSRCFFDUTPZZHD-UHFFFAOYSA-N 3-methyl-2h-1,3-benzothiazole 1-oxide Chemical class C1=CC=C2N(C)CS(=O)C2=C1 XSRCFFDUTPZZHD-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 5
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XQWPDHWIZIUXDD-UHFFFAOYSA-N 4-chloro-2-methoxy-1,3-benzothiazole Chemical compound C1=CC=C2SC(OC)=NC2=C1Cl XQWPDHWIZIUXDD-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000008707 rearrangement Effects 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- -1 Furthermore Chemical compound 0.000 description 2
- AWIVZNKPSYRYGJ-UHFFFAOYSA-N 2-methyl-1,3-benzothiazole 1-oxide Chemical compound C1=CC=C2S(=O)C(C)=NC2=C1 AWIVZNKPSYRYGJ-UHFFFAOYSA-N 0.000 description 2
- XWSYNAXBWICDFH-UHFFFAOYSA-N 4-chloro-3-methyl-2h-1,3-benzothiazole 1-oxide Chemical compound C1=CC(Cl)=C2N(C)CS(=O)C2=C1 XWSYNAXBWICDFH-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical compound CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- IHDKBHLTKNUCCW-UHFFFAOYSA-N 1,3-thiazole 1-oxide Chemical class O=S1C=CN=C1 IHDKBHLTKNUCCW-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 description 1
- JWLJBISFJGEYMT-UHFFFAOYSA-M benzyl(triethyl)azanium;iodide Chemical compound [I-].CC[N+](CC)(CC)CC1=CC=CC=C1 JWLJBISFJGEYMT-UHFFFAOYSA-M 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- DVBJBNKEBPCGSY-UHFFFAOYSA-M cetylpyridinium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 DVBJBNKEBPCGSY-UHFFFAOYSA-M 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 description 1
Landscapes
- Thiazole And Isothizaole Compounds (AREA)
Description
本発明は、一般式（）
で表わされる２−メトキシベンゾチアゾール誘導
体を熱転位させて、一般式（）
で表わされるＮ−メチルベンゾチアゾロン誘導体
を製造する方法において、転位を四級アンモニウ
ム塩の存在下に行なうことを特徴とするＮ−メチ
ルベンゾチアゾロン誘導体の製造方法である。
（上記一般式（）、（）において、Ｒは水素
原子、ハロゲン原子または低級アルキル基を意味
する。）
従来、２−メトキシベンゾチアゾールを経るＮ
−メチルベンゾチアゾロンの製法としては、W.
H.Davis et al、J.Chem.Soc.、P304（1942）に
示されるごとく、無溶媒にて高温、長時間加熱し
てＮ−メチルベンゾチアゾロンを得る方法が知ら
れているにすぎず、触媒に関してはヨウ素で試み
ているが効果なしとの記述がある。
前記の従来法では、転位に際して高温で、長時
間の加熱を必要とし、その反応収率のみならず安
全性ならびにエネルギー多消費である点で工業的
規模で実施するには、少なからず困難を有してい
た。
本発明者らは、上記の欠点を克服すべく研究を
重ねた結果、四級アンモニウム塩の存在下に転位
を行なわせることにより、非常に緩和な条件下で
容易に目的とするＮ−メチルベンゾチアゾロン誘
導体をほぼ定量的に得ることができることを見出
し、本発明を完成するに至つたのである。
以下に本発明の実施態様を述べ、さらに詳しく
説明する。
本発明に必須の四級アンモニウム塩としては、
任意のものを使用することができるが、テトラ−
ｎ−ブチルアンモニウムブロミド、テトラ−ｎ−
ブチルアンモニウムクロリド、テトラ−ｎ−ブチ
ルアンモニウムヨージド、テトラ−ｎ−ブチルア
ンモニウムヒドロキシド、トリエチルベンジルア
ンモニウムクロリド、トリエチルベンジルアンモ
ニウムブロミド、トリエチルベンジルアンモニウ
ムヨージド、トリメチルベンジルアンモニウムク
ロリド、ｎ−セチルピリジニウムプロミド、テト
ラ−ｎ−ブチルアンモニウムハイドロジエンサル
フエート、テトラ−ｎ−ブチルアンモニウムパー
クロレート等を例示することができる。
使用される四級アンモニウム塩の量は、反応基
質である２−メトキシベンゾチアゾールに対して
広い範囲において任意であり、同一温度条件下で
は添加量の多い程反応速度的に有利であるが、実
用上は該チアゾール１モルに対して1/1000〜1/10
モル程度、殊に1/1000〜1/100モル程度の使用で
充分効果が認められる（第１表参照）。
反応は、有機溶媒の存在下、非存在下どちらで
も実施可能である。有機溶媒としては非プロトン
性有機溶媒を用いることができ、好適な溶媒とし
ては原料である２−メトキシベゾチアゾールの溶
解度の高いトルエン、ｏ−、ｍ−およびｐ−キシ
レン等芳香族炭化水素類ならびにモノクロルベン
ゼン、ジクロルベンゼン等の塩素化炭化水素類を
例示することができる。
また、反応温度は溶媒の非存在下では生成物で
あるＮ−メチルベンゾチアゾロン類の融点以上任
意であり、通常は融点より５〜10℃高めの温度
で、また溶媒の存在下では、溶媒の還流温度近傍
でと緩和な条件下で実施される。
本発明で得られるＮ−メチルベンゾチアゾロン
誘導体は、農薬、医薬などとして有用な化合物で
ある。
以下に本発明化合物の具体的の若干をあげる。
The present invention is based on the general formula () By thermally rearranging the 2-methoxybenzothiazole derivative represented by the general formula () This is a method for producing an N-methylbenzothiazolone derivative represented by the formula, characterized in that the rearrangement is carried out in the presence of a quaternary ammonium salt. (In the above general formulas () and (), R means a hydrogen atom, a halogen atom, or a lower alkyl group.) Conventionally, N via 2-methoxybenzothiazole
-The method for producing methylbenzothiazolone is W.
As shown in H. Davis et al, J.Chem.Soc., P304 (1942), the only known method is to obtain N-methylbenzothiazolone by heating at high temperature and for a long time without a solvent. There is a statement that iodine has been tried as a catalyst, but it has no effect. The conventional method described above requires heating at high temperatures and for a long time during rearrangement, and it is difficult to carry out on an industrial scale not only because of the reaction yield but also because of safety and high energy consumption. Was. As a result of repeated research in order to overcome the above-mentioned drawbacks, the present inventors have found that the desired N-methylbenzoyl chloride can be easily obtained under very mild conditions by carrying out the rearrangement in the presence of a quaternary ammonium salt. They discovered that thiazolone derivatives can be obtained almost quantitatively, leading to the completion of the present invention. Embodiments of the present invention will be described below and explained in more detail. Quaternary ammonium salts essential to the present invention include:
Any one can be used, but tetra-
n-butylammonium bromide, tetra-n-
Butylammonium chloride, tetra-n-butylammonium iodide, tetra-n-butylammonium hydroxide, triethylbenzylammonium chloride, triethylbenzylammonium bromide, triethylbenzylammonium iodide, trimethylbenzylammonium chloride, n-cetylpyridinium bromide, Examples include tetra-n-butylammonium hydrogen sulfate and tetra-n-butylammonium perchlorate. The amount of the quaternary ammonium salt to be used is arbitrary within a wide range relative to the reaction substrate 2-methoxybenzothiazole, and under the same temperature conditions, the larger the amount added, the more advantageous the reaction rate is. The above is 1/1000 to 1/10 per mole of the thiazole.
Sufficient effects are observed when used in a molar amount, particularly in a range of 1/1000 to 1/100 molar (see Table 1). The reaction can be carried out either in the presence or absence of an organic solvent. As the organic solvent, an aprotic organic solvent can be used, and suitable solvents include aromatic hydrocarbons such as toluene, o-, m-, and p-xylene in which the raw material 2-methoxybezothiazole has high solubility. Also, chlorinated hydrocarbons such as monochlorobenzene and dichlorobenzene can be exemplified. In the absence of a solvent, the reaction temperature can be any value higher than the melting point of the product N-methylbenzothiazolones, and is usually 5 to 10°C higher than the melting point. The test is carried out under mild conditions near the reflux temperature. The N-methylbenzothiazolone derivatives obtained in the present invention are useful compounds as agricultural chemicals, medicines, and the like. Some specific examples of the compounds of the present invention are listed below.
【表】
限定されるものではない。
実施例 １
２−メトキシベンゾチアゾール2.00ｇ
（0.012mol）にテトラ−ｎ−ブチルアンモニウム
プロミド24mg（７×10-5mol）を加え、120℃、
２時間30分加熱撹拌する。冷却後、クロロホルム
に溶解させ、クロロホルム層を水洗して減圧下溶
媒を留去して融点73〜75℃の白色結晶としてＮ−
メチルベンゾチアゾロン1.85ｇを得た。収率92.5
％、純度96.0％
実施例 ２
２−メトキシ−４−クロロベンゾチアゾール
4.00ｇ（0.02mol）をトルエン８ｇに溶解させ、
さらにトリエチルベンジルアンモニウムクロリド
230mg（0.001mol）を加え、還流下、５時間撹拌
する。冷却後、トルエン層を水洗して減圧下溶媒
を留去して融点130〜132℃の白色結晶として４−
クロロ−Ｎ−メチルベンゾチアゾロン3.90ｇを得
た。収率97.5％、純度99.1％
実施例 ３
２−メトキシ−４−クロロベンゾチアゾール
5.00ｇ（0.025mol）にテトラ−ｎ−ブチルアンモ
ニウムプロミド162mg）（５×10-4mol）を加え、
140℃で10分間加熱撹拌する。冷却した後、クロ
ロホルムに溶解させ、クロロホルム層を水洗し減
圧下溶媒を留去して融点130〜132℃の白色結晶と
して４−クロロ−Ｎ−メチルベンゾチアゾロン
4.88ｇを得た。収率97.6％、純度98.8％
実施例 ４〜９
実施例３と同様にして、触媒の種類もしくは添
加量の一方または双方を変化させた結果を第１表
に示した。[Table] Not limited. Example 1 2-methoxybenzothiazole 2.00g
(0.012 mol) was added with 24 mg (7×10 -5 mol) of tetra-n-butylammonium bromide, and heated at 120°C.
Heat and stir for 2 hours and 30 minutes. After cooling, it was dissolved in chloroform, the chloroform layer was washed with water, and the solvent was distilled off under reduced pressure to obtain N- as white crystals with a melting point of 73-75°C.
1.85 g of methylbenzothiazolone was obtained. Yield 92.5
%, purity 96.0% Example 2 2-methoxy-4-chlorobenzothiazole
Dissolve 4.00g (0.02mol) in 8g of toluene,
Furthermore, triethylbenzylammonium chloride
Add 230 mg (0.001 mol) and stir under reflux for 5 hours. After cooling, the toluene layer was washed with water and the solvent was distilled off under reduced pressure to obtain 4-
3.90 g of chloro-N-methylbenzothiazolone was obtained. Yield 97.5%, purity 99.1% Example 3 2-methoxy-4-chlorobenzothiazole
Add 162 mg of tetra-n-butylammonium bromide (5 x 10 -4 mol) to 5.00 g (0.025 mol),
Heat and stir at 140℃ for 10 minutes. After cooling, it was dissolved in chloroform, the chloroform layer was washed with water, and the solvent was distilled off under reduced pressure to obtain 4-chloro-N-methylbenzothiazolone as white crystals with a melting point of 130-132°C.
4.88g was obtained. Yield: 97.6%, Purity: 98.8% Examples 4 to 9 Table 1 shows the results of changing the type of catalyst and/or the amount added in the same manner as in Example 3.
【表】
実施例 10〜16
２−メトキシ−４−クロロベンゾチアゾール
1.50ｇ（0.075mol）に各種の四級アンモニウム塩
（４×10-4mol）を加え、150℃にて３時間加熱撹
拌した後、４−クロロ−Ｎ−メチルベンゾチアゾ
ロンへの転化率をガスクロマトグラフイーで分析
した結果を第２表に示した。[Table] Examples 10 to 16 2-methoxy-4-chlorobenzothiazole
Various quaternary ammonium salts (4 x 10 -4 mol) were added to 1.50 g (0.075 mol), and after heating and stirring at 150°C for 3 hours, the conversion rate to 4-chloro-N-methylbenzothiazolone was determined. The results of gas chromatography analysis are shown in Table 2.
【表】【table】
Claims (1)
アルキル基を示す。） で表わされる２−メトキシベンゾチアゾール誘導
体を熱転位させて、一般式 （式中、Ｒは前記の意味を有する。） で表わされるＮ−メチルベンゾチアゾロン誘導体
を製造する方法において、転位を四級アンモニウ
ム塩の存在下に行なうことを特徴とするＮ−メチ
ルベンゾチアゾロン誘導体の製造方法。[Claims] 1. General formula (In the formula, R represents a hydrogen atom, a halogen atom, or a lower alkyl group.) By thermally rearranging the 2-methoxybenzothiazole derivative represented by the general formula (In the formula, R has the above-mentioned meaning.) A method for producing an N-methylbenzothiazolone derivative represented by Method for producing zolon derivatives.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7511178A JPS552642A (en) | 1978-06-20 | 1978-06-20 | Preparation of n-methyl-benzthiazolone derivative |
| IT7968299A IT7968299A0 (en) | 1978-06-19 | 1979-06-18 | PROCEDURE FOR THE PREPARATION OF DERIVATIVES OF N ALKYLBENZOTHIAZOLONES PARTICULARLY USEFUL AS FUNGICIDES |
| GB7921150A GB2026475A (en) | 1978-06-19 | 1979-06-18 | Method of preparing n-alkyl benzothiazolone derivatives |
| NL7904750A NL7904750A (en) | 1978-06-19 | 1979-06-18 | PROCESS FOR PREPARING N-ALKYL-BENZOTHIAZOL DERIVATIVES. |
| FR7915594A FR2429211A1 (en) | 1978-06-19 | 1979-06-18 | PROCESS FOR THE PRODUCTION OF N-METHYLBENZOTHIAZOLONE DERIVATIVES SUBSTITUTED IN POSITION 4 |
| US06/049,634 US4293702A (en) | 1978-06-19 | 1979-06-18 | Method for preparing 4-substituted-N-methylbenzothiazolone derivatives |
| DE19792924712 DE2924712A1 (en) | 1978-06-19 | 1979-06-19 | PROCESS FOR THE PREPARATION OF N-ALKYLBENZOTHIAZOLONE DERIVATIVES |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7511178A JPS552642A (en) | 1978-06-20 | 1978-06-20 | Preparation of n-methyl-benzthiazolone derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS552642A JPS552642A (en) | 1980-01-10 |
| JPS6230188B2 true JPS6230188B2 (en) | 1987-07-01 |
Family
ID=13566729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7511178A Granted JPS552642A (en) | 1978-06-19 | 1978-06-20 | Preparation of n-methyl-benzthiazolone derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS552642A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110068627A (en) * | 2019-05-16 | 2019-07-30 | 江苏出入境检验检疫局轻工产品与儿童用品检测中心 | A kind of method of derivative-pyrolysis-high resolution gas chromatography-mass spectrometry identification cashew nut paint |
-
1978
- 1978-06-20 JP JP7511178A patent/JPS552642A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS552642A (en) | 1980-01-10 |
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