JPH0149247B2 - - Google Patents
Info
- Publication number
- JPH0149247B2 JPH0149247B2 JP17809182A JP17809182A JPH0149247B2 JP H0149247 B2 JPH0149247 B2 JP H0149247B2 JP 17809182 A JP17809182 A JP 17809182A JP 17809182 A JP17809182 A JP 17809182A JP H0149247 B2 JPH0149247 B2 JP H0149247B2
- Authority
- JP
- Japan
- Prior art keywords
- difluorobenzene
- fluoro
- benzenediazonium tetrafluoroborate
- thermal decomposition
- yield
- 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
- -1 2-fluoro-1-benzenediazonium tetrafluoroborate Chemical compound 0.000 claims description 11
- GOYDNIKZWGIXJT-UHFFFAOYSA-N 1,2-difluorobenzene Chemical compound FC1=CC=CC=C1F GOYDNIKZWGIXJT-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229920002545 silicone oil Polymers 0.000 claims description 6
- 238000000034 method Methods 0.000 description 6
- 238000005979 thermal decomposition reaction Methods 0.000 description 6
- FTZQXOJYPFINKJ-UHFFFAOYSA-N 2-fluoroaniline Chemical compound NC1=CC=CC=C1F FTZQXOJYPFINKJ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000006193 diazotization reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000012025 fluorinating agent Substances 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BWSQKOKULIALEW-UHFFFAOYSA-N 2-[2-[4-fluoro-3-(trifluoromethyl)phenyl]-3-[2-(piperidin-3-ylamino)pyrimidin-4-yl]imidazol-4-yl]acetonitrile Chemical compound FC1=C(C=C(C=C1)C=1N(C(=CN=1)CC#N)C1=NC(=NC=C1)NC1CNCCC1)C(F)(F)F BWSQKOKULIALEW-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- RBHJBMIOOPYDBQ-UHFFFAOYSA-N carbon dioxide;propan-2-one Chemical compound O=C=O.CC(C)=O RBHJBMIOOPYDBQ-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明はＯ−ジフルオロベンゼンの新規製法に
関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new method for producing O-difluorobenzene.
Ｏ−ジフルオロベンゼンは公知化合物であつて
公知の抗菌剤（例えば特開昭53−141286号を参
照）の合成中間体として有用である。 O-difluorobenzene is a known compound and is useful as an intermediate for the synthesis of known antibacterial agents (see, for example, JP-A-53-141286).
このＯ−ジフルオロベンゼンの製法としては、
Ｏ−フルオロアニリンをジアゾ化して得られる２
−フルオロ−１−ベンゼンジアゾニウムテトラフ
ルオロボレートを熱分解する方法が知られている
〔Schiemann＆Pillars、Ber.62、3035（1929）お
よびBergmann、Engel＆Sandor、Z.Physik.
Chem.、10B、106（1930）〕。しかしながら、この
公知方法ではきわめて収率が悪く、ことにその熱
分解工程ではわずかに30％程度の収率しか挙げら
れていない。 The method for producing this O-difluorobenzene is as follows:
2 obtained by diazotizing O-fluoroaniline
A method of thermally decomposing -fluoro-1-benzenediazonium tetrafluoroborate is known [Schiemann & Pillars, Ber. 62 , 3035 (1929) and Bergmann, Engel & Sandor, Z. Physik.
Chem., 10B , 106 (1930)]. However, the yield of this known method is extremely poor, especially in the thermal decomposition step, which yields only about 30%.
本発明者らはこの化合物を高収率で得る改良方
法を見出すべく種々研究を重ねるうちに、上記ジ
アゾニウム塩の熱分解に際して少量のシリコンオ
イルを添加することにより意外にもきわめて収率
よく目的とするＯ−ジフルオロベンゼンが得られ
ることを知り、本発明を完成するに至つた。 The inventors of the present invention have carried out various studies in order to find an improved method for obtaining this compound in high yield, and have surprisingly found that by adding a small amount of silicone oil during the thermal decomposition of the diazonium salt, the desired compound can be obtained with an extremely high yield. The present invention was completed based on the knowledge that O-difluorobenzene can be obtained.
すなわち、本発明は２−フルオロ−１−ベンゼ
ンジアゾニウムテトラフルオロボレートをシリコ
ンオイルの存在下に熱分解することにより高収率
でＯ−ジフルオロベンゼンを得る改良されたＯ−
ジフルオロベンゼンの製法を提供するものであ
る。 That is, the present invention provides an improved O-difluorobenzene in high yield by thermally decomposing 2-fluoro-1-benzenediazonium tetrafluoroborate in the presence of silicone oil.
A method for producing difluorobenzene is provided.
本発明方法によれば、目的とするＯ−ジフルオ
ロベンゼンは、その出発物質の製法を含めて、下
記の反応式にしたがつて製造される。 According to the method of the present invention, the target O-difluorobenzene is produced according to the following reaction formula, including the method for producing the starting material.
上記反応式で示されるように、Ｏ−フルオロア
ニリン(1)を不活性水性溶媒中で塩酸、硫酸、臭化
水素酸などの鉱酸の存在化、亜硝酸ナトリウムな
どの亜硝酸塩を作用させてジアゾ化を行なう。こ
のジアゾ化は通常、低温、例えば−30〜20℃、好
ましくは−15〜−５℃にて数十分〜数時間反応さ
せることにより行なわれ、亜硝酸塩は化合物(1)に
対して等モル以上、通常１〜1.5倍モル程度用い
られる。このジアゾ化後、ホウフツ化水素酸
（HBF4）などのフツ素化剤を作用させて置換反
応を行なつて２−フルオロ−１−ベンゼンジアゾ
ニウムテトラフルオロボレート(2)に導かれる。こ
のフツ素化剤も等モル以上、通常１〜1.5倍モル
程度用いられる。このようにして得られる２−フ
ルオロ−１−ベンゼンジアゾニウムテトラフルオ
ロボレート(2)は単離することなく次の熱分解反応
に供してもよいが、好ましくは単離したのちに使
用される。 As shown in the above reaction formula, O-fluoroaniline (1) is reacted with a mineral acid such as hydrochloric acid, sulfuric acid, or hydrobromic acid in an inert aqueous solvent, or with a nitrite such as sodium nitrite. Perform diazotization. This diazotization is usually carried out by reacting at a low temperature, for example -30 to 20°C, preferably -15 to -5°C, for several tens of minutes to several hours, and the nitrite is equimolar to compound (1). The above amount is usually used in a molar range of 1 to 1.5 times. After this diazotization, a fluorinating agent such as hydroborofluoric acid (HBF 4 ) is applied to carry out a substitution reaction, leading to 2-fluoro-1-benzenediazonium tetrafluoroborate (2). This fluorinating agent is also used in an amount equal to or more than the same mole, usually about 1 to 1.5 times the mole. The 2-fluoro-1-benzenediazonium tetrafluoroborate (2) thus obtained may be subjected to the next thermal decomposition reaction without being isolated, but is preferably used after isolation.
２−フルオロ−１−ベンゼンジアゾニウムテト
ラフルオロボレート(2)の熱分解は、少量のシリコ
ンオイルを添加して加熱することにより行なわれ
る。用いられるシリコンオイルとしては公知のす
べてのシリコンオイルが用いられ、その用量は、
あまり多量では分解後目的物の蒸留単離が困難と
なるため、原料のジアゾニウム塩(2)に対して約４
〜５重量％が好ましい。この熱分解反応は通常無
溶媒下で温度100〜180℃、好ましくは130〜160℃
にて約１〜５時間加熱することにより達成され
る。 Thermal decomposition of 2-fluoro-1-benzenediazonium tetrafluoroborate (2) is carried out by adding a small amount of silicone oil and heating. All known silicone oils are used, and the dosage is as follows:
If the amount is too large, it will be difficult to isolate the target product by distillation after decomposition, so approximately 4
~5% by weight is preferred. This thermal decomposition reaction is usually carried out without solvent at a temperature of 100 to 180°C, preferably 130 to 160°C.
This is achieved by heating for about 1 to 5 hours.
本発明方法によれば熱分解反応はきわめて穏や
かに進行し反応容器も比較的少容積で済み、目的
物の収率も80％以上ときわめて高い特徴がある。 According to the method of the present invention, the thermal decomposition reaction proceeds very slowly, the volume of the reaction vessel is relatively small, and the yield of the target product is extremely high, at 80% or more.
つぎに実施例により本発明方法をさらに具体的
に説明する。 Next, the method of the present invention will be explained in more detail with reference to Examples.
実施例
(A) ２−フルオロ−１−ベンゼンジアゾニウムテ
トラフルオロボレートの製造：
温度計、撹拌機および滴下ロートを付設した
５容の三口フラスコに濃塩酸２（23.3モ
ル）および水200mlを仕込み、室温下にＯ−フ
ルオロアニリン1.0Kg（9.0モル）を滴下する。
滴下後、30分間撹拌し、ついでドライアイス−
アセトンにて内温を−15℃に冷却し、亜硝酸ナ
トリウム660g（9.5モル）を水１に溶かした容
液を滴下する。滴下後、30分間撹拌し、ついで
これに42％ホウフツ化水素酸（HBF4）1920ml
（9.2モル）を加え、生じた析出晶を取し、氷
水、メタノールおよびジエチルエーテルの順で
洗浄し、乾燥して２−フルオロ−１−ベンゼン
ジアゾニウムテトラフルオロボレート1480g
（収率78％）を得る。Example (A) Production of 2-fluoro-1-benzenediazonium tetrafluoroborate: A 5-volume three-necked flask equipped with a thermometer, a stirrer, and a dropping funnel was charged with concentrated hydrochloric acid 2 (23.3 mol) and 200 ml of water, and the mixture was heated to room temperature. 1.0 kg (9.0 mol) of O-fluoroaniline is added dropwise to the bottom.
After dropping, stir for 30 minutes and then add dry ice.
The internal temperature was cooled to -15°C with acetone, and a solution of 660 g (9.5 mol) of sodium nitrite dissolved in 1 part of water was added dropwise. After dropping, stir for 30 minutes, then add 1920 ml of 42% hydroborofluoric acid (HBF 4 ).
(9.2 mol) was added, and the resulting precipitated crystals were collected, washed with ice water, methanol, and diethyl ether in that order, and dried. 1480 g of 2-fluoro-1-benzenediazonium tetrafluoroborate.
(yield 78%).
(B) Ｏ−ジフルオロベンゼンの製造：
温度計および留出管（留出管として100ml容
フラスコを付け、さらにドライアイス−アセト
ントラツプおよびNaOHトラツプを付ける）
を付設した１容三口フラスコ中に、上記で得
られた２−フルオロ−１−ベンゼンジアゾニウ
ムテトラフルオロボレート300g（1.43モル）と
シリコンオイル12mlを仕込み、油浴上で加熱す
る。140℃で分解が始まり、生成物は留出して
留出管のフラスコ内にたまる。140〜150℃にて
２時間加熱したのち、160℃でさらに30分間加
熱して分解を完了する。フラスコ内およびトラ
ツプ内にたまつた生成物を集め、よく水洗後、
常圧にて蒸留してＯ−ジフルオロベンゼン
132g（収率81％）を得る。沸点88℃／760mmHg。(B) Production of O-difluorobenzene: Thermometer and distillation tube (a 100 ml flask is attached as a distillation tube, and a dry ice-acetone trap and a NaOH trap are attached)
300 g (1.43 mol) of the 2-fluoro-1-benzenediazonium tetrafluoroborate obtained above and 12 ml of silicone oil were placed in a 1-volume three-necked flask equipped with a water bottle, and heated on an oil bath. Decomposition begins at 140°C, and the products are distilled out and collected in the flask of the distillation tube. After heating at 140-150°C for 2 hours, heating at 160°C for an additional 30 minutes completes the decomposition. Collect the product accumulated in the flask and trap, wash thoroughly with water,
O-difluorobenzene is distilled at normal pressure.
Obtain 132 g (81% yield). Boiling point 88℃/760mmHg.
Claims (1)
トラフルオロボレートをシリコンオイルの存在下
に熱分解することを特徴とするＯ−ジフルオロベ
ンゼンの製造法。1. A method for producing O-difluorobenzene, which comprises thermally decomposing 2-fluoro-1-benzenediazonium tetrafluoroborate in the presence of silicone oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17809182A JPS5967232A (en) | 1982-10-08 | 1982-10-08 | Novel method for preparing o-difluorobenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17809182A JPS5967232A (en) | 1982-10-08 | 1982-10-08 | Novel method for preparing o-difluorobenzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5967232A JPS5967232A (en) | 1984-04-16 |
| JPH0149247B2 true JPH0149247B2 (en) | 1989-10-24 |
Family
ID=16042473
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17809182A Granted JPS5967232A (en) | 1982-10-08 | 1982-10-08 | Novel method for preparing o-difluorobenzene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5967232A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870636B (en) * | 2010-04-01 | 2013-01-23 | 大唐(杭州)医药化工有限公司 | Preparation method of 2-bromo-6-fluoronaphthalene |
-
1982
- 1982-10-08 JP JP17809182A patent/JPS5967232A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5967232A (en) | 1984-04-16 |
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