JPS60126290A - Production of boronic chelate compound - Google Patents
Production of boronic chelate compoundInfo
- Publication number
- JPS60126290A JPS60126290A JP23483383A JP23483383A JPS60126290A JP S60126290 A JPS60126290 A JP S60126290A JP 23483383 A JP23483383 A JP 23483383A JP 23483383 A JP23483383 A JP 23483383A JP S60126290 A JPS60126290 A JP S60126290A
- Authority
- JP
- Japan
- Prior art keywords
- boron trifluoride
- formula
- difluoro
- dihydro
- methyl
- 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.)
- Granted
Links
Abstract
Description
【発明の詳細な説明】
本発明はホウ素キレート化合物の製造法に関する。さら
に詳しくは９本発明は式
（式中、Ｒ１は水素原子又は低級アルキル基を。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing boron chelate compounds. More specifically, the present invention relates to the formula (wherein R1 is a hydrogen atom or a lower alkyl group).
比及びｍは同じ又は異なる低級アルキル基を。The ratio and m are the same or different lower alkyl groups.
Ｘ、及びｘ２は同じ又は異なるハロゲン原子を表わす）
で表わされる化合物と三フッ化ホウ素又は三フッ化ホウ
素錯体とを酸無水物中で反応させることからなる式
（式中＋ ＲＩ、 ＸＩ及びｋは前記に同じ）で表わさ
れる化合物の製造法に関する。X and x2 represent the same or different halogen atoms)
A method for producing a compound represented by the formula (wherein + RI, .
式（ＩＩ）の化合物は特開昭５７−４６１）８６号公報
に記載された抗菌物質の合成中間体としてきわめて重要
な化合物である。The compound of formula (II) is an extremely important compound as a synthetic intermediate for the antibacterial substance described in JP-A-57-461)86.
従来２式（Ｉｔ）の化合物の製造法としては９式（１）
の化合物を三フッ化ホウ素又は三フッ化ホウ素錯体と反
応させることからなる製造法が知られている。（特開昭
５８−２９７８９号公報参照）しかしながら、この製造
法では反応温度を２００〜２４０℃に保った場合には目
的化合物が収率良く得られるが１反応温度をそれよりも
低く保った場合、収率が低下している。従って。The conventional method for producing the compound of formula 2 (It) is formula 9 (1)
A production process is known which consists of reacting a compound of with boron trifluoride or a boron trifluoride complex. (Refer to JP-A No. 58-29789) However, in this production method, the target compound can be obtained in good yield when the reaction temperature is kept at 200 to 240°C, but when the reaction temperature is kept lower than that, , the yield is decreasing. Therefore.
目的化合物を収率良く得るには反応温度を２００℃以上
という高温に保たねばならず、設備面、材質面及び危険
性等から、従４１シ造法は工業的製造法として満足でき
るものではない。In order to obtain the target compound in good yield, the reaction temperature must be kept at a high temperature of 200°C or higher, and the conventional 41-method is not satisfactory as an industrial manufacturing method due to equipment, material, and danger factors. do not have.
本発明者等は、従来法のかかる欠点を克服すべく鋭意検
討した結果本発明を完成した。The present inventors completed the present invention as a result of intensive studies to overcome these drawbacks of conventional methods.
即ち１本発明は式（１）の化合物と三ツ、化ホウ素又は
三フッ化ホウ素錯体とを酸無水物中で反応させることか
らなる式（ＩＩ）の化合物の製造法である。Specifically, the present invention is a method for producing a compound of formula (II), which comprises reacting a compound of formula (1) with a complex of boron trifluoride or boron trifluoride in an acid anhydride.
三フッ化ホウ素錯体としては三フッ化ホウ素のテトラヒ
ドロフラン錯体、ジエチルエーテル錯体、ジブチルエー
テル錯体、酢酸錯体及びメタノール錯体等があげられる
。Examples of boron trifluoride complexes include tetrahydrofuran complexes, diethyl ether complexes, dibutyl ether complexes, acetic acid complexes, and methanol complexes of boron trifluoride.
三フフ化ホウ素及び三フッ化ホウ素錯体は。Boron trifluoride and boron trifluoride complexes.
それぞれ単独又は２ｆａ以上混合して使用され。Each is used alone or in a mixture of 2fa or more.
その使用量は通常式（１）の化合物に対し１〜３倍モル
の範囲、好ましくは１〜２倍モルの範囲である。The amount used is usually 1 to 3 times the mole, preferably 1 to 2 times the mole of the compound of formula (1).
酸無水物としては無水酢酸、無水プロピオン酸及び無水
酪酸等の脂肪族カルボン酸の無水物並びに安息香酸等の
炭素環式カルボン酸の無水物があげられる。これらの酸
無水物は通常単独で使用されるが、２種以上混合して使
用してもよく、その使用量は通常式（１）の化合物１部
に対して０．５〜５部の範囲が好適である。Examples of acid anhydrides include anhydrides of aliphatic carboxylic acids such as acetic anhydride, propionic anhydride, and butyric anhydride, and anhydrides of carbocyclic carboxylic acids such as benzoic acid. These acid anhydrides are usually used alone, but two or more types may be used in combination, and the amount used is usually in the range of 0.5 to 5 parts per 1 part of the compound of formula (1). is suitable.
反応は８０〜１５０”Ｃ，好ましくは１００〜１４０℃
で３０分〜４時間、好ましくは１〜２時間保つことによ
り実施される。The reaction temperature is 80-150"C, preferably 100-140"C.
It is carried out by keeping it for 30 minutes to 4 hours, preferably 1 to 2 hours.
反応が進行すると、カルボン酸のｆルキルエステル、カ
ルボン酸並びにテトラヒドロ７ラン。As the reaction progresses, f-alkyl esters of carboxylic acids, carboxylic acids, and tetrahydro7ranes are produced.
ジエチルエーテル、酢酸及びメタノール等の錯体溶媒の
如き副生物が生成するが、これらを反応系外に除去しな
がら９例えば低沸点のものを留去しながら反応を行うと
目的化合物の収率が一層向上することがある。By-products such as complex solvents such as diethyl ether, acetic acid, and methanol are produced, but if the reaction is carried out while removing these from the reaction system9, for example, while distilling off those with low boiling points, the yield of the target compound can be further increased. It may improve.
反応経了後２反応液を冷却し析出する結晶をそのまま濾
取しメタノール等で洗浄するか、もしくは反応液にメタ
ノール又はエタノール等のアルコール系溶媒、アセトン
等のケトン系溶媒。After the completion of the reaction, the reaction solution is cooled and the precipitated crystals are collected by filtration and washed with methanol or the like, or the reaction solution is mixed with an alcoholic solvent such as methanol or ethanol, or a ketone solvent such as acetone.
酢酸エステル等のエステル系溶媒、エチレンジクロリド
等の塩素系溶媒あるいはベンゼン等の芳香族系溶媒を理
論した後析出した結晶を濾取してメタノール等で洗浄す
ると、目的とする式（ｎ）の化合物を容易に得ることが
できる。After using ester solvents such as acetic ester, chlorine solvents such as ethylene dichloride, or aromatic solvents such as benzene, the precipitated crystals are collected by filtration and washed with methanol etc. to obtain the desired compound of formula (n). can be easily obtained.
本発明は比較的低温で目的とする式（１１）の化合物を
高収率及び高純度で得ることができ、工業的にきわめて
有用な製造法である。The present invention can obtain the target compound of formula (11) at a relatively low temperature in high yield and purity, and is an extremely useful manufacturing method industrially.
実施例１
７．８−ジフルオロ−２，８−ジヒドロ−３−メチル−
４１（−１，４−ベンズオキサジン５．２１１及ヒシエ
チルエトキシメチレンマロネート７．４２の混合物を１
３０〜１４０℃で生成するエタノールを留去しながら５
時間加熱攪拌し。Example 1 7.8-difluoro-2,8-dihydro-3-methyl-
41 (-1,4-benzoxazine 5.211 and hisethyl ethoxymethylene malonate 7.42)
5 while distilling off the ethanol produced at 30-140°C.
Heat and stir for an hour.
（７，８−ジフルオロ−２，８−ジヒドロ−３−メチル
−４Ｈ−１，４−ベンズオキサジン−４−イル）メチレ
ンマロン酸ジエチルを生成させる。Diethyl (7,8-difluoro-2,8-dihydro-3-methyl-4H-1,4-benzoxazin-4-yl)methylenemalonate is produced.
減圧下にエタノールを留去し、残香に三フッ化ボウ素テ
Ｙラヒドロ７ラン錯体８９及び無水酢酸１０−を加え、
１時間攪拌還流する。その後１０２〜１３５℃で低沸点
留分を留去しながら１時間攪拌する。冷接エチレンジク
ロリド８０−を加え析出した結晶を濾取し、メタノール
で洗浄して乾燥する。得られた結晶のＩＲ，ＮＭＲ１元
素分析及びＴＬＣ等は既知の９，１０−ジフルオロ−３
−メチル−７−オキソ−２，８−ジヒドロ−７Ｈ−ピリ
ド（１，２，８−ｄｅ ） （１，４）ベンズオキサジ
ン−６−カルボン酸−ＢＦ２−キレートと一致した。収
量８．Ｏｌり（収率８５．２％）
実施例２
７．８−ジフルオロ−２，８−ジヒドロ−３−メチル−
４Ｈ−１，４−ベンズオキサジン９．８８９及びジエチ
ルエトキシメチレンマロネート１８．１２の混合物を実
施例１と同様に反応させて（７，８−ジフルオロ−２，
８−ジヒドロ−８−メチル−４Ｈ−１，４−ベンズオキ
サジン−４−イル）メチレンマロン酸ジエチルを生成さ
せる。Ethanol was distilled off under reduced pressure, boron trifluoride tetrahydro7rane complex 89 and acetic anhydride 10- were added to the residual aroma,
Stir and reflux for 1 hour. Thereafter, the mixture is stirred at 102 to 135° C. for 1 hour while distilling off the low boiling point fraction. The crystals precipitated by adding 80% of cold ethylene dichloride are collected by filtration, washed with methanol, and dried. IR, NMR1 elemental analysis, TLC, etc. of the obtained crystals revealed that 9,10-difluoro-3
-Methyl-7-oxo-2,8-dihydro-7H-pyrido(1,2,8-de) (1,4)benzoxazine-6-carboxylic acid-BF2-chelate. Yield 8. Olli (yield 85.2%) Example 2 7.8-difluoro-2,8-dihydro-3-methyl-
A mixture of 9.889% of 4H-1,4-benzoxazine and 18.12% of diethyl ethoxymethylene malonate was reacted in the same manner as in Example 1 to form (7,8-difluoro-2,
Diethyl 8-dihydro-8-methyl-4H-1,4-benzoxazin-4-yl)methylenemalonate is produced.
減圧下にエタノールを留去し、残香を無水酢酸１８ｆｎ
１．に溶解後１００〜１２０°Ｃで攪拌下に三フッ化ホ
ウ素テトラヒドロフラン錯体７．７６りを滴下する。滴
下後８０分間攪拌還流し９次いで１０２〜１１７℃で低
沸点の物質を留去しガから１時間攪拌する。冷接、エチ
レンジクロリド５４−で晶析させる。析出した結晶を濾
取しメタノール５４−で洗浄し、９．１０−ジフルオロ
−８−メチル−７−オキソ−２，８−ジヒドロ−７８−
ピリド（１，２，ａ −ｄｏ ） （１，４）ベンズオ
キサジン−６−カルボン酸−ＢＦ２−キレートを得る。Ethanol was distilled off under reduced pressure, and the residual aroma was extracted with acetic anhydride (18fn).
1. After dissolving in the solution, 7.76 g of boron trifluoride tetrahydrofuran complex was added dropwise at 100 to 120° C. while stirring. After the dropwise addition, the mixture was stirred and refluxed for 80 minutes, and then low-boiling substances were distilled off at 102 to 117°C, and the mixture was stirred for 1 hour. Cold welding, crystallization with ethylene dichloride 54-. The precipitated crystals were collected by filtration and washed with 54-methanol to give 9.10-difluoro-8-methyl-7-oxo-2,8-dihydro-78-
Pyrido(1,2,a-do)(1,4)benzoxazine-6-carboxylic acid-BF2-chelate is obtained.
収量１８．７２２（収率８２．８％）実施例３
７．８−ジフルオロ−２，３−ジヒドロ−３−メチル−
４Ｈ−１，４−ベンズオキサジン１８．１５り及びジエ
チルエトキシメチレンマロネート１６．８９９の混合物
を実施例１と同様に反応させて（７，８−ジフルオロ−
２，８−ジヒドロ−８−メチル−４８−１，４−ベンズ
オキサジン−４−イル）メチレンマロン酸ジエチルを生
成させる。減圧下にエタノールを留去し、残香を無水酢
酸２４−に溶解し、１００〜１２０’Ｃで攪拌下三フッ
化ホウ素テトラヒドロ７ラン錯体１０．９８りを滴下す
る。滴下後８０分間攪拌還流し、ついで低沸点留分を留
去しながら２時間攪拌する。冷接アセトン８ｏ−で晶析
させる。Yield 18.722 (yield 82.8%) Example 3 7.8-difluoro-2,3-dihydro-3-methyl-
A mixture of 18.15% of 4H-1,4-benzoxazine and 16.899% of diethyl ethoxymethylene malonate was reacted in the same manner as in Example 1 (7,8-difluoro-
Diethyl 2,8-dihydro-8-methyl-48-1,4-benzoxazin-4-yl)methylenemalonate is produced. Ethanol is distilled off under reduced pressure, and the residual aroma is dissolved in 24% of acetic anhydride, and 10.98 g of boron trifluoride tetrahydro 7 run complex is added dropwise to the solution under stirring at 100 to 120'C. After the dropwise addition, the mixture was stirred and refluxed for 80 minutes, and then stirred for 2 hours while distilling off low-boiling fractions. Crystallize with cold acetone 8o.
析出した結晶を濾取し、メタノール５ｏ−で洗浄し、９
．１０−ジフルオロ−８−メチル−７−オキソ−２，３
−ジヒドロ−７Ｈ−ピリド（１＃２１８−ｄｅ）（１，
４）ベンズオキサジン−６−カルボン酸−ＢＦ２−キレ
ートを得る。収ｆｆ１２０．１４９（収率８６．２％）
実施例４
７．８−ジフルオロ−２，８−ジヒドロ−８−メチル−
４Ｈ−１，４−ベンズオキサジン２．８４７及ヒシエチ
ルエトキシメチレンマロネート８．２９ｇの混合物を実
施例１と同様に反応させる０減圧下にエタノールを留去
し、残香をジイソプロピルエーテルで再結晶すると白色
結晶の（７，８−ジフルオロ−２，８−ジヒドロ−８−
メチル−４Ｈ−１，４−ベンズオキサジン−４−イル）
メチレンマロン酸ジエチルを得る。融点６８℃。The precipitated crystals were collected by filtration, washed with methanol 5o-
．． 10-difluoro-8-methyl-7-oxo-2,3
-dihydro-7H-pyrido (1#218-de) (1,
4) Obtain benzoxazine-6-carboxylic acid-BF2-chelate. Yield ff 120.149 (yield 86.2%) Example 4 7.8-difluoro-2,8-dihydro-8-methyl-
A mixture of 2.847 g of 4H-1,4-benzoxazine and 8.29 g of hisethylethoxymethylene malonate was reacted in the same manner as in Example 1. Ethanol was distilled off under reduced pressure, and the residual aroma was recrystallized with diisopropyl ether. White crystals of (7,8-difluoro-2,8-dihydro-8-
methyl-4H-1,4-benzoxazin-4-yl)
Diethyl methylenemalonate is obtained. Melting point: 68°C.
Ｎ Ｍ Ｒ（Ｃ；ＤＧｔ３．δ＋ｐｐｍ）６．６７〜６
．８７ （２Ｈ，ｍ、芳香族プロトン）４、０〜４．４
７ （７Ｈ，ｍ、−（Ｈ７ＧＨ３，−０−ＣＪＪ２−Ｃ
ｉＪｉ−Ｎ ）７．７４ （ＬＨ，ｓ、 Ｊ：：Ｎ−０
旦−ｃ＜ ）１．１８〜１．会？ （９Ｈ，−（３Ｈ２
−ａＨ３，’；ａＨ−ｃル）得られた結晶８りに三フッ
化ホウ素テトラヒドロ７ラン錯体１．５４ｇ及び無水酢
酸８−を加え、外温１５０°Ｃで低沸点の物質を留去し
なから１時間攪拌する。冷後析出した結晶を濾取し。NMR(C;DGt3.δ+ppm)6.67~6
．． 87 (2H, m, aromatic proton) 4, 0-4.4
7 (7H, m, -(H7GH3, -0-CJJ2-C
iJi-N)7.74 (LH,s, J::N-0
Dan-c< )1.18~1. Meeting? (9H, -(3H2
-aH3,'; aH-cl) 1.54 g of boron trifluoride tetrahydro 7-lane complex and acetic anhydride 8- were added to the obtained crystal 8, and low boiling point substances were distilled off at an external temperature of 150°C. Stir for 1 hour. After cooling, the precipitated crystals were collected by filtration.
冷メタノール１０−で洗浄し、９．１０−ジフルオロ−
８−メチル−７−オキソ−２，８−ジヒド０−７Ｈ−ピ
リド（１，２，３−（１６） （１，４）ベンズオキサ
ジン−６−カルボン酸−Ｂｐｚ−キレートを得る。収量
２．８１ｇ（収率８８．１％）実施例５
（７，８−ジフルオロ−２，８−ジヒドロ−８−メチル
−４Ｈ−１，４−ベンズオキサジン−４−イル）メチレ
ンマロン酸ジエチル３ｇに三フッ化ホウ素テトラヒドロ
７ラン錯体１．５４り及び無水酢酸８ｒｎｔを加え、攪
拌下１時間還流する。Wash with cold methanol 10-9,10-difluoro-
8-Methyl-7-oxo-2,8-dihydro-7H-pyrido(1,2,3-(16) (1,4)benzoxazine-6-carboxylic acid-Bpz-chelate is obtained. Yield: 2. 81 g (yield 88.1%) Example 5 Trifluorofluoride was added to 3 g of diethyl (7,8-difluoro-2,8-dihydro-8-methyl-4H-1,4-benzoxazin-4-yl)methylenemalonate. 1.54 rnt of boron tetrahydro 7rane complex and 8 rnt of acetic anhydride are added, and the mixture is refluxed for 1 hour while stirring.
冷後析出した結晶を濾取し、冷メタノール１〇−で洗浄
すると９，１０−ジフルオロ−８−メチル−７−オキソ
−２，３−ジヒドロ−７Ｈ−ピリド（１，２，３−ｄｅ
） （１，４）ベンズオキサジン−６−カルボン酸−
ＢＦ２−キレートが得られる。After cooling, the precipitated crystals were collected by filtration and washed with cold methanol 10- to give 9,10-difluoro-8-methyl-7-oxo-2,3-dihydro-7H-pyrido (1,2,3-de
) (1,4)benzoxazine-6-carboxylic acid-
A BF2-chelate is obtained.
収量２，１８ｇ（収率７８．５％）
実施例６
７．８−ジフルオロ−２，８−ジヒドロ−３−メチル−
４Ｈ−１，４−ベンズオキサジン１．５６７及びジエチ
ルエトキシメチレンマロネート２．１９７の混合物を実
施例１と同様に反応させて、（７，８−ジフルオロ−２
，８−ジヒドロ−８−メチル−４Ｈ−１，４−ベンズオ
キサジン−４−イル）メチレンマロン酸ジエチルを生成
させる。減圧下にエタノールを留去し、残香に無水プロ
ピオン酸３ｔｎｌ及び三フッ化ホウ素テトラヒ遠
ドロフラン錯体１．５４りを加え１時間攪拌＃流する。Yield 2,18 g (yield 78.5%) Example 6 7,8-difluoro-2,8-dihydro-3-methyl-
A mixture of 1.567% of 4H-1,4-benzoxazine and 2.197% of diethyl ethoxymethylene malonate was reacted in the same manner as in Example 1 to form (7,8-difluoro-2
, 8-dihydro-8-methyl-4H-1,4-benzoxazin-4-yl)methylenemalonate. Ethanol was distilled off under reduced pressure, and 3 tnl of propionic anhydride and 1.54 ml of boron trifluoride tetrahydrofuran complex were added to the residual aroma, and the mixture was stirred for 1 hour.
次いで、外温１５０°Ｃで低沸点の物質を留去しながら
１時間攪拌する。反発後氷冷しエチレンジクロリド１０
−で晶析させる。析出した結晶を濾取し冷メタノールで
洗浄し乾燥すると、９．Ｎｏ−ジフルオロ−３−メチル
−７−オキソ−２，３−ジヒドロ−７Ｈ−ピリド（１，
２，８−ａｓ）（１，４）ベンズオキサジン−６−カル
ボン酸−ＢＦ２−キレートを得る。収量２．２６ｇ（収
率８１．３％）
実施例７
７．８−ジフルオロ−２，３−ジヒドロ−８−メチル−
４Ｈ−１，４−ベンズオキサジン１．５６９及びジエチ
ルエトキシメチレンマロネート２．１９２の混合物を実
施例１と同様に反応させて、（７，８−ジフルオロ−２
，８−ジヒドロ−８−メチル−４Ｈ−１，４−ベンズオ
キサジン−４−イル）メチレンマロン酸ジエチルを生成
させる。減圧下にエタノールを留去し、残香に三フッ化
ホウ素テトラヒドロフラン錯体１．５４り及び無水酪酸
８−を加え、１時間攪拌還流する。Next, the mixture is stirred for 1 hour at an external temperature of 150°C while distilling off low-boiling substances. After repulsion, ice-cool ethylene dichloride 10
-Crystallize at -. 9. The precipitated crystals were collected by filtration, washed with cold methanol, and dried. No-difluoro-3-methyl-7-oxo-2,3-dihydro-7H-pyrido (1,
2,8-as)(1,4)benzoxazine-6-carboxylic acid-BF2-chelate is obtained. Yield 2.26 g (yield 81.3%) Example 7 7.8-difluoro-2,3-dihydro-8-methyl-
A mixture of 1.569% of 4H-1,4-benzoxazine and 2.192% of diethyl ethoxymethylene malonate was reacted in the same manner as in Example 1 to form (7,8-difluoro-2
, 8-dihydro-8-methyl-4H-1,4-benzoxazin-4-yl)methylenemalonate. Ethanol was distilled off under reduced pressure, and 1.54 g of boron trifluoride tetrahydrofuran complex and 8-butyric anhydride were added to the residual aroma, and the mixture was stirred and refluxed for 1 hour.
次いで、外温１５０℃で低沸点の物質を留去しながら１
時間攪拌する。反発後氷冷し、エチレンジクロリド１０
−で晶析させる。析出した結晶を濾取し、冷メタノール
で洗浄し、乾燥すると９．１０−ジフルオロ−８−メチ
ル−７−オキソ−２，３−ジヒドロ−７Ｈ−ピリド（１
；２，８−ａｅ）（１，４）ベンズオキサジン−６−カ
ルボン酸−ＢＦ２−キレートが得られる。収量２．２１
９（収率７９．５％）
実施例８
７．８−ジフルオロ−２，３−ジヒドロ−８−メチル−
４Ｈ−１，４−ベンズオキサジン２．８４！７及びジエ
チルエトキシメチレンマロネート８．２’ｌの混合物を
実施例１と同様に反応させて＋（７＋８−ジフルオロ−
２，８−ジヒドロ−８−メチル−４Ｈ−１，４−ベンズ
オキサジン−４−イル）メチレンマロン酸ジエチルを生
成させる。減圧下にエタノールを留去し、残香に三フッ
化ホウ素テトラヒドロフラン錯体１．９４ｇ及び無水安
息香酸５ｇｎｔを加え、１時間攪拌還流する。次いで、
外温１５０℃で低沸点の物質を留去しながら１時間攪拌
する。反発後氷冷し、エチレンジクロリド１５ｇｎｔで
晶析させる。析出した結晶を濾取し、メタノールで洗浄
し乾燥すると、９．１０−ジフルオロ−８−メチル−７
−オキソ−２，８−ジヒドロ−７Ｈ−ピリド（１，２，
８−ａｅ）（１，４）ベンズオキサジン−６−カルボン
酸−ＢＦ２−キレートが得られる。収量３．４２９（収
率８２．４％）Next, while distilling off low boiling point substances at an external temperature of 150°C,
Stir for an hour. After repulsion, cool on ice and add ethylene dichloride 10
-Crystallize at -. The precipitated crystals were collected by filtration, washed with cold methanol, and dried to give 9.10-difluoro-8-methyl-7-oxo-2,3-dihydro-7H-pyrido (1
;2,8-ae)(1,4)benzoxazine-6-carboxylic acid-BF2-chelate is obtained. Yield 2.21
9 (yield 79.5%) Example 8 7.8-difluoro-2,3-dihydro-8-methyl-
A mixture of 2.84!7 4H-1,4-benzoxazine and 8.2'l of diethyl ethoxymethylene malonate was reacted in the same manner as in Example 1 to give +(7+8-difluoro-
Diethyl 2,8-dihydro-8-methyl-4H-1,4-benzoxazin-4-yl)methylenemalonate is produced. Ethanol is distilled off under reduced pressure, and 1.94 g of boron trifluoride tetrahydrofuran complex and 5 gnt of benzoic anhydride are added to the residual aroma, and the mixture is stirred and refluxed for 1 hour. Then,
Stir for 1 hour at an external temperature of 150°C while distilling off low-boiling substances. After repulsion, it is cooled on ice and crystallized with 15 gnt of ethylene dichloride. The precipitated crystals were collected by filtration, washed with methanol, and dried to give 9.10-difluoro-8-methyl-7.
-oxo-2,8-dihydro-7H-pyrido (1,2,
8-ae)(1,4)benzoxazine-6-carboxylic acid-BF2-chelate is obtained. Yield 3.429 (yield 82.4%)
Claims (1)
表わされる化合物と三フッ化ホウ素又は三フッ化ホウ素
錯体とを酸無水物中で反応させることを特徴とする式 （式中、 Ｒ１，Ｘ、及びｘ２は前記に同じ）で表わさ
れる化合物の製造法[Scope of Claims] A compound represented by the formula (wherein RI represents a hydrogen atom or a lower alkyl group; & and ~ represent the same or different lower alkyl groups; Xl and k represent the same or different halogen atoms); A method for producing a compound represented by the formula (wherein R1, X, and x2 are the same as above), which comprises reacting boron trifluoride or a boron trifluoride complex in an acid anhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23483383A JPS60126290A (en) | 1983-12-13 | 1983-12-13 | Production of boronic chelate compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23483383A JPS60126290A (en) | 1983-12-13 | 1983-12-13 | Production of boronic chelate compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60126290A true JPS60126290A (en) | 1985-07-05 |
| JPH0372230B2 JPH0372230B2 (en) | 1991-11-18 |
Family
ID=16977088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23483383A Granted JPS60126290A (en) | 1983-12-13 | 1983-12-13 | Production of boronic chelate compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60126290A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5300644A (en) * | 1987-04-08 | 1994-04-05 | Chinoin Gyogyser- Es Vegyeszeti Termekek Gyara Rt. | Process for the preparation of quinoline carboxylic acids |
-
1983
- 1983-12-13 JP JP23483383A patent/JPS60126290A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5300644A (en) * | 1987-04-08 | 1994-04-05 | Chinoin Gyogyser- Es Vegyeszeti Termekek Gyara Rt. | Process for the preparation of quinoline carboxylic acids |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0372230B2 (en) | 1991-11-18 |
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