JP2731853B2 - Method for producing tri-lower alkanoyloxyboron - Google Patents
Method for producing tri-lower alkanoyloxyboronInfo
- Publication number
- JP2731853B2 JP2731853B2 JP923489A JP923489A JP2731853B2 JP 2731853 B2 JP2731853 B2 JP 2731853B2 JP 923489 A JP923489 A JP 923489A JP 923489 A JP923489 A JP 923489A JP 2731853 B2 JP2731853 B2 JP 2731853B2
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- Japan
- Prior art keywords
- anhydride
- acid
- general formula
- compound
- alkanoyloxyboron
- 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.)
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Description
【発明の詳細な説明】 産業上の利用分野 本発明は、トリ低級アルカノイルオキシホウ素の製造
法に関する。Description: TECHNICAL FIELD The present invention relates to a method for producing tri-lower alkanoyloxyboron.
従来の技術及びその問題点 従来トリ低級アルカノイルオキシホウ素は、ホウ酸と
無水低級アルカン酸とを反応させることにより製造され
ている［A.Pictet and A.Geleznoff,Ber.,36,2219（190
3）,Imperial Chemical Industries Ltd.Brit.,1357955
（1974）参照］。Prior art and its problems Conventionally, tri-lower alkanoyloxyboron has been produced by reacting boric acid with lower alkanoic anhydride [A. Pictet and A. Geleznoff, Ber., 36 , 2219 (190
3), Imperial Chemical Industries Ltd.Brit., 1357955
(1974)].
しかしながら、この方法によれば、急激な発熱を伴い
爆発の危険性があり［Leon M.Lerner,Chem.Eng.News,19
73,51（34）］、また反応時間も長い等操作が煩雑で、
大量合成を行ない得ず、従って工業的製法として不適当
であるという欠点を有している。However, according to this method, there is a danger of explosion with rapid heat generation [Leon M. Lerner, Chem. Eng. News, 19
73,51 (34)]
It has the disadvantage that large scale synthesis cannot be carried out and is therefore unsuitable as an industrial process.
一方、無水ホウ酸と無水低級アルカン酸とを反応させ
ることによりトリ低級アルカノイルオキシホウ素を得る
方法も知られている［A.Pictet and A.Geleznoff,Ber.,
36,2219（1903）参照］。On the other hand, a method of obtaining tri-lower alkanoyloxyboron by reacting boric anhydride with lower alkanoic anhydride is also known [A. Pictet and A. Geleznoff, Ber.,
36 , 2219 (1903)].
しかしながら、この方法によれば、反応が非常に不活
性であり、長時間の加熱を必要とし、これにより目的物
を高収率、高純度で製造し難いという欠点を有してい
る。However, this method has the drawback that the reaction is very inert and requires a long heating, which makes it difficult to produce the target product in high yield and high purity.
４問題点を解決するための手段 本発明は、上記欠点を有しないトリ低級アルカノイル
オキシホウ素の製造法を提供するものである。Means for Solving the Four Problems The present invention provides a method for producing tri-lower alkanoyloxyboron which does not have the above-mentioned disadvantages.
即ち、本発明は、低級アルカン酸の存在下に無水ホウ
酸と無水低級アルカン酸とを反応させることを特徴とす
るトリ低級アルカノイルオキシホウ素の製造法に係る。That is, the present invention relates to a method for producing tri-lower alkanoyloxyboron, comprising reacting boric anhydride and lower alkanoic anhydride in the presence of lower alkanoic acid.
本発明で得られるトリ低級アルカノイルオキシホウ素
は、抗菌剤を合成するための中間体として有用な一般式 ［式中R1は低級アルキル基、Ｘ及びX1はそれぞれハロゲ
ン原子を示す。R2は基 （R3及びR4はそれぞれ低級アルキル基）を示す。］ で表わされるベンゾヘテロ環化合物及びその塩を製造す
る際の有用な試薬である。例えば上記一般式（１）のベ
ンゾヘテロ環化合物は、下記反応式に従い製造される。The tri-lower alkanoyloxyboron obtained in the present invention has a general formula useful as an intermediate for synthesizing an antibacterial agent. [Wherein R 1 represents a lower alkyl group, and X and X 1 each represent a halogen atom. R 2 is a group (R 3 and R 4 are each a lower alkyl group). ] It is a useful reagent when producing the benzoheterocyclic compound represented by these, and its salt. For example, the benzoheterocyclic compound of the above general formula (1) is produced according to the following reaction formula.
［式中R1、R2、R3、R4、Ｘ及びX1は前記に同じ。R5は低
級アルキル基を示す。R6は水素原子又は低級アルキル基
を示す。］ 一般式（1a）の化合物と本発明の一般式（２）の化合
物の反応は、適当な溶媒中にて行なわれる。ここで使用
される溶媒としては、例えばジエチルエーテル、ジオキ
サン、テトラヒドロフラン、モノグライム、ジグライム
等のエーテル類、ベンゼン、トルエン、キシレン等の芳
香族炭化水素類、ｎ−ヘキサン、ヘプタン、シクロヘキ
サン等の脂肪族炭化水素類、無水酢酸等の無水低級アル
カン酸類、ジメチルホルムアミド（DMF）、ジメチルス
ルホキシド（DMSO）、ヘキサメチルリン酸トリアミド
（HMPA）、アセトニトリル、Ｎ−メチルプロリドン等の
非プロトン性極性溶媒等が挙げられる。該反応は、通常
室温〜200℃程度、好ましくは室温〜150℃付近にて進行
し、一般に10〜５時間程度にて終了する。一般式（２）
の化合物の使用量は、一般式（1a）の化合物に対して少
なくとも等モル程度、好ましくは等モル〜10倍モルとす
るのがよい。 [Wherein R 1 , R 2 , R 3 , R 4 , X and X 1 are the same as above. R 5 represents a lower alkyl group. R 6 represents a hydrogen atom or a lower alkyl group. The reaction between the compound of the general formula (1a) and the compound of the general formula (2) of the present invention is carried out in a suitable solvent. Examples of the solvent used here include ethers such as diethyl ether, dioxane, tetrahydrofuran, monoglyme and diglyme, aromatic hydrocarbons such as benzene, toluene and xylene, and aliphatic hydrocarbons such as n-hexane, heptane and cyclohexane. Hydrogens, lower alkanoic anhydrides such as acetic anhydride, aprotic polar solvents such as dimethylformamide (DMF), dimethylsulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), acetonitrile, N-methylprolidone and the like. Can be The reaction proceeds usually at about room temperature to about 200 ° C., preferably at about room temperature to about 150 ° C., and is generally completed in about 10 to 5 hours. General formula (2)
The amount of the compound of the formula (I) is at least about equimolar to the compound of the general formula (1a), preferably from equimolar to 10-fold molar.
ここで、一般式（１）の化合物は、例えば抗菌剤とし
て有用な一般式 ［式中R1及びＸは前記に同じ。R7は基 （R8は水素原子又は低級アルキル基を示す。）又は （Ｚは酸素原子、硫黄原子又はメチレン基を示す。ｍは
１又は２を示す、R9は水素原子、低級アルキル基、低級
アルコキシ基、水酸基、フェニル低級アルキル基、低級
アルカノイルオキシ基、置換基として低級アルキル基又
は低級アルカノイル基を有することのあるアミノ基、オ
キソ基又はカルバモイル基を示す。）を示す。］ で表わされるベンゾヘテロ環化合物を合成するための中
間体として有用である。Here, the compound represented by the general formula (1) is, for example, a compound represented by the general formula: Wherein R 1 and X are as defined above. R 7 is a group (R 8 represents a hydrogen atom or a lower alkyl group.) (Z represents an oxygen atom, a sulfur atom or a methylene group; m represents 1 or 2; R 9 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a hydroxyl group, a phenyl lower alkyl group, a lower alkanoyloxy group, a substituent Represents an amino group, oxo group or carbamoyl group which may have a lower alkyl group or a lower alkanoyl group). ] It is useful as an intermediate for synthesizing the benzoheterocyclic compound represented by
一般式（１）の化合物を合成中間体として用いると、
一般式（Ａ）のベンゾヘテロ環化合物を緩和な条件下、
短時間で、高収率、高純度にてしかも工業的規模にて製
造することができる。When the compound of the general formula (1) is used as a synthetic intermediate,
Under mild conditions, the benzoheterocyclic compound of the general formula (A)
It can be produced in a short time, with high yield and high purity, and on an industrial scale.
また一般式（Ａ）の化合物は、上記一般式（１）の化
合物と一般式R7H（R7は前記と同じ）で表わされる化合
物とから、下記に示す方法によっても製造され得る。The compound of the general formula (A) can also be produced from the compound of the above general formula (1) and a compound represented by the general formula R 7 H (R 7 is the same as described above) by the following method.
［式中R1、R2、R7、X1及びＸは前記に同じ。］ 一般式（１）の化合物と一般式（３）の化合物との反
応において、両者の使用割合は特に限定がなく広い範囲
から適宜選択できるが、通常前者に対して後者を少なく
とも等モル程度、好ましくは等モル〜５倍モル程度使用
するのがよい。該反応は不活性溶媒、具体的には水、メ
タノール、エタノール、イソプロパノール、ブタノー
ル、アミルアルコール、イソアミルアルコール等のアル
コール類、ベンゼン、トルエン、キシレン等の芳香族炭
化水素類、テトラヒドロフラン、ジオキサン、ジグライ
ム等のエーテル類、ジメチルアセタミド、DMF、DMSO、H
MPA、アセトニトリル、Ｎ−メチルピロリドン等又はこ
れらの混合溶媒中で行なわれる。これらのうちDMF、DMS
O、HMPA、アセトニトリル及びＮ−メチルピロリドンが
好ましい。また該反応は脱酸剤、具体的には炭酸ナトリ
ウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カ
リウム、水素化ナトリウム等の無機炭酸塩類、ピリジ
ン、キノリン、トリエチルアミン等の有機塩基類等の存
在下に行なうこともできる。また弗化カリウム等のアル
カリ金属ハロゲン化物を添加してもよい。反応は通常１
〜20気圧、好ましくは１〜10気圧の圧力下、室温〜250
℃程度、好ましくは室温〜200℃の温度下に行なわれ、
一般に10分〜30時間程度で終了する。 [Wherein R 1 , R 2 , R 7 , X 1 and X are the same as above. In the reaction between the compound of the general formula (1) and the compound of the general formula (3), the ratio of the two can be appropriately selected from a wide range without any particular limitation. Preferably, it is used in an equimolar to about 5-fold molar amount. The reaction is carried out with an inert solvent, specifically water, alcohols such as methanol, ethanol, isopropanol, butanol, amyl alcohol, isoamyl alcohol, aromatic hydrocarbons such as benzene, toluene, xylene, tetrahydrofuran, dioxane, diglyme, etc. Ethers, dimethylacetamide, DMF, DMSO, H
The reaction is performed in MPA, acetonitrile, N-methylpyrrolidone, or the like, or a mixed solvent thereof. Of these, DMF, DMS
O, HMPA, acetonitrile and N-methylpyrrolidone are preferred. The reaction is carried out in the presence of a deoxidizing agent, specifically, an inorganic carbonate such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride, or an organic base such as pyridine, quinoline or triethylamine. You can do it. Further, an alkali metal halide such as potassium fluoride may be added. Reaction is usually 1
~ 20 atm, preferably 1-10 atm, room temperature ~ 250
C., preferably at a temperature of room temperature to 200 ° C.,
Generally, it is completed in about 10 minutes to 30 hours.
上記で製造された一般式（Ａ′）の化合物を酸又は塩
基性化合物で処理することによりキレートを分解させ、
対応するR2が水素原子である化合物（Ａ）に導くことが
できる。ここで使用される酸としては、塩酸、硫酸等の
鉱酸、酢酸、ｐ−トルエンスルホン酸等の有機酸が挙げ
られる。塩基性化合物としては、水酸化ナトリウム、水
酸化カリウム、炭酸水素ナトリウム、炭酸水素カリウ
ム、炭酸カリウム等の無機塩基、トリエチルアミン等の
有機塩基が挙げられる。外反応は、０〜150℃程度、好
ましくは０〜100℃付近にて好適に進行する。酸又は塩
基性化合物の使用量しては、原料化合物に対して通常少
なくとも等モル程度、好ましくは１〜10倍量使用するの
がよい。A chelate is decomposed by treating the compound of the general formula (A ′) produced above with an acid or a basic compound,
It can lead to compounds (A) in which the corresponding R 2 is a hydrogen atom. Examples of the acid used here include mineral acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid and p-toluenesulfonic acid. Examples of the basic compound include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, and potassium carbonate, and organic bases such as triethylamine. The external reaction suitably proceeds at about 0 to 150 ° C, preferably at about 0 to 100 ° C. The amount of the acid or basic compound to be used is usually at least about equimolar, preferably 1 to 10 times, relative to the starting compound.
本発明の方法は、低級アルカン酸の存在下、無水ホウ
酸と無水低級アルカン酸とを反応させることにより実施
される。The method of the present invention is carried out by reacting boric anhydride with lower alkanoic anhydride in the presence of lower alkanoic acid.
本明細書において、低級アルカノイルオキシ基として
は、例えばアセチルオキシ、プロピオニルオキシ、ブチ
リルオキシ、イソブチリルオキシ、ペンタノイルオキ
シ、tert−ブチルカルボニルオキシ、ヘキサノイルオキ
シ基等の炭素数２〜６の直鎖又は分枝鎖状アルカノイル
オキシ基が挙げられる。In the present specification, examples of the lower alkanoyloxy group include a straight chain having 2 to 6 carbon atoms such as acetyloxy, propionyloxy, butyryloxy, isobutyryloxy, pentanoyloxy, tert-butylcarbonyloxy, and hexanoyloxy groups. Or a branched alkanoyloxy group.
無水低級アルカン酸としては、例えば無水酢酸、無水
プロピオン酸、無水酪酸、無水イソ酪酸、無水吉草酸、
無水イソ吉草酸、無水ピバリン酸、無水ヘキサン酸等の
炭素数２〜６の直鎖又は分枝鎖状無水アルカン酸を挙げ
ることができる。Examples of the lower alkanoic anhydride include acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride,
Examples thereof include linear or branched alkanoic anhydrides having 2 to 6 carbon atoms such as isovaleric anhydride, pivalic anhydride, and hexanoic anhydride.
低級アルカン酸としては、例えば酢酸、プロピオン
酸、酪酸、イソ酪酸、吉草酸、イソ吉草酸、ピバリン
酸、ヘキサン酸等の炭素数２〜６の直鎖又は分枝鎖状ア
ルカン酸を挙げることができる。Examples of the lower alkanoic acid include linear or branched alkanoic acids having 2 to 6 carbon atoms, such as acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, and hexanoic acid. it can.
本発明の反応は、通常室温〜200℃、好ましくは室温
〜150℃付近にて行なわれ、一般に0.5〜２時間程度で終
了する。The reaction of the present invention is carried out usually at room temperature to 200 ° C., preferably at room temperature to around 150 ° C., and is generally completed in about 0.5 to 2 hours.
本発明において、無水低級アルカン酸は、無水ホウ酸
に対して通常大過剰量、好ましくは３〜20倍モル量使用
するのがよい。また低級アルカン酸の使用量としては、
特に限定されず、通常無水ホウ酸に対して１〜50倍重量
使用するのがよい。In the present invention, the lower alkanoic anhydride is usually used in a large excess amount, preferably 3 to 20-fold molar amount, based on boric anhydride. The amount of lower alkanoic acid used is
There is no particular limitation, and it is usually preferable to use 1 to 50 times the weight of boric anhydride.
斯くして得られる本発明の目的化合物は、通常の分離
手段により容易に単離、精製できる。該分離手段として
は、例えば溶媒抽出法、希釈法、再結晶法、カラムクロ
マトグラフィー、プレパラティブ薄層クロマトグラフィ
ー等が挙げられる。The target compound of the present invention thus obtained can be easily isolated and purified by ordinary separation means. Examples of the separation means include a solvent extraction method, a dilution method, a recrystallization method, column chromatography, and preparative thin-layer chromatography.
発明の効果 本発明による製造法は、従来の方法に比し、反応時間
が短く、爆発の危険性もなく、また反応操作は極めて簡
便であり、高収率、高純度にて大量合成も容易であり、
従って工業的に極めて有利な方法である。Effect of the Invention The production method according to the present invention has a shorter reaction time and no danger of explosion than conventional methods, the reaction operation is extremely simple, and high-volume synthesis with high yield and high purity is easy. And
Therefore, it is an industrially advantageous method.
実施例 以下に実施例及び参考例を掲げて本発明をより一層明
らかにする。Examples Hereinafter, the present invention will be further clarified with reference to Examples and Reference Examples.
実施例１ 無水ホウ酸0.56g、無水酢酸9.2g及び酢酸2.9gを混合
し、均一溶液になるまで約１時間加熱還流する。反応終
了後、反応液を濃縮し、得られた残渣に石油エーテルを
加え、析出する結晶を取し、これを乾燥させてトリア
セチルオキシホウ素3.0g（収率98.5％）を得る。Example 1 A mixture of 0.56 g of boric anhydride, 9.2 g of acetic anhydride and 2.9 g of acetic acid was heated and refluxed for about 1 hour until a homogeneous solution was obtained. After completion of the reaction, the reaction solution was concentrated, petroleum ether was added to the obtained residue, and the precipitated crystals were collected and dried to obtain 3.0 g of triacetyloxyboron (yield 98.5%).
融点121℃、白色結晶 元素分析（C6H9O6Bとして） Ｃ Ｈ 計算値（％） 38.34 4.83 実測値（％） 38.56 4.95 参考例１ 8,9−ジフルオロ−５−メチル−6,7−ジヒドロ−１−オ
キソ−1H,5H−ベンゾ［ij］キノリジン−２−カルボン
酸 −Ｂ（OCOCH3）２キレート0.81g、４−ヒドロキシピ
ペリジン0.81g及びアセトニトリル2.8mlを混合し、50〜
80℃にて30分〜４時間撹拌する。反応混合物に濃塩酸8.
1mlを加え、10分間加熱還流後冷却し、析出晶を取す
る。50％エタノールより再結晶して0.50gの９−フルオ
ロ−８−（４−ヒドロキシ−１−ピペリジニル）−５−
メチル−6,7−ジヒドロ−１−オキソ−1H,5H−ベンゾ
［ij］キノリジン−２−カルボン酸を得る。Melting point 121 ° C, white crystal Elemental analysis (as C 6 H 9 O 6 B) Calculated value of CH (%) 38.34 4.83 Actual value (%) 38.56 4.95 Reference Example 1 8,9-difluoro-5-methyl-6,7 -Dihydro-1-oxo-1H, 5H-benzo [ij] quinolidine-2-carboxylic acid-B (OCOCH 3 ) 0.81 g of 2- chelate, 0.81 g of 4-hydroxypiperidine and 2.8 ml of acetonitrile were mixed, and 50-
Stir at 80 ° C. for 30 minutes to 4 hours. Add concentrated hydrochloric acid to the reaction mixture.
1 ml is added, and the mixture is heated under reflux for 10 minutes and cooled, and the precipitated crystals are collected. Recrystallization from 50% ethanol gave 0.50 g of 9-fluoro-8- (4-hydroxy-1-piperidinyl) -5-.
Methyl-6,7-dihydro-1-oxo-1H, 5H-benzo [ij] quinolidine-2-carboxylic acid is obtained.
融点247℃（分解）、白色結晶 参考例２ 8,9−ジフルオロ−５−メチル−6,7−ジヒドロ−１−オ
キソ−1H,5H−ベンゾ［ij］キノリジン−２−カルボン
酸 −Ｂ（OCOCH3）２キレート3.46gを用い、参考例２と
同様にして９−フルオロ−８−（４−メチル−１−ピペ
ラジニル）−５−メチル−6,7−ジヒドロ−１−オキソ
−1H,5H−ベンゾ［ij］キノリジン−２−カルボン酸を2
7.48gを得る。Melting point 247 ° C. (decomposition), white crystals Reference Example 2 8,9-difluoro-5-methyl-6,7-dihydro-1-oxo-1H, 5H-benzo [ij] quinolidine-2-carboxylic acid-B (OCOCH 3 ) 9-Fluoro-8- (4-methyl-1-piperazinyl) -5-methyl-6,7-dihydro-1-oxo-1H, 5H- using 3.46 g of 2- chelate in the same manner as in Reference Example 2. Benzo [ij] quinolidine-2-carboxylic acid is converted to 2
7.48 g are obtained.
融点261℃（分解）、白色結晶 参考例３ 無水ホウ酸24.8g、無水酢酸407ml及び酢酸123mlを混
合し、均一溶液になるまで約１時間加熱還流する。得ら
れたトリアセチルオキシホウ素は、単離することなく、
上記反応液に8,9−ジフルオロ−５−メチル−6,7−ジヒ
ドロ−１−オキソ−1H,5H−ベンゾ［ij］キノリジン−
２−カルボン酸182gを加え、更に１時間加熱還流する。
その後溶媒を濃縮後、更にトルエン共沸を繰り返した
後、トルエンを留去する。265.37gの8,9−ジフルオロ−
５−メチル−6,7−ジヒドロ−１−オキソー1H,5H−ベン
ゾ［ij］キノリジン−２−カルボン酸−Ｂ（OCOCH3）２
キレートを得る。Melting point: 261 ° C. (decomposition), white crystals Reference Example 3 24.8 g of boric anhydride, 407 ml of acetic anhydride and 123 ml of acetic acid were mixed, and the mixture was heated under reflux for about 1 hour until a homogeneous solution was obtained. The obtained triacetyloxyboron can be isolated without isolation.
8,9-Difluoro-5-methyl-6,7-dihydro-1-oxo-1H, 5H-benzo [ij] quinolidine-
182 g of 2-carboxylic acid is added, and the mixture is further heated under reflux for 1 hour.
Then, after concentrating the solvent and repeating the toluene azeotrope, the toluene is distilled off. 265.37 g of 8,9-difluoro-
5-methyl-6,7-dihydro-1-oxo 1H, 5H-benzo [ij] quinolidine-2-carboxylic acid-B (OCOCH 3 ) 2
Get a chelate.
融点205℃（分解）、白色結晶 参考例４ 参考例３と同様にして適当な出発原料を用いて以下の
化合物を得る。Melting point 205 ° C. (decomposition), white crystals Reference Example 4 The following compound is obtained in the same manner as in Reference Example 3 using appropriate starting materials.
８−ブロモ−９−フルオロ−５−メチル−6,7−ジヒド
ロ−１−オキソ−1H,5H−ベンゾ［ij］キノリジン−２
−カルボン酸−Ｂ（OCOCH3）２キレート 融点215℃（分解）、白色結晶8-bromo-9-fluoro-5-methyl-6,7-dihydro-1-oxo-1H, 5H-benzo [ij] quinolidine-2
-Carboxylic acid-B (OCOCH 3 ) 2 chelate Melting point 215 ° C (decomposition), white crystals
Claims (2)
水低級アルカン酸とを反応させることを特徴とするトリ
低級アルカノイルオキシホウ素の製造法。1. A process for producing tri-lower alkanoyloxyboron, comprising reacting boric anhydride with lower alkanoic anhydride in the presence of lower alkanoic acid.
ン原子を示す。R2は基 （R3及びR4はそれぞれ低級アルキル基）を示す。〕 で表わされるベンゾヘテロ環化合物又はその塩。2. The general formula [Wherein R 1 represents a lower alkyl group, and X and X 1 each represent a halogen atom. R 2 is a group (R 3 and R 4 are each a lower alkyl group). ] The benzo heterocyclic compound represented by these, or its salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP923489A JP2731853B2 (en) | 1989-01-17 | 1989-01-17 | Method for producing tri-lower alkanoyloxyboron |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP923489A JP2731853B2 (en) | 1989-01-17 | 1989-01-17 | Method for producing tri-lower alkanoyloxyboron |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02188589A JPH02188589A (en) | 1990-07-24 |
| JP2731853B2 true JP2731853B2 (en) | 1998-03-25 |
Family
ID=11714715
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP923489A Expired - Lifetime JP2731853B2 (en) | 1989-01-17 | 1989-01-17 | Method for producing tri-lower alkanoyloxyboron |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2731853B2 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6750224B1 (en) | 1999-05-07 | 2004-06-15 | Wockhardt Limited | Antibacterial optically pure benzoquinolizine carboxylic acids, processes, compositions and methods of treatment |
| EP1175217B8 (en) | 1999-05-07 | 2009-03-18 | Wockhardt Limited | (s)-benzoquinolizine carboxylic acids and their use as antibacterial agents |
| US6514986B2 (en) | 2000-11-22 | 2003-02-04 | Wockhardt Limited | Chiral fluoroquinolone arginine salt forms |
| US6608078B2 (en) | 2000-05-08 | 2003-08-19 | Wockhardt Limited | Antibacterial chiral 8-(substituted piperidino)-benzo [i,j] quinolizines, processes, compositions and methods of treatment |
| US7098219B2 (en) | 2000-08-01 | 2006-08-29 | Wockhart Limited | Inhibitors of cellular efflux pumps of microbes |
| US6964966B2 (en) | 2001-04-25 | 2005-11-15 | Wockhardt Limited | Generation triple-targeting, chiral, broad-spectrum antimicrobial 7-substituted piperidino-quinolone carboxylic acid derivatives, their preparation, compositions and use as medicaments |
| US6878713B2 (en) | 2001-04-25 | 2005-04-12 | Wockhardt Limited | Generation triple-targeting, chiral, broad-spectrum antimicrobial 7-substituted piperidino-quinolone carboxylic acid derivatives, their preparation, compositions and use as medicaments |
| US6664267B1 (en) | 2002-05-28 | 2003-12-16 | Wockhardt Limited | Crystalline fluoroquinolone arginine salt form |
| JP5255183B2 (en) | 2003-09-04 | 2013-08-07 | ウォックハート リミテッド | Benzoquinolidine-2-carboxylic acid arginine salt tetrahydrate |
-
1989
- 1989-01-17 JP JP923489A patent/JP2731853B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02188589A (en) | 1990-07-24 |
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