JPH04243882A - Production of tri-lower alkanoyloxyboron - Google Patents
Production of tri-lower alkanoyloxyboronInfo
- Publication number
- JPH04243882A JPH04243882A JP1921991A JP1921991A JPH04243882A JP H04243882 A JPH04243882 A JP H04243882A JP 1921991 A JP1921991 A JP 1921991A JP 1921991 A JP1921991 A JP 1921991A JP H04243882 A JPH04243882 A JP H04243882A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- formula
- acid
- anhydride
- raw material
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000004327 boric acid Substances 0.000 claims abstract description 10
- -1 boric acid ester Chemical class 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 13
- KWZWNVAHEQHCTQ-UHFFFAOYSA-N diacetyloxyboranyl acetate Chemical compound CC(=O)OB(OC(C)=O)OC(C)=O KWZWNVAHEQHCTQ-UHFFFAOYSA-N 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 238000004880 explosion Methods 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 5
- 229940079593 drug Drugs 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 4
- XOQQVKDBGLYPGH-UHFFFAOYSA-N 2-oxo-1h-quinoline-3-carboxylic acid Chemical compound C1=CC=C2NC(=O)C(C(=O)O)=CC2=C1 XOQQVKDBGLYPGH-UHFFFAOYSA-N 0.000 abstract description 3
- 150000008065 acid anhydrides Chemical class 0.000 abstract description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 8
- 235000010338 boric acid Nutrition 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- BXMFEHXUVNKJHI-UHFFFAOYSA-N diacetyloxyboron Chemical compound CC(=O)O[B]OC(C)=O BXMFEHXUVNKJHI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 1
- FREZLSIGWNCSOQ-UHFFFAOYSA-N 3-methylbutanoyl 3-methylbutanoate Chemical compound CC(C)CC(=O)OC(=O)CC(C)C FREZLSIGWNCSOQ-UHFFFAOYSA-N 0.000 description 1
- 229910015444 B(OH)3 Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- POCFBDFTJMJWLG-UHFFFAOYSA-N dihydrosinapic acid methyl ester Natural products COC(=O)CCC1=CC(OC)=C(O)C(OC)=C1 POCFBDFTJMJWLG-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- LSACYLWPPQLVSM-UHFFFAOYSA-N isobutyric acid anhydride Chemical compound CC(C)C(=O)OC(=O)C(C)C LSACYLWPPQLVSM-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- DUCKXCGALKOSJF-UHFFFAOYSA-N pentanoyl pentanoate Chemical compound CCCCC(=O)OC(=O)CCCC DUCKXCGALKOSJF-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- LTEHWCSSIHAVOQ-UHFFFAOYSA-N tripropyl borate Chemical compound CCCOB(OCCC)OCCC LTEHWCSSIHAVOQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、トリアルカノイルオキ
シホウ素の新規な製造法に関する。後記トリアルカノイ
ルオキシホウ素（ＩＩＩ）は、ホウ酸アルカン酸無水物
またはトリアシルホウ酸とも呼ばれ、医薬、農薬等の製
造、とくにキノロンカルボン酸系医薬の製造原料として
重要な化合物である（特開昭６０−７５４８９号、特開
昭６０−７８９８６号各公報）。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel method for producing trialkanoyloxyboron. Trialkanoyloxyboron (III), which will be described later, is also called boric alkanoic anhydride or triacylboric acid, and is an important compound for the production of medicines, agricultural chemicals, etc., especially as a raw material for the production of quinolone carboxylic acid medicines (Japanese Unexamined Patent Application Publication No. 1989-1983) -75489 and Japanese Patent Application Laid-Open No. 60-78986).
【０００２】0002
【従来の技術】従来トリアルカノイルオキシホウ素を合
成する方法は、
（１）ホウ酸と無水低級アルカン酸とを反応させる方法
［Ｃｈｅｍ． Ｂｅｒ．， ３６，２２１９（１９０３
）、英国特許第１３５７９５５号明細書、Ｊ． Ｃｈｅ
ｍ． Ｅｄｕｃ．， ５１，６８８（１９７４）］
Ｂ（ＯＨ）３＋３（ＣＨ３ ＣＯ）２Ｏ→Ｂ（ＯＣＯＣ
Ｈ３）３ ＋３ＣＨ３ ＣＯ２ Ｈ
（２）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方法［特開平２−１８８５
８９号公報］
Ｂ２ Ｏ３ ＋３（ＲＣＯ）２Ｏ→２Ｂ（ＯＣＯＲ）３
（３）無水ホウ酸と無水低級アルカン酸とを反応させる
方法［Ｃｈｅｍ． Ｂｅｒ．， ３６，２２１９（１９
０３）］が知られている。BACKGROUND OF THE INVENTION Conventional methods for synthesizing trialkanoyloxyboron include (1) a method of reacting boric acid with lower alkanoic anhydride [Chem. Ber. , 36, 2219 (1903
), British Patent No. 1357955, J. Che
m. Educ. , 51, 688 (1974)] B(OH)3+3(CH3CO)2O→B(OCOC
H3)3 +3CH3 CO2 H (2) A method of reacting boric anhydride and lower alkanoic anhydride in the presence of a lower alkanoic acid [JP-A-2-1885
No. 89] B2 O3 +3(RCO)2O→2B(OCOR)3
(3) Method of reacting boric anhydride and lower alkanoic anhydride [Chem. Ber. , 36,2219 (19
03)] is known.
【０００３】（１）の方法は、爆発の危険性があること
が報告されており［Ｃｈｅｍ． Ｅｎｇ． Ｎｅｗｓ
３４，５１（１９７３）］、発熱のコントロールはホウ
酸が固体であるため難しく、工業的製造方法としては適
していない。
（２）の方法は、（１）の方法の爆発危険性を回避する
ため、無水ホウ酸を使用しているが、２種類の比較的多
量の溶媒を必要とし、その高沸点溶媒を減圧留去しなけ
ればならず、生産性が低い。
（３）の方法は、反応が非常に遅く長時間の加熱を必要
とし、目的物を高収率、高純度で得ることは難しい。ま
た、これらいずれの方法も固体の原料を使用しているた
め、工業的な製造法としては原料物質の仕込み、反応の
制御、反応の均一性等の点で好ましくない。It has been reported that method (1) has a risk of explosion [Chem. Eng. News
34, 51 (1973)], control of heat generation is difficult because boric acid is a solid, and it is not suitable as an industrial production method. Method (2) uses boric anhydride to avoid the explosion hazard of method (1), but it requires two relatively large amounts of solvent, and the high boiling point solvent can be removed by distillation under reduced pressure. productivity is low. In method (3), the reaction is very slow and requires long-term heating, making it difficult to obtain the target product in high yield and purity. Furthermore, since all of these methods use solid raw materials, they are not preferred as industrial production methods in terms of charging raw materials, controlling the reaction, and uniformity of the reaction.
【０００４】0004
【発明が解決しようとする課題】本発明は、工業的な製
造法として、原料物質の仕込み、反応の制御、反応の均
一性等の点で優れている液体物質を反応させることによ
り、安全にかつ収率よくトリアルカノイルオキシホウ素
を得ることを目的とする。[Problems to be Solved by the Invention] The present invention is an industrial manufacturing method that uses a liquid substance that is excellent in terms of preparation of raw materials, control of the reaction, uniformity of the reaction, etc., and enables safe production. The object is to obtain trialkanoyloxyboron in good yield.
【０００５】[0005]
【課題を解決するための手段】本発明は、一般式（Ｉ）
で示されるホウ酸エステルと一般式（ＩＩ）で示される
無水アルカン酸とを反応させることを特徴とする、一般
式（ＩＩＩ） で示されるトリアルカノイルオキシホウ
素の製造方法である。[Means for Solving the Problems] The present invention provides general formula (I)
This is a method for producing trialkanoyloxyboron represented by general formula (III), which is characterized by reacting a boric acid ester represented by formula (III) with an alkanoic anhydride represented by general formula (II).
【化２】
（式中Ｒ１ 及びＲ２ は同一でも異なっても良く、炭
素数１〜５のアルキル基を表す）[Formula 2] (In the formula, R1 and R2 may be the same or different and represent an alkyl group having 1 to 5 carbon atoms)
【０００６】本製法に使用されるホウ酸アルキルエステ
ル（Ｉ）としては、トリメチルホウ酸、トリエチルホウ
酸、トリプロピルホウ酸、トリイソプロピルホウ酸、ト
リブチルホウ酸、トリアミルホウ酸、トリイソブチルホ
ウ酸等が挙げられる。[0006] As the boric acid alkyl ester (I) used in this production method, trimethylboric acid, triethylboric acid, tripropylboric acid, triisopropylboric acid, tributylboric acid, triamylboric acid, triisobutylboric acid, etc. Can be mentioned.
【０００７】本製法に使用される無水アルカン酸（ＩＩ
）としては、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、無水イソ吉草酸等が挙げら
れる。Alkanoic anhydride (II) used in this production method
) include acetic anhydride, propionic anhydride, butyric anhydride,
Examples include isobutyric anhydride, valeric anhydride, isovaleric anhydride, and the like.
【０００８】本製法で得られるトリアルカノイルオキシ
ホウ素（ＩＩＩ）としては、トリアセチルオキシホウ素
、トリプロピオニルオキシホウ素、トリブチリルオキシ
ホウ素、トリイソブチリルオキシホウ素等が挙げられる
。[0008] Trialkanoyloxyboron (III) obtained by this production method includes triacetyloxyboron, tripropionyloxyboron, tributyryloxyboron, triisobutyryloxyboron, and the like.
【０００９】ホウ酸アルキルエステル（Ｉ）と無水アル
カン酸（ＩＩ）とのモル比は、通常１：５である。どち
らかを過剰に使用して、反応後除去する方法を行えば、
反応速度が上がり、反応時間が短縮される。どちらの原
料を過剰にするかは除去のし易さにもよるが、通常無水
アルカン酸を過剰量使用するほうが良い。The molar ratio of boric acid alkyl ester (I) to alkanoic anhydride (II) is usually 1:5. If either is used in excess and removed after the reaction,
The reaction rate is increased and the reaction time is shortened. Which raw material to use in excess depends on the ease of removal, but it is usually better to use an excess amount of alkanoic acid anhydride.
【００１０】本製法では原料が液体であるため、通常溶
媒は必要でない。しかし、本反応は溶媒の存在下でも実
施可能である。その際溶媒としては、反応に関与しない
ベンゼン、トルエン、キシレン等の芳香族炭化水素類、
ジエチルエーテル、ジイソプロピルエーテル、ジブチル
エーテル、テトラヒドロフラン等のエーテル類、塩化メ
チレン、クロロホルム、ジクロルエタン等のハロゲン化
炭化水素類、または使用する無水アルカン酸と同一のア
ルカン酸も使用可能である。[0010] In this production method, since the raw material is liquid, a solvent is usually not required. However, this reaction can also be carried out in the presence of a solvent. In this case, as a solvent, aromatic hydrocarbons such as benzene, toluene, xylene, etc. that do not participate in the reaction,
Ethers such as diethyl ether, diisopropyl ether, dibutyl ether and tetrahydrofuran, halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane, or the same alkanoic acid as the alkanoic anhydride used can also be used.
【００１１】反応温度は使用する原料の沸点に依存する
が、室温から１５０℃の範囲で実施可能である。より好
ましくは２５〜８０℃の範囲である。反応液の濃度には
とくに制約はなく、前述したように無溶媒でも実施でき
る。反応は通常２時間以内に完結する。[0011] The reaction temperature depends on the boiling point of the raw materials used, but it can be carried out in the range from room temperature to 150°C. More preferably, the temperature is in the range of 25 to 80°C. There are no particular restrictions on the concentration of the reaction solution, and as described above, the reaction can be carried out without a solvent. The reaction is usually completed within 2 hours.
【００１２】反応終了後の操作としては、反応混合物を
減圧下に濃縮した後、生成物を目的物が溶解しにくい溶
媒で洗浄する方法、又は冷却により目的物を析出させる
方法が推奨される。本洗浄溶媒としては、ヘキサン、ペ
ンタン、オクタン、リグロイン、石油エーテル、シクロ
ヘキサン等の飽和炭化水素溶媒；エチルエーテル、イソ
プロピルエーテル、ブチルエーテル等のエーテル系溶媒
；塩化メチレン等のハロゲン化炭化水素溶媒が優れてい
る。[0012] Recommended operations after completion of the reaction include a method in which the reaction mixture is concentrated under reduced pressure and then the product is washed with a solvent in which the target product is hardly dissolved, or a method in which the target product is precipitated by cooling. As the main cleaning solvent, saturated hydrocarbon solvents such as hexane, pentane, octane, ligroin, petroleum ether, and cyclohexane; ether solvents such as ethyl ether, isopropyl ether, and butyl ether; and halogenated hydrocarbon solvents such as methylene chloride are excellent. There is.
【００１３】[0013]
【実施例】以下に実施例を挙げて、さらに本発明の製法
について説明する。
実施例１
ホウ酸トリメチル４．５７ｇ と無水酢酸２０．４ｇ
とを混合し、１．５時間加熱還流した。反応終了後冷却
し、無水酢酸を減圧下に留去して、石油エーテル４０ｍ
ｌを加えた。析出結晶をろ過、乾燥して、無色固体のト
リアセチルオキシホウ素５．５ｇ を得た。融点１２０
〜１２３℃。[Examples] The production method of the present invention will be further explained with reference to Examples below. Example 1 4.57 g of trimethyl borate and 20.4 g of acetic anhydride
and heated under reflux for 1.5 hours. After the reaction was completed, it was cooled and acetic anhydride was distilled off under reduced pressure to obtain 40ml of petroleum ether.
Added l. The precipitated crystals were filtered and dried to obtain 5.5 g of triacetyloxyboron as a colorless solid. Melting point 120
~123℃.
【００１４】実施例２
ホウ酸トリブチル１０．１ｇ と無水酢酸２０．４ｇ
とを混合し、２時間加熱還流した。反応終了後冷却し、
無水酢酸を減圧下に留去して、石油エーテル４０ｍｌを
加えた。析出結晶をろ過、乾燥して、無色固体のトリア
セチルオキシホウ素５．３ｇ を得た。融点１２０〜１
２３℃。Example 2 10.1 g of tributyl borate and 20.4 g of acetic anhydride
and heated under reflux for 2 hours. After the reaction is completed, cool
Acetic anhydride was distilled off under reduced pressure, and 40 ml of petroleum ether was added. The precipitated crystals were filtered and dried to obtain 5.3 g of triacetyloxyboron as a colorless solid. Melting point 120-1
23℃.
【００１５】参考例１
実施例１で製造したトリアセチルオキシホウ素８．２６
ｇ を無水酢酸２０．４ｇ に加え、さらに１−シクロ
プロピル−６，７−ジフルオロ−８−メトキシ−１，４
−ジヒドロ−４−オキソ−３−キノロンカルボン酸アリ
ルエステル１３．４ｇ と、７０℃で１．５時間反応さ
せた。
反応終了後、冷却してイソプロピルエーテル４０ｍｌを
加え、５℃に冷却した。析出物をろ過し、イソプロピル
エーテルで洗浄し、１−シクロプロピル−６，７−ジフ
ルオロ−８−メトキシ−１，４−ジヒドロ−４−オキソ
−３−キノロンカルボン酸ジアセチルオキシホウ素キレ
ートを１６．１ｇ （９５．２％）得た。融点１０４〜
１０８℃。この化合物は １ＨＮＭＲ、マススペクトル
（ｍ／ｅ ３６４（Ｍ＋ −ＯＡｃ））からホウ酸と
無水酢酸から製造したトリアセチルオキシホウ素を使用
して製造したものと、同一化合物であることを確認した
。Reference Example 1 Triacetyloxyboron produced in Example 1 8.26
g to 20.4 g of acetic anhydride, and further added 1-cyclopropyl-6,7-difluoro-8-methoxy-1,4
-Dihydro-4-oxo-3-quinolonecarboxylic acid allyl ester (13.4 g) was reacted at 70°C for 1.5 hours. After the reaction was completed, the mixture was cooled, 40 ml of isopropyl ether was added, and the mixture was cooled to 5°C. The precipitate was filtered and washed with isopropyl ether, and 16.1 g of 1-cyclopropyl-6,7-difluoro-8-methoxy-1,4-dihydro-4-oxo-3-quinolonecarboxylic acid diacetyloxyboron chelate was obtained. (95.2%). Melting point 104~
108℃. This compound was confirmed from 1H NMR and mass spectra (m/e 364 (M+ -OAc)) to be the same compound as that produced using triacetyloxyboron produced from boric acid and acetic anhydride.
【００１６】参考例２
実施例１で製造したトリアセチルオキシホウ素を単離す
ることなく、反応混合物に、１−シクロプロピル−６，
７−ジフルオロ−８−メトキシ−１，４−ジヒドロ−４
−オキソ−３−キノロンカルボン酸アリルエステル１３
．４ｇ を加え、参考例１と同様に反応させた。１−シ
クロプロピル−６，７−ジフルオロ−８−メトキシ−１
，４−ジヒドロ−４−オキソ−３−キノロンカルボン酸
ジアセチルオキシホウ素キレートを１６．７ｇ 得た。
融点１０４〜１０８℃。Reference Example 2 Without isolating the triacetyloxyboron produced in Example 1, 1-cyclopropyl-6,
7-difluoro-8-methoxy-1,4-dihydro-4
-oxo-3-quinolonecarboxylic acid allyl ester 13
．． 4 g was added, and the reaction was carried out in the same manner as in Reference Example 1. 1-cyclopropyl-6,7-difluoro-8-methoxy-1
, 16.7 g of diacetyloxyboron chelate of 4-dihydro-4-oxo-3-quinolonecarboxylic acid was obtained. Melting point 104-108°C.
【００１７】参考例３
実施例２で製造したトリアセチルオキシホウ素を単離す
ることなく、反応混合物に、１−シクロプロピル−６，
７−ジフルオロ−８−メトキシ−１，４−ジヒドロ−４
−オキソ−３−キノロンカルボン酸アリルエステル１４
．０ｇ を加え、参考例１と同様に反応させた。１−シ
クロプロピル−６，７−ジフルオロ−８−メトキシ−１
，４−ジヒドロ−４−オキソ−３−キノロンカルボン酸
ジアセチルオキシホウ素キレートを１６．４ｇ 得た。
融点１０４〜１０８℃。Reference Example 3 Without isolating the triacetyloxyboron produced in Example 2, 1-cyclopropyl-6,
7-difluoro-8-methoxy-1,4-dihydro-4
-Oxo-3-quinolonecarboxylic acid allyl ester 14
．． 0 g was added, and the reaction was carried out in the same manner as in Reference Example 1. 1-cyclopropyl-6,7-difluoro-8-methoxy-1
, 16.4 g of diacetyloxyboron chelate of 4-dihydro-4-oxo-3-quinolonecarboxylic acid was obtained. Melting point 104-108°C.
【００１８】[0018]
【発明の効果】本発明の製造方法は、従来の方法に比べ
て温和な反応で爆発の危険性はない。また液体原料を使
用するので、反応操作は簡便で、かつ高収率、高純度で
目的物を得ることができる。使用する試薬量が比較的少
ないので生産性が高く、後処理も容易で工業的に有利な
方法である。Effects of the Invention The production method of the present invention has a milder reaction than conventional methods, and there is no danger of explosion. Furthermore, since a liquid raw material is used, the reaction operation is simple and the target product can be obtained in high yield and purity. Since the amount of reagents used is relatively small, productivity is high and post-treatment is easy, making it an industrially advantageous method.
【構成】 ホウ酸エステル（Ｉ）と無水アルカン酸（
ＩＩ）とを反応させることを特徴とするトリアルカノイ
ルオキシホウ素（ＩＩＩ）の製造方法。[Composition] Boric acid ester (I) and alkanoic anhydride (
1. A method for producing trialkanoyloxyboron (III), which comprises reacting the compound with II).
【化３】（式中Ｒ１ 及びＲ２ は炭素数１〜５のアル
キル基を表す）[Formula 3] (wherein R1 and R2 represent an alkyl group having 1 to 5 carbon atoms)
【効果】本発明の製造方法は、従来の方法に比べて温和
な反応で爆発の危険性がなく、液体原料を使用するので
、反応操作は簡便で、高収率、高純度で目的物を得るこ
とができる。トリアルカノイルオキシホウ酸は、キノロ
ンカルボン酸系医薬の原料として有用である。[Effects] Compared to conventional methods, the production method of the present invention is a milder reaction with no risk of explosion, and since liquid raw materials are used, the reaction operation is simple and produces the desired product in high yield and purity. Obtainable. Trialkanoyloxyboric acid is useful as a raw material for quinolone carboxylic acid drugs.
Claims (1)
ルと一般式（ＩＩ）で示される無水アルカン酸とを反応
させることを特徴とする、一般式（ＩＩＩ）で示される
トリアルカノイルオキシホウ素の製造方法。 【化１】 （式中Ｒ１ 及びＲ２ は同一でも異なっても良く、炭
素数１〜５のアルキル基を表す）Claim 1: A trialkanoyloxyboron represented by the general formula (III), which is obtained by reacting a boric acid ester represented by the general formula (I) with an alkanoic anhydride represented by the general formula (II). manufacturing method. [Chemical formula 1] (In the formula, R1 and R2 may be the same or different and represent an alkyl group having 1 to 5 carbon atoms)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1921991A JP2502198B2 (en) | 1991-01-21 | 1991-01-21 | Method for producing tri-lower alkanoyloxyboron |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1921991A JP2502198B2 (en) | 1991-01-21 | 1991-01-21 | Method for producing tri-lower alkanoyloxyboron |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04243882A true JPH04243882A (en) | 1992-08-31 |
| JP2502198B2 JP2502198B2 (en) | 1996-05-29 |
Family
ID=11993257
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1921991A Expired - Fee Related JP2502198B2 (en) | 1991-01-21 | 1991-01-21 | Method for producing tri-lower alkanoyloxyboron |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2502198B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002138092A (en) * | 2000-10-30 | 2002-05-14 | Sumitomo Bakelite Co Ltd | Method for synthesizing tetrax (acyloxy) borate (1-) and substituted onium tetrax (acyloxy) borate (1-) |
| JP2002138091A (en) * | 2000-10-30 | 2002-05-14 | Sumitomo Bakelite Co Ltd | Method for synthesizing tetrax (acyloxy) borate (1-) and substistuted onium tetrax (acyloxy) borate (1-) |
| JP2002167390A (en) * | 2000-11-30 | 2002-06-11 | Sumitomo Bakelite Co Ltd | Synthesizing method of tetrakis(acyloxy)borate(1-) and substituted onium tetrakis(acyloxy)borate(1-) |
| CN105859764A (en) * | 2016-05-04 | 2016-08-17 | 江苏苏南药业实业有限公司 | Preparation method of key intermediate of moxifloxacin |
-
1991
- 1991-01-21 JP JP1921991A patent/JP2502198B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002138092A (en) * | 2000-10-30 | 2002-05-14 | Sumitomo Bakelite Co Ltd | Method for synthesizing tetrax (acyloxy) borate (1-) and substituted onium tetrax (acyloxy) borate (1-) |
| JP2002138091A (en) * | 2000-10-30 | 2002-05-14 | Sumitomo Bakelite Co Ltd | Method for synthesizing tetrax (acyloxy) borate (1-) and substistuted onium tetrax (acyloxy) borate (1-) |
| JP2002167390A (en) * | 2000-11-30 | 2002-06-11 | Sumitomo Bakelite Co Ltd | Synthesizing method of tetrakis(acyloxy)borate(1-) and substituted onium tetrakis(acyloxy)borate(1-) |
| CN105859764A (en) * | 2016-05-04 | 2016-08-17 | 江苏苏南药业实业有限公司 | Preparation method of key intermediate of moxifloxacin |
| CN105859764B (en) * | 2016-05-04 | 2018-06-01 | 江苏苏南药业实业有限公司 | A kind of preparation method of Moxifloxacin important intermediate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2502198B2 (en) | 1996-05-29 |
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