JP3387579B2 - Method for producing 2-oxaindane derivative - Google Patents

Method for producing 2-oxaindane derivative

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Publication number
JP3387579B2
JP3387579B2 JP25855893A JP25855893A JP3387579B2 JP 3387579 B2 JP3387579 B2 JP 3387579B2 JP 25855893 A JP25855893 A JP 25855893A JP 25855893 A JP25855893 A JP 25855893A JP 3387579 B2 JP3387579 B2 JP 3387579B2
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JP
Japan
Prior art keywords
compound represented
general formula
oxaindane
formula
alkyl group
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 - Lifetime
Application number
JP25855893A
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Japanese (ja)
Other versions
JPH07112977A (en
Inventor
大塚  晋
厚 嘉悦
治 真柄
晋 竹村
好美 山田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Filing date
Publication date
Application filed by Sumitomo Chemical Co Ltd filed Critical Sumitomo Chemical Co Ltd
Priority to JP25855893A priority Critical patent/JP3387579B2/en
Publication of JPH07112977A publication Critical patent/JPH07112977A/en
Application granted granted Critical
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Expired - Lifetime legal-status Critical Current

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Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は、2−オキサインダン化
合物の製造法に関する。さらに詳しくは、特開平2−1
31481号公報等に記載されている農園芸用殺菌剤の
有効成分である化合物を製造する際の有用な中間体であ
る2−オキサインダン化合物の製造法に関する。
FIELD OF THE INVENTION The present invention relates to a method for producing a 2-oxaindane compound. For more details, see Japanese Patent Laid-Open No. 2-1
The present invention relates to a method for producing a 2-oxaindane compound which is a useful intermediate when producing a compound which is an active ingredient of an agricultural and horticultural fungicide described in Japanese Patent No. 31481.

【従来の技術および発明が解決しようとする課題】従
来、2−オキサインダン化合物の製造法としては、特開
平2−131481号公報に下記スキーム 化5
2. Description of the Related Art Conventionally, as a method for producing a 2-oxaindane compound, the following scheme 5 is described in JP-A-2-131481.

【化5】 で示されるように、式(I)のヘミケタール化合物を水
素雰囲気下に反応させることによって、式(II)の2
−オキサインダン化合物を得る方法が記載されている。
しかしながら、該製造法では、原料化合物である式
(I)のヘミケタール化合物が不安定であるため、条件
によっては目的とする式(II)の2−オキサインダン
化合物の品質(純度)の低下を引き起こす場合があり、
必ずしも該製造法は2−オキサインダン化合物の工業的
な製造法として充分とは言えない。
[Chemical 5] As shown in the formula, by reacting the hemiketal compound of the formula (I) under a hydrogen atmosphere, the hemiketal compound of the formula (II) 2
-A method for obtaining oxaindane compounds is described.
However, in this production method, the hemiketal compound of the formula (I), which is the starting material compound, is unstable, and therefore, depending on the conditions, the quality (purity) of the desired 2-oxaindane compound of the formula (II) is deteriorated. There is
This production method is not always sufficient as an industrial production method of a 2-oxaindane compound.

【0002】[0002]

【課題を解決するための手段】本発明者らはこのような
状況に鑑み、後記一般式 化9で示される2−オキサイ
ンダン化合物を安定して純度よく得る方法について鋭意
検討した結果、後記一般式 化6で示されるヘミケター
ル化合物と後記一般式 化7で示されるアルコール化合
物とを反応させて、後記一般式 化8で示されるケター
ル化合物が容易に得られること、さらに、該ケタール化
合物を加水素分解することにより目的とする後記一般式
化9で示される2−オキサインダン化合物が容易に純
度よく得られることを見い出し、本発明を完成した。即
ち、本発明は一般式 化6
In view of such a situation, the present inventors have earnestly studied a method for stably obtaining a 2-oxaindane compound represented by the following general formula 9 with high purity. By reacting the hemiketal compound represented by the chemical formula 6 with an alcohol compound represented by the general formula (7) below to easily obtain the ketal compound represented by the general formula (8) below, and further by hydrogenolysis of the ketal compound By doing so, it was found that the desired 2-oxaindane compound represented by the following general formula (9) can be easily obtained with high purity, and the present invention was completed. That is, the present invention has the general formula

【化6】 (式中、R1、R2及びR3は同一または相異なり、低級
アルキル基〔例えばメチル基、エチル基等のC1〜C4
ルキル基〕を表わす。) で示されるヘミケタール化合物と一般式 化7
[Chemical 6] (Wherein R 1 , R 2 and R 3 are the same or different and each represents a lower alkyl group [for example, a C 1 -C 4 alkyl group such as a methyl group or an ethyl group]) and a general formula Conversion 7

【化7】R4−OH (式中、R4は低級アルキル基〔例えばメチル基、エチ
ル基等のC1〜C4アルキル基〕、低級アルコキシで置換
された低級アルキル基〔例えば、2−メトキシエチル
基、2−ブトキシエチル基、2−エトキシエチル基、2
−プロポキシエチル基等のC1〜C4アルコキシで置換さ
れたC1〜C4アルキル基〕またはヒドロキシ基で置換さ
れた低級アルキル基〔例えば2−ヒドロキシエチル基等
のヒドロキシ基で置換されたC1〜C4アルキル基〕を表
わす。) で示されるアルコール化合物とを反応させて、一般式
化8
Embedded image R 4 —OH (wherein R 4 is a lower alkyl group [for example, a C 1 -C 4 alkyl group such as a methyl group or an ethyl group]), a lower alkyl group substituted with a lower alkoxy [for example, 2- Methoxyethyl group, 2-butoxyethyl group, 2-ethoxyethyl group, 2
A C 1 -C 4 alkyl group substituted with a C 1 -C 4 alkoxy such as a propoxyethyl group or a lower alkyl group substituted with a hydroxy group [eg, a C substituted with a hydroxy group such as a 2-hydroxyethyl group] represent 1 -C 4 alkyl group]. ) Is reacted with an alcohol compound represented by
Conversion 8

【化8】 (式中、R1、R2、R3及びR4は前記と同じ意味を表わ
す。) で示されるケタール化合物とした(以下反応1と称
す。)後、該ケタール化合物を加水素分解する(以下反
応2と称す。)ことを特徴とする、一般式 化9
[Chemical 8] (Wherein R 1 , R 2 , R 3 and R 4 have the same meanings as described above) (hereinafter referred to as reaction 1), and the ketal compound is subjected to hydrogenolysis ( Hereinafter, referred to as reaction 2.)

【化9】 (式中、R1、R2及びR3は前記と同じ意味を表わ
す。) で示される2−オキサインダン化合物の製造法、および
該製造法において重要中間体となる一般式 化8で示さ
れるケタール化合物を提供する。
[Chemical 9] (In the formula, R 1 , R 2 and R 3 have the same meanings as described above.), And a ketal represented by the general formula 8 which is an important intermediate in the production process. A compound is provided.

【0003】反応1において、反応はトルエン等の炭化
水素類等の溶媒の存在下に行なってもよく、反応に供す
る試剤の量は一般式 化6で示されるヘミケタール化合
物1モルに対し、一般式 化7のアルコール化合物は通
常1〜1000モルの割合である。反応温度は通常20
℃〜150℃の範囲、好ましくは40℃〜100℃また
は溶媒の沸点の範囲である。反応時間は通常0.5時間
〜10時間である。該反応は一般式 化6で示されるヘ
ミケタール化合物1モルに対し、0.001〜0.1モ
ルの割合の無機酸(例えば硫酸)の存在下に行なうのが
好ましい。反応終了後の反応液は、そのまま反応2の原
料として使用することもできるし、必要に応じ、炭酸水
素ナトリウム水溶液等の塩基で中性〜弱アルカリ性とし
た後、有機溶媒抽出、濃縮等の通常の後処理を行うこと
により、一般式 化3で示されるケタール化合物を単離
することもできる。必要に応じて、クロマトグラフィー
等の手段により更に精製することもできる。反応2にお
いて、反応は通常トルエン等の炭化水素類、メタノー
ル、エタノール、ブチルセロソルブ、エチレングリコー
ル等のアルコール類、又はそれらの混合溶媒中、パラジ
ウム炭素、白金化合物等の触媒を用い、水素雰囲気下で
行なわれる。触媒量は一般式 化8で示されるケタール
化合物に対し、通常0.1〜10wt%量であり、好まし
くは1〜5wt%である。反応温度は、通常50℃〜10
0℃の範囲であり、好ましくは70℃〜100℃の範囲
である。反応時間は通常0.5時間〜10時間である。
反応終了後は、触媒を濾別した後、濾液を減圧下で濃縮
することにより、所望の一般式 化9で示される2−オ
キサインダン化合物を単離することができる。必要に応
じて、クロマトグラフィー等の手段により更に精製する
こともできる。このようにして得た一般式 化9で示さ
れる2−オキサインダン化合物は、例えば、特開平2−
131481号公報に記載された方法により、該公報等
に記載された優れた農園芸用殺菌効力を有する置換ピラ
ゾールカルボン酸化合物に容易に導くことができる。本
発明において用いられる原料化合物である一般式 化6
で示されるヘミケタール化合物は、例えば、特開平2−
131481号公報に記載された方法により製造するこ
とができる。
In the reaction 1, the reaction may be carried out in the presence of a solvent such as hydrocarbons such as toluene, and the amount of the reagent to be used in the reaction is 1 mol of the hemiketal compound represented by the general formula: The alcohol compound of Chemical formula 7 is usually in a proportion of 1 to 1000 mol. Reaction temperature is usually 20
C. to 150.degree. C., preferably 40.degree. C. to 100.degree. C. or the boiling point of the solvent. The reaction time is usually 0.5 hours to 10 hours. The reaction is preferably carried out in the presence of 0.001 to 0.1 mol of an inorganic acid (for example, sulfuric acid) with respect to 1 mol of the hemiketal compound represented by the general formula. The reaction liquid after completion of the reaction can be used as it is as a raw material for the reaction 2, or if necessary, after neutralized to weakly alkaline with a base such as an aqueous solution of sodium hydrogencarbonate, it is usually subjected to organic solvent extraction, concentration, etc. The ketal compound represented by the general formula 3 can also be isolated by carrying out the post-treatment. If necessary, it can be further purified by means such as chromatography. In Reaction 2, the reaction is usually carried out in a hydrogen atmosphere using a catalyst such as palladium carbon or a platinum compound in a hydrocarbon such as toluene, an alcohol such as methanol, ethanol, butyl cellosolve or ethylene glycol, or a mixed solvent thereof. Be done. The amount of the catalyst is usually 0.1 to 10% by weight, preferably 1 to 5% by weight, based on the ketal compound represented by the general formula. The reaction temperature is usually 50 ° C to 10 ° C.
It is in the range of 0 ° C, and preferably in the range of 70 ° C to 100 ° C. The reaction time is usually 0.5 hours to 10 hours.
After completion of the reaction, the desired 2-oxaindane compound represented by the general formula 9 can be isolated by filtering off the catalyst and concentrating the filtrate under reduced pressure. If necessary, it can be further purified by means such as chromatography. The 2-oxaindane compound represented by the general formula 9 thus obtained is described in, for example, JP-A-2-
By the method described in Japanese Patent No. 131481, it is possible to easily lead to the substituted pyrazole carboxylic acid compound having the excellent bactericidal effect for agricultural and horticultural use, which is described in this document. The compound represented by the general formula:
The hemiketal compound represented by
It can be manufactured by the method described in Japanese Patent No. 131481.

【0004】[0004]

【実施例】次に、本発明を製造例にてより詳しく説明す
るが、本発明は下記の製造例のみに限定されるものでは
ない。尚、以下の例において、生成物の純度は下記条件
の高速液体クロマトグラフィーによるクロマトグラムの
面百値から求めた。 カラム:SUMIPAX,ODS−A−212,直径6
mm×長さ15cm カラム温度:40℃ 移動相:CH3CN/H2O=4/6(v/v) 移動相の流量:1.0ml/分 検出:UV254nm 製造例 1−ヒドロキシ−2−オキサ−1,3,3−トリメチル
−7−アセトアミドインダン11.76gをメタノール
24g及びトルエン24gに溶かし、これに濃硫酸0.
10gを加え、45〜50℃で3時間撹拌した。冷却
後、反応液を飽和炭酸水素ナトリウム水50g中に注ぎ
こみ、酢酸エチル80gで抽出した。抽出液を飽和食塩
水20gで洗浄後、無水硫酸マグネシウムで乾燥した。
硫酸マグネシウムをグラスフィルターにて濾別し、濾液
をエバポレーターにて濃縮した。得られた油状物をシリ
カゲルカラムクロマトグラフィーに付し、1−メトキシ
−2−オキサ−1,3,3−トリメチル−7−アセトア
ミドインダン8.4gを白色結晶として得た。1 H−NMR(CDCl3/TMS) δ(ppm):1.5(3H,s)、1.5(3H,s)、
1.7(3H,s)、2.2(3H,s)、3.1(3
H,s)、6.85(1H,d,J=8.0Hz)、7.
3(1H,t,J=8.0Hz)、7.8(1H,br
s)、8.15(1H,d,J=8.0Hz) 1−メトキシ−2−オキサ−1,3,3−トリメチル−
7−アセトアミドインダン31.8gをメタノール60
gとトルエン30gの混合溶媒に溶かし、4.0wt%量
の5%パラジウム炭素を加え、水素雰囲気下、内圧5.
0kg/cm2、内温70〜75℃で5時間撹拌した。反応
混合物を、セライトを敷いたグラスフィルターにて濾過
し、残渣をメタノールとトルエンの混合物にて洗浄し
た。濾液と洗浄液とを合わせて濃縮することにより、
1,3,3−トリメチル−2−オキサ−7−アセトアミ
ドインダン27.7gを得た。1 H−NMR(CDCl3/TMS) δ(ppm):1.4(3H,s)、1.4(3H,d,J=
6.0Hz)、1.5(3H,s)、2.1(3H,s)、
5.4(1H,q,J=6.0Hz)、6.8〜7.4
(3H,m)、8.1(1H,s) 純度 99.0%
EXAMPLES The present invention will now be described in more detail with reference to production examples, but the present invention is not limited to the following production examples. In the following examples, the purity of the product was obtained from the area percentage of the chromatogram by high performance liquid chromatography under the following conditions. Column: SUMPIPAX, ODS-A-212, diameter 6
mm × length 15 cm Column temperature: 40 ° C. Mobile phase: CH 3 CN / H 2 O = 4/6 (v / v) Flow rate of mobile phase: 1.0 ml / min Detection: UV254 nm Production Example 1-Hydroxy-2- 11.76 g of oxa-1,3,3-trimethyl-7-acetamidoindane was dissolved in 24 g of methanol and 24 g of toluene, and concentrated sulfuric acid of 0.
10g was added and it stirred at 45-50 degreeC for 3 hours. After cooling, the reaction solution was poured into 50 g of saturated aqueous sodium hydrogen carbonate and extracted with 80 g of ethyl acetate. The extract was washed with 20 g of saturated saline and dried over anhydrous magnesium sulfate.
Magnesium sulfate was filtered off with a glass filter, and the filtrate was concentrated with an evaporator. The obtained oily substance was subjected to silica gel column chromatography to obtain 8.4 g of 1-methoxy-2-oxa-1,3,3-trimethyl-7-acetamidoindane as white crystals. 1 H-NMR (CDCl 3 / TMS) δ (ppm): 1.5 (3H, s), 1.5 (3H, s),
1.7 (3H, s), 2.2 (3H, s), 3.1 (3
H, s), 6.85 (1H, d, J = 8.0 Hz), 7.
3 (1H, t, J = 8.0 Hz), 7.8 (1H, br
s), 8.15 (1H, d, J = 8.0 Hz) 1-methoxy-2-oxa-1,3,3-trimethyl-
31.8 g of 7-acetamidoindane was added to methanol 60
dissolved in a mixed solvent of 30 g of toluene and 30 g of toluene, 4.0% by weight of 5% palladium carbon was added, and the internal pressure was adjusted to 5.
The mixture was stirred at 0 kg / cm 2 and an internal temperature of 70 to 75 ° C. for 5 hours. The reaction mixture was filtered through a glass filter covered with Celite, and the residue was washed with a mixture of methanol and toluene. By combining and concentrating the filtrate and the washing solution,
27.7 g of 1,3,3-trimethyl-2-oxa-7-acetamidoindane was obtained. 1 H-NMR (CDCl 3 / TMS) δ (ppm): 1.4 (3H, s), 1.4 (3H, d, J =
6.0 Hz), 1.5 (3H, s), 2.1 (3H, s),
5.4 (1H, q, J = 6.0 Hz), 6.8 to 7.4
(3H, m), 8.1 (1H, s) Purity 99.0%

【0005】[0005]

【発明の効果】本発明により、高純度の一般式 化9で
示される2−オキサインダン化合物を得ることができ
る。
According to the present invention, a highly pure 2-oxaindane compound represented by the general formula 9 can be obtained.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 竹村 晋 兵庫県宝塚市高司4丁目2番1号 住友 化学工業株式会社内 (72)発明者 山田 好美 兵庫県宝塚市高司4丁目2番1号 住友 化学工業株式会社内 (56)参考文献 特開 平2−131481(JP,A) (58)調査した分野(Int.Cl.7,DB名) C07D 307/87 CA(STN) REGISTRY(STN)─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Susumu Takemura 4-2-1 Takashi Takarazuka-shi, Hyogo Sumitomo Chemical Co., Ltd. (72) Inventor Yoshimi Yamada 4-2-1 Takashi Takarazuka-shi Hyogo Sumitomo Within Kagaku Kogyo Co., Ltd. (56) Reference JP-A-2-131481 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) C07D 307/87 CA (STN) REGISTRY (STN)

Claims (2)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】 一般式 化1 【化1】 (式中、R1、R2及びR3は同一または相異なり、低級
アルキル基を表わす。) で示されるヘミケタール化合物と一般式 化2 【化2】R4−OH (式中、R4は低級アルキル基、低級アルコキシ基で置
換された低級アルキル基またはヒドロキシ基で置換され
た低級アルキル基を表わす。) で示されるアルコール化合物とを反応させて、一般式
化3 【化3】 (式中、R1、R2、R3及びR4は前記と同じ意味を表わ
す。) で示されるケタール化合物とした後、該ケタール化合物
を加水素分解することを特徴とする、一般式 化4 【化4】 (式中、R1、R2及びR3は前記と同じ意味を表わ
す。) で示される2−オキサインダン化合物の製造法。
1. A general formula: (Wherein R 1 , R 2 and R 3 are the same or different and each represents a lower alkyl group) and a hemiketal compound represented by the following general formula: embedded image R 4 —OH (wherein R 4 is A lower alkyl group, a lower alkyl group substituted with a lower alkoxy group, or a lower alkyl group substituted with a hydroxy group is reacted with an alcohol compound represented by
Chemical formula 3 (Wherein R 1 , R 2 , R 3 and R 4 have the same meanings as defined above), and the ketal compound is subjected to hydrogenolysis. 4 [Chemical 4] (In the formula, R 1 , R 2 and R 3 have the same meanings as described above.) A method for producing a 2-oxaindane compound represented by the formula:
【請求項2】請求項1記載の一般式 化3で示されるケ
タール化合物。
2. A ketal compound represented by the general formula 3 according to claim 1 .
JP25855893A 1993-10-15 1993-10-15 Method for producing 2-oxaindane derivative Expired - Lifetime JP3387579B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP25855893A JP3387579B2 (en) 1993-10-15 1993-10-15 Method for producing 2-oxaindane derivative

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP25855893A JP3387579B2 (en) 1993-10-15 1993-10-15 Method for producing 2-oxaindane derivative

Publications (2)

Publication Number Publication Date
JPH07112977A JPH07112977A (en) 1995-05-02
JP3387579B2 true JP3387579B2 (en) 2003-03-17

Family

ID=17321901

Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Status (1)

Country Link
JP (1) JP3387579B2 (en)

Also Published As

Publication number Publication date
JPH07112977A (en) 1995-05-02

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