JPH0412254B2 - - Google Patents
Info
- Publication number
- JPH0412254B2 JPH0412254B2 JP59043091A JP4309184A JPH0412254B2 JP H0412254 B2 JPH0412254 B2 JP H0412254B2 JP 59043091 A JP59043091 A JP 59043091A JP 4309184 A JP4309184 A JP 4309184A JP H0412254 B2 JPH0412254 B2 JP H0412254B2
- Authority
- JP
- Japan
- Prior art keywords
- fluoride
- hydrogen fluoride
- acyl
- reaction
- acid
- 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
Links
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 32
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 32
- 150000001265 acyl fluorides Chemical class 0.000 claims description 23
- 229910015900 BF3 Inorganic materials 0.000 claims description 15
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 15
- 150000008065 acid anhydrides Chemical class 0.000 claims description 9
- 150000001491 aromatic compounds Chemical class 0.000 claims description 9
- 150000008365 aromatic ketones Chemical class 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 238000005917 acylation reaction Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- AOMUALOCHQKUCD-UHFFFAOYSA-N dodecyl 4-chloro-3-[[3-(4-methoxyphenyl)-3-oxopropanoyl]amino]benzoate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC=C(Cl)C(NC(=O)CC(=O)C=2C=CC(OC)=CC=2)=C1 AOMUALOCHQKUCD-UHFFFAOYSA-N 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 3
- 230000010933 acylation Effects 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- GNKZMNRKLCTJAY-UHFFFAOYSA-N 4'-Methylacetophenone Chemical compound CC(=O)C1=CC=C(C)C=C1 GNKZMNRKLCTJAY-UHFFFAOYSA-N 0.000 description 2
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JWQJVJAAWCEUKY-UHFFFAOYSA-N 1-(6-methylnaphthalen-1-yl)ethanone Chemical compound CC1=CC=C2C(C(=O)C)=CC=CC2=C1 JWQJVJAAWCEUKY-UHFFFAOYSA-N 0.000 description 1
- KEAGRYYGYWZVPC-UHFFFAOYSA-N 1-[4-(2-methylpropyl)phenyl]ethanone Chemical compound CC(C)CC1=CC=C(C(C)=O)C=C1 KEAGRYYGYWZVPC-UHFFFAOYSA-N 0.000 description 1
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 1
- 229940073735 4-hydroxy acetophenone Drugs 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000004817 gas chromatography 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
- 150000002576 ketones Chemical class 0.000 description 1
- -1 kyumene Chemical compound 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- RARSHUDCJQSEFJ-UHFFFAOYSA-N p-Hydroxypropiophenone Chemical compound CCC(=O)C1=CC=C(O)C=C1 RARSHUDCJQSEFJ-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- RGCLLPNLLBQHPF-HJWRWDBZSA-N phosphamidon Chemical compound CCN(CC)C(=O)C(\Cl)=C(/C)OP(=O)(OC)OC RGCLLPNLLBQHPF-HJWRWDBZSA-N 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- LEMQFBIYMVUIIG-UHFFFAOYSA-N trifluoroborane;hydrofluoride Chemical compound F.FB(F)F LEMQFBIYMVUIIG-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Description
本発明は芳香族炭化水素、フエノール類等の芳
香族化合物をフツ化アシルでアシル化して芳香族
ケトンを製造する方法に関する。
芳香族化合物をフツ化水素、フツ化硼素等の触
媒存在下酸フツ化物でアシル化する方法は特開昭
54−135756として知られている。こゝでは酸フツ
化物の製法としてフツ化水素の存在下オレフイン
に一酸化炭素を反応させる方法が示されている。
しかしかゝる方法により酸フツ化物を製造するに
は20〜50Kg／cm2の圧力を要する欠点がある。本発
明においてはかゝる欠点を解消し、酸無水物と芳
香族化合物から芳香族ケトンを収率良く製造する
と共にすぐれた回収率で触媒を回収しこれを循環
再使用することの出来る方法である。
即ち本発明は芳香族化合物をフツ化水素、又は
フツ化水素及びフツ化硼素の存在下、フツ化アシ
ルと反応させて芳香族ケトンを製造するに際し、
酸無水物を予じめフツ化水素と反応させてフツ化
アシルを合成し、これから単離されたフツ化アシ
ルをアシル化剤として使用する方法である。
本発明において使用する原料芳香族化合物と
は、トルエン、キシレン、トリメチルベンゼン、
エチルベンゼン、キユメン、ブチルベンゼン等の
アルキルベンゼン類、ナフタレン、メチルナフタ
レンその他のアルキルナフタレン類及びフエノー
ル、ナフトール類、さらには、アニソール、フエ
ニルエーテル等の芳香族エーテル類で芳香環置換
基のバラ位が空位の化合物が特に好適である。
一方のアシル化原料としては豊富に入手可能
な、無水酢酸、無水プロピオン酸、無水イソ酪
酸、無水安息香酸等の酸無水物が使用でき、従つ
て製造し得る芳香族ケトンとしては、４−メチル
アセトフエノン（香料、農薬）、４−イソブチル
アセトフエノン（医薬原料）、４−ヒドロキシア
セトフエノン、４−ヒドロキシプロピオフエノン
（医薬原料）、種々のベンゾフエノン類、２−アセ
チル−６−アルキルナフタレン及び２−イソブチ
リル−６−アルキルナフタレン（２，６−ナフタ
レンジカルボン酸原料）等の有用な化合物が包含
される。
本発明のアシル化剤は、先ずアシル化原料の酸
無水物を弗化水素と混合し、次式(1)の反応により
フツ化アシルを発生せしめ、同時に生成する遊離
酸と分離することにより得られる。
（RCO）2O＋HF→RCOF＋RCOOH …(1)
（こゝでＲは炭素数１〜12のアルキル基、又は
アリール基である）
こゝで上記の反応は酸無水物がやゝ過剰の条件
で反応を進めることが肝要である。即ち、もしフ
ツ化水素が当量よりも過剰であるとフツ化水素と
有機酸の結合した最高共沸混合物を形成して分離
不可能となり、フツ化水素の損失につながると同
時に生成した酸がフツ素により汚染され、これを
除くために特別の処理を要することになる。酸無
水物が過剰のときは、このようなことはなく、フ
ツ化水素は定量的にフツ化アシルとして回収され
る。しかし、余り過剰である必要はなく、フツ化
水素に対する酸無水物の過剰率は５モル％以下で
よい。
フツ化アシルの発生装置はフツ化アシルと遊離
カルボン酸を蒸留するに必要な若干の段数を持つ
た通常の蒸留塔でよい。酸無水物とフツ化水素は
予じめ混合するか、または別々に蒸留塔の適当な
段に供給し、塔底は、酸の沸点迄加熱し、塔頂は
適当な還流を施す通常の蒸留操作により、塔頂か
ら純粋のフツ化アシルを、塔底からフツ素を含ま
ない酸を回収することが出来る。
この反応は反応速度が速いので殆んど滞留時間
を要しない。圧力は常圧以下で操作出来、流通操
作でも回分操作でもよい。生成したフツ化アシル
と酸の沸点差は極めて大きく、両者は容易に分離
出来る。
生成したフツ化アシルはアシル化剤としてアシ
ル化反応に供せられる。原料芳香族化合物に対す
るフツ化アシルのモル比は１以下であり、特に
0.9〜0.5が好ましい。
フツ化アシルを過剰にすると、反応の終了時点
で、フツ化アシルが残存し、触媒回収操作時に好
ましくない。又フツ化アシルが多く存在すると、
全体の反応速度（アシル化生成物の空時収量）を
低下させる。
触媒はフツ化水素単独でも良いが、更にフツ化
硼素を併用すると反応は促進され、高沸物の生成
等の副反応は減少する。フツ化水素単独の場合は
充分な反応速度を得る為にはアシル化剤に対する
フツ化水素の割合を５モル倍以上、好ましくは10
〜20モル倍の範囲で使用する。20モル倍以上のフ
ツ化水素を用いても効果が少なく、プロセス経済
上得策でない。
触媒としてフツ化硼素を併用する場合には、フ
ツ化硼素をアシル化剤に対し当量かまたはわずか
に過剰に用いるのが良く、余り過剰率が高いと反
応の選択性に好ましくない。フツ化硼素を併用す
る場合にはフツ化水素の使用量はアシル化剤に対
して３モル倍以上、好ましくは５〜15モル倍の範
囲で用いる。
アシル化反応の温度はフツ化水素単独触媒の場
合は０〜50℃、好ましくは20〜40℃であり、フツ
化硼素を併用する場合は−20〜＋30℃、好ましく
は０〜20℃である。いずれの場合にも、温度を上
げれば反応速度は増すが、副反応速度も増加す
る。また、原料の融点等も考慮して反応温度を決
定することが必要である。
反応圧力は、通常の条件下で、常圧から２Kg／
cm2Ｇ迄の間の若干の加圧であるが、これは使用す
る触媒のモル比と温度によつて定まる。
反応は均一液相か場合によつては原料芳香族化
合物相と触媒相の２液相で進行するため、激しい
撹拌を要しない。
反応液は、アシル化反応生成物である芳香族ケ
トンまたはそのフツ化硼素錯体のフツ化水素溶液
であり、これを加熱することによりケトンとフツ
化水素、又はフツ化水素、フツ化硼素との結合が
分解され、フツ化水素又はフツ化水素−フツ化硼
素として気化分離することができる。
この触媒回収操作は出来るだけ迅速に進めて、
生成物の加熱変質を避ける必要がある。そのため
には、多段の気液接触装置（蒸留塔）を使用した
流通操作で実施するのが良い。触媒の回収のため
にはフツ化水素については40〜100℃、フツ化硼
素については100〜180℃の温度への加熱が必要で
ある。触媒回収操作の圧力は常圧ないしは加圧で
実施するのがプロセス上有利である。錯体の熱分
解を順調に進める為にフツ化水素、フツ化硼素に
対し不活性な分解助剤、たとえばベンゼン、トル
エン、クロロベンゼン等の芳香族炭化水素、ハロ
ゲン化芳香族炭化水素の還流下に加熱分解するの
は好ましい方法である。
本発明によれば単純な操作、低い反応圧力下で
芳香族化合物をアシル化することが出来ると共
に、触媒として使用するフツ化水素、フツ化硼素
を完全に回収し、循環使用することが出来、工業
的に極めて有利である。
実施例 １
（フツ化アシルの製造）
外部から電熱ヒーターで加熱出来るステンレス
製オートクレーブに、内径30ｍ／ｍ、長さ100
ｍ／ｍで塔頂に冷却器を設けたステンレス製蒸留
塔（３ｍ／ｍデイクソンパツキン充填）を組合わ
せてフツ化アシル発生器として使用した。
先ずオートクレーブ内に無水酢酸1430ｇ（14.0
モル）を仕込み、続いて無水フツ化水素267ｇ
（13.4モル）を仕込んだ。フツ化水素の仕込みと
同時に内液の温度は常温から約40℃に上昇した。
続いて蒸留塔々頂冷却器に冷却水を通じ、少量の
還流を与えるよう調節しながら、オートクレーブ
のガスを蒸留塔を通して解放し、塔頂部からフツ
化アセチルのガスを抜きながらゆつくりオートク
レーブの加熱を開始した。塔頂から連続して発生
するフツ化アセチルは氷水を通した別の冷却器で
凝縮せしめステンレス容器中に捕集した。
内液の温度が酢酸の沸点である118℃になる迄
加熱を続け、フツ化アセチルの発生操作を終え
た。フツ化アセチル発生中の塔頂凝縮部の温度は
20℃であつた。
採取したフツ化アセチルの収量は831gr（13.4モ
ル）であり、使用したフツ化水素に対し定量的で
あり、オートクレーブ中の酢酸は実質的にフツ素
不含であつた。
その他のフツ化アシルの発生につき同様の操作
で実施し、その結果を第１表にまとめた。
The present invention relates to a method for producing aromatic ketones by acylating aromatic compounds such as aromatic hydrocarbons and phenols with acyl fluoride. A method of acylating aromatic compounds with an acid fluoride in the presence of a catalyst such as hydrogen fluoride or boron fluoride is described in JP-A-Sho.
It is known as 54−135756. Here, as a method for producing acid fluoride, a method is shown in which olefin is reacted with carbon monoxide in the presence of hydrogen fluoride.
However, the production of acid fluorides by such a method has the drawback of requiring a pressure of 20 to 50 kg/cm 2 . The present invention eliminates these drawbacks and provides a method that can produce aromatic ketones from acid anhydrides and aromatic compounds in high yields, recover catalysts with excellent recovery rates, and recycle and reuse them. be. That is, in the present invention, when producing an aromatic ketone by reacting an aromatic compound with an acyl fluoride in the presence of hydrogen fluoride, or hydrogen fluoride and boron fluoride,
In this method, an acyl fluoride is synthesized by reacting an acid anhydride with hydrogen fluoride in advance, and the acyl fluoride isolated from the synthesized acyl fluoride is used as an acylating agent. The raw material aromatic compounds used in the present invention include toluene, xylene, trimethylbenzene,
Alkylbenzenes such as ethylbenzene, kyumene, and butylbenzene, naphthalene, methylnaphthalene, and other alkylnaphthalenes, phenols, naphthols, and aromatic ethers such as anisole and phenyl ether in which the rose position of the aromatic ring substituent is vacant. Particularly preferred are the compounds of On the other hand, as raw materials for acylation, acid anhydrides such as acetic anhydride, propionic anhydride, isobutyric anhydride, and benzoic anhydride, which are abundantly available, can be used. Therefore, the aromatic ketone that can be produced is 4-methyl Acetophenone (fragrance, pesticide), 4-isobutylacetophenone (pharmaceutical raw material), 4-hydroxyacetophenone, 4-hydroxypropiophenone (pharmaceutical raw material), various benzophenones, 2-acetyl-6-alkyl Useful compounds such as naphthalene and 2-isobutyryl-6-alkylnaphthalene (2,6-naphthalene dicarboxylic acid raw material) are included. The acylating agent of the present invention can be obtained by first mixing an acid anhydride as an acylation raw material with hydrogen fluoride, generating acyl fluoride by the reaction of the following formula (1), and separating it from the free acid generated at the same time. It will be done. (RCO) 2 O+HF→RCOF+RCOOH...(1) (Here, R is an alkyl group having 1 to 12 carbon atoms or an aryl group) The above reaction is carried out under conditions where the acid anhydride is slightly excess. It is essential to move forward with this. That is, if hydrogen fluoride is in excess of the equivalent amount, the highest azeotropic mixture of hydrogen fluoride and organic acid is formed and cannot be separated, leading to loss of hydrogen fluoride and at the same time, the generated acid is This means that special treatment is required to remove this contamination. When the acid anhydride is in excess, this does not occur and hydrogen fluoride is quantitatively recovered as acyl fluoride. However, it does not need to be in excess, and the excess ratio of acid anhydride to hydrogen fluoride may be 5 mol % or less. The acyl fluoride generator may be a conventional distillation column having the number of plates necessary to distill the acyl fluoride and free carboxylic acid. The acid anhydride and hydrogen fluoride are either mixed in advance or fed separately to appropriate stages of the distillation column, and the bottom of the column is heated to the boiling point of the acid, and the top of the column is subjected to appropriate reflux. The operation allows recovery of pure acyl fluoride from the top of the column and fluorine-free acid from the bottom of the column. This reaction has a fast reaction rate and requires almost no residence time. The pressure can be operated at normal pressure or lower, and either flow operation or batch operation may be used. The difference in boiling point between the produced acyl fluoride and the acid is extremely large, and the two can be easily separated. The produced acyl fluoride is used as an acylating agent in an acylation reaction. The molar ratio of acyl fluoride to the raw material aromatic compound is 1 or less, especially
0.9-0.5 is preferred. If the acyl fluoride is used in excess, the acyl fluoride will remain at the end of the reaction, which is not preferable during the catalyst recovery operation. Also, if there is a large amount of acyl fluoride,
Decrease the overall reaction rate (space-time yield of acylated product). Hydrogen fluoride alone may be used as the catalyst, but when boron fluoride is used in combination, the reaction is accelerated and side reactions such as the formation of high-boiling substances are reduced. In the case of using hydrogen fluoride alone, in order to obtain a sufficient reaction rate, the ratio of hydrogen fluoride to the acylating agent should be at least 5 times the mole, preferably 10 times.
Use in a range of ~20 moles. Even if 20 moles or more of hydrogen fluoride is used, the effect is small and it is not a good idea in terms of process economics. When boron fluoride is used in combination as a catalyst, it is preferable to use boron fluoride in an equivalent amount or slightly in excess of the acylating agent; if the excess is too high, it is not favorable for the selectivity of the reaction. When boron fluoride is used in combination, the amount of hydrogen fluoride used is 3 times or more, preferably 5 to 15 times, by mole relative to the acylating agent. The temperature of the acylation reaction is 0 to 50°C, preferably 20 to 40°C when hydrogen fluoride is used as a single catalyst, and -20 to +30°C, preferably 0 to 20°C when boron fluoride is used in combination. . In either case, increasing the temperature increases the reaction rate, but also increases the rate of side reactions. Furthermore, it is necessary to determine the reaction temperature by taking into consideration the melting point of the raw materials and the like. The reaction pressure is 2Kg/2Kg from normal pressure under normal conditions.
The pressure is slightly increased up to cm 2 G, which is determined by the molar ratio of the catalyst used and the temperature. Since the reaction proceeds in a homogeneous liquid phase or in some cases in two liquid phases of a raw material aromatic compound phase and a catalyst phase, vigorous stirring is not required. The reaction solution is a hydrogen fluoride solution of an aromatic ketone or its boron fluoride complex, which is an acylation reaction product, and by heating it, the reaction mixture between the ketone and hydrogen fluoride, or between hydrogen fluoride and boron fluoride. The bond is decomposed and hydrogen fluoride or hydrogen fluoride-boron fluoride can be vaporized and separated. This catalyst recovery operation should proceed as quickly as possible.
It is necessary to avoid heat alteration of the product. For this purpose, it is preferable to perform a flow operation using a multi-stage gas-liquid contact device (distillation column). For recovery of the catalyst, heating to a temperature of 40-100°C for hydrogen fluoride and 100-180°C for boron fluoride is required. It is advantageous for the process to carry out the catalyst recovery operation at normal pressure or increased pressure. In order to smoothly proceed with thermal decomposition of the complex, heat under reflux a decomposition aid inert to hydrogen fluoride and boron fluoride, such as aromatic hydrocarbons and halogenated aromatic hydrocarbons such as benzene, toluene, and chlorobenzene. Decomposition is the preferred method. According to the present invention, aromatic compounds can be acylated with simple operations and under low reaction pressure, and hydrogen fluoride and boron fluoride used as catalysts can be completely recovered and recycled, It is extremely advantageous industrially. Example 1 (Production of acyl fluoride) A stainless steel autoclave that can be heated from the outside with an electric heater has an inner diameter of 30 m/m and a length of 100 m.
A stainless steel distillation column (packed with 3 m/m Dixon packing) equipped with a condenser at the top of the column was used as an acyl fluoride generator. First, add 1430 g of acetic anhydride (14.0
mol), followed by 267g of anhydrous hydrogen fluoride.
(13.4 mol) was charged. At the same time as hydrogen fluoride was charged, the temperature of the internal solution rose from room temperature to approximately 40°C.
Next, cooling water was passed through the distillation tower overhead cooler, and while adjusting to give a small amount of reflux, the gas in the autoclave was released through the distillation tower, and the autoclave was slowly heated while removing the acetyl fluoride gas from the top of the tower. It started. The acetyl fluoride continuously generated from the top of the column was condensed in a separate cooler passing ice water and collected in a stainless steel container. Heating was continued until the temperature of the internal solution reached 118°C, which is the boiling point of acetic acid, and the operation for generating acetyl fluoride was completed. The temperature of the top condensation section during generation of acetyl fluoride is
It was 20℃. The yield of acetyl fluoride collected was 831 gr (13.4 mol), which was quantitative with respect to the hydrogen fluoride used, and the acetic acid in the autoclave was substantially fluorine-free. Similar operations were performed to generate other acyl fluorides, and the results are summarized in Table 1.
【表】
実施例 ２
（アシル化反応）
内容積500mlのジヤケツトつきステンレス製オ
ートクレーブをアシル化器として使用した。
オートクレーブにβ−メチルナフタレン142gr
（１モル）を53gr（0.85モル）のフツ化アセチルに
溶解させて仕込み、次に液体フツ化水素170gr
（8.5モル）を加えた後、ジヤケツトに冷媒を通
じ、撹拌しながらフツ化硼素ガス60gr（0.87モル）
を計量槽より約10分間でゆつくり供給した。フツ
化硼素の吸収に伴なう発熱をジヤケツト冷却で除
去し、温度が10℃を超えないように維持する。そ
の後ゆつくり撹拌しながら温度20℃で１時間反応
後、内容物を氷水中にとり出しベンゼン200grで
稀釈後、油層をアルカリ水と水で洗浄し、蒸留に
よりベンゼンを除き、順次蒸留によりβ−メチル
ナフタリン37gr（0.26モル）と184〜190℃（15mm
Hg）の留分としてアシル化メチルナフタリン
151gr（0.82モル％、ガスクロ分析による異性体組
成：α−アセチル−６−メチルナフタレン84.7
％、その他15.3％）を得、また釜残として高沸物
3.7ｇが残つた。
同様の操作により各種の原料についてアシル化
反応を行なつた結果を第２表に示す。[Table] Example 2 (Acylation reaction) A stainless steel autoclave with a jacket and an internal volume of 500 ml was used as an acylation device. β-Methylnaphthalene 142gr in autoclave
(1 mole) was dissolved in 53gr (0.85mol) of acetyl fluoride, then 170g of liquid hydrogen fluoride was added.
After adding (8.5 mol), the refrigerant was passed through the jacket and 60 gr (0.87 mol) of boron fluoride gas was added while stirring.
was slowly fed from the measuring tank over a period of about 10 minutes. The heat generated by the absorption of boron fluoride is removed by jacket cooling, and the temperature is maintained at no higher than 10°C. Thereafter, after reacting for 1 hour at a temperature of 20℃ with gentle stirring, the contents were taken out into ice water and diluted with 200g of benzene.The oil layer was washed with alkaline water and water, and the benzene was removed by distillation, and the β-methyl Naphthalene 37gr (0.26mol) and 184~190℃ (15mm
Acylated methylnaphthalene as a fraction of Hg)
151gr (0.82mol%, isomer composition by gas chromatography: α-acetyl-6-methylnaphthalene 84.7
%, other 15.3%), and high-boiling substances as residue from the pot.
3.7g remained. Table 2 shows the results of acylation reactions of various raw materials performed in the same manner.
Claims (1)
及びフツ化硼素の存在下、フツ化アシルと反応さ
せて芳香族ケトンを製造するに際し、酸無水物を
予じめフツ化水素と反応させてフツ化アシルを合
成し、これから単離されたフツ化アシルをアシル
化剤として使用することを特徴とする芳香族ケト
ンの製造法1. When producing an aromatic ketone by reacting an aromatic compound with an acyl fluoride in the presence of hydrogen fluoride, or hydrogen fluoride and boron fluoride, the acid anhydride is reacted with the hydrogen fluoride in advance. A method for producing an aromatic ketone, which comprises synthesizing an acyl fluoride and using the acyl fluoride isolated from the synthesized acyl fluoride as an acylating agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59043091A JPS60188343A (en) | 1984-03-07 | 1984-03-07 | Preparation of aromatic ketone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59043091A JPS60188343A (en) | 1984-03-07 | 1984-03-07 | Preparation of aromatic ketone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60188343A JPS60188343A (en) | 1985-09-25 |
| JPH0412254B2 true JPH0412254B2 (en) | 1992-03-04 |
Family
ID=12654166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59043091A Granted JPS60188343A (en) | 1984-03-07 | 1984-03-07 | Preparation of aromatic ketone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60188343A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4593125A (en) * | 1985-03-13 | 1986-06-03 | Celanese Corporation | Acylation of naphthalenes |
| DE3806656A1 (en) * | 1988-03-02 | 1989-09-14 | Hoechst Ag | METHOD FOR PRODUCING HALOGENIC AROMATIC COMPOUNDS |
| US4990681A (en) * | 1989-12-04 | 1991-02-05 | Curtis Thomas A | Method for removing hydrogen fluoride from mixtures comprising aromatic ketones |
| US5208383A (en) * | 1991-06-14 | 1993-05-04 | Mitsubishi Gas Chemical Company, Inc. | Process for producing aromatic acylation product |
| CA2093511C (en) * | 1991-08-08 | 1999-09-21 | Koji Sumitani | Process for producing dialkylnaphthalene |
| TW306910B (en) * | 1992-09-11 | 1997-06-01 | Hoechst Ag | |
| EP1961727A1 (en) * | 2007-02-26 | 2008-08-27 | Bayer CropScience AG | Method for manufacturing 2,4-dihydroxyphenyl-4-methoxybenzyl ketones |
-
1984
- 1984-03-07 JP JP59043091A patent/JPS60188343A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60188343A (en) | 1985-09-25 |
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