JPS62185055A - Production of diphenylcarboxylic acid - Google Patents
Production of diphenylcarboxylic acidInfo
- Publication number
- JPS62185055A JPS62185055A JP61026911A JP2691186A JPS62185055A JP S62185055 A JPS62185055 A JP S62185055A JP 61026911 A JP61026911 A JP 61026911A JP 2691186 A JP2691186 A JP 2691186A JP S62185055 A JPS62185055 A JP S62185055A
- Authority
- JP
- Japan
- Prior art keywords
- diphenyl
- water
- mol
- brominated
- carbon monoxide
- 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.)
- Pending
Links
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 125000006267 biphenyl group Chemical group 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 8
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 150000002367 halogens Chemical class 0.000 claims abstract description 7
- NXYICUMSYKIABQ-UHFFFAOYSA-N 1-iodo-4-phenylbenzene Chemical group C1=CC(I)=CC=C1C1=CC=CC=C1 NXYICUMSYKIABQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- GPYDMVZCPRONLW-UHFFFAOYSA-N 1-iodo-4-(4-iodophenyl)benzene Chemical group C1=CC(I)=CC=C1C1=CC=C(I)C=C1 GPYDMVZCPRONLW-UHFFFAOYSA-N 0.000 claims abstract description 5
- PKJBWOWQJHHAHG-UHFFFAOYSA-N 1-bromo-4-phenylbenzene Chemical group C1=CC(Br)=CC=C1C1=CC=CC=C1 PKJBWOWQJHHAHG-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- HQJQYILBCQPYBI-UHFFFAOYSA-N 1-bromo-4-(4-bromophenyl)benzene Chemical group C1=CC(Br)=CC=C1C1=CC=C(Br)C=C1 HQJQYILBCQPYBI-UHFFFAOYSA-N 0.000 claims 1
- 150000002506 iron compounds Chemical class 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 9
- 235000010290 biphenyl Nutrition 0.000 abstract description 8
- 239000004305 biphenyl Substances 0.000 abstract description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 14
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 8
- -1 cyanide compound Chemical class 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical compound CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 description 2
- RZTDESRVPFKCBH-UHFFFAOYSA-N 1-methyl-4-(4-methylphenyl)benzene Chemical group C1=CC(C)=CC=C1C1=CC=C(C)C=C1 RZTDESRVPFKCBH-UHFFFAOYSA-N 0.000 description 2
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000007704 transition Effects 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、新規なジフェニルカルボン酸の製造方法に間
する。詳しくはヨウ素化ジフェニル又は臭素化ジフェニ
ルを塩基性物質、遷移金属化合物を含有する触媒の存在
下、水単独又は水を含有する溶媒系として、水を該ヨウ
素化ジフェニル又は臭素化ジフェニルのハロゲンに対し
て当量以上用い、一酸化炭素と反応させることを特徴と
するジフェニルカルボン酸を製造する方法である。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a novel method for producing diphenylcarboxylic acid. Specifically, iodinated diphenyl or brominated diphenyl is reacted with water against the halogen of the iodinated diphenyl or brominated diphenyl in the presence of a catalyst containing a basic substance and a transition metal compound, water alone or as a solvent system containing water. This is a method for producing diphenylcarboxylic acid, which is characterized by using at least an equivalent amount of diphenylcarboxylic acid and reacting it with carbon monoxide.
（従来の技術）
ジフェニルカルボン酸の製造法については、１）ｐ−ク
ロル安息酸を反応させる方法、２）ｐ−ブロムトルエン
を反応させて４，４′−ジメチルジフェニルとし酸化す
る方法、３）ハロゲン化ジフェニルをシアン化合物と反
応させてジニトリルとし、加水分解する方法、４）ジフ
ェニルをクロルメチル化し、酸化する方法、等が知られ
ている。(Prior art) Methods for producing diphenylcarboxylic acid include 1) a method of reacting p-chlorobenzoic acid, 2) a method of reacting p-bromotoluene and oxidizing it to 4,4'-dimethyldiphenyl, and 3) a method of reacting p-bromotoluene to form 4,4'-dimethyldiphenyl. Known methods include a method in which halogenated diphenyl is reacted with a cyanide compound to form dinitrile and then hydrolyzed, and 4) a method in which diphenyl is chloromethylated and oxidized.
（発明が解決ようとする問題点）
しかし、これらの方法では、反応工程が長かったり、用
いる原料が高価である等の欠点がある。(Problems to be Solved by the Invention) However, these methods have drawbacks such as long reaction steps and expensive raw materials.
（問題点を解決するための手段、及び作用）本発明者等
は該カルボン酸を安価な原料を用い、しかも反応工程が
簡単な反応方法を種々検討の結果、安価なジフェニルか
ら容易に合成出来るヨウ素化ジフェニル又は臭素化ジフ
ェニルを塩基性物質、遷移金属化合物を含有する触媒の
存在下、水単独又は水を含有する溶媒系として、水を該
ヨウ素化ジフェニル又は臭素化ジフェニルのハロゲンに
対して当量以上用い、一酸化炭素と反応させることによ
ってカルボン酸を得ることが出来ることを見出し本発明
を完成させるに至った。即ち、本発明はヨウ素化ジフェ
ニル又は臭素化ジフェニルを塩基性物質、遷移金属化合
物を含有する触媒の存在下、水単独又は水を含有する溶
媒系として、水を該ヨウ素化ジフェニル又は臭素化ジフ
ェニルのハロゲンに対して当量以上用い、一酸化炭素と
反応させることを特徴とするジフェニルカルボン酸の製
造方法である。(Means and effects for solving the problem) The present inventors have investigated various reaction methods using inexpensive raw materials and simple reaction steps, and found that the carboxylic acid can be easily synthesized from inexpensive diphenyl. Iodinated diphenyl or brominated diphenyl is treated in the presence of a catalyst containing a basic substance and a transition metal compound, water alone or as a solvent system containing water, and water is added in an amount equivalent to the halogen of the iodinated diphenyl or brominated diphenyl. Using the above methods, they discovered that carboxylic acids can be obtained by reacting with carbon monoxide, and have completed the present invention. That is, in the present invention, iodinated diphenyl or brominated diphenyl is mixed with water alone or as a solvent system containing water in the presence of a catalyst containing a basic substance and a transition metal compound. This is a method for producing diphenylcarboxylic acid, which is characterized by using an equivalent or more amount of halogen and reacting with carbon monoxide.
本発明の原料として使用するヨウ素化ジフェニルは、４
−ヨードジフェニル、４，４′−ジヨードジフェニルな
どであり、臭素化ジフェニルは、４−ブロムジフェニル
、４，４′−ジブロムジフェニルなどであり、種々の方
法で得ることが出来る。例えば４−ヨードジフェニル、
４，４′−ジヨードジフェニルは、ジフェニルを硝酸存
在下、ヨウ素と反応させることによりヨウ素化ジフェニ
ルを高収率で得ることが出□来、反応させるヨウ素の量
を変えることにより各々を選“択的に得ることが出来る
。The iodinated diphenyl used as a raw material in the present invention is 4
-iododiphenyl, 4,4'-diiododiphenyl, etc. Brominated diphenyls include 4-bromidiphenyl, 4,4'-dibromidiphenyl, etc., and can be obtained by various methods. For example, 4-iododiphenyl,
4,4'-diiododiphenyl can be obtained in high yield by reacting diphenyl with iodine in the presence of nitric acid, and each can be selected by changing the amount of iodine to be reacted. can be obtained selectively.
本発明で用いられる塩基性物質は、有機塩基、無機塩基
どちらも用いることが出来、反応で生成するヨウ化水素
等を捕捉出来るものであれば良く、例えば、脂肪族アミ
−ン、芳香族アミン、水酸化第四級アンモニウム、アル
カリ金属アルコラード、アルカリ金属水酸化物、アルカ
リ金属炭酸塩等が挙げられる。好ましくは脂肪族アミン
、水酸化第４級アンモニウム、アルカリ金属水酸化物、
アルカリ金属炭酸塩を用いることができる。使用量は、
脂肪族アミン、芳香族アミン等の有機アミン類は反応さ
せるヨウ素化ジフェニル又は臭素化ジフェニルのハロゲ
ンに対し当量以上であれば良い、これに対し、アルカリ
金属水酸化物等の強塩基を用いる場合は、反応させるヨ
ウ素化ジフェニル又は臭素化ジフェニルのハロゲンに対
して当量程度用いることが収率の点で好ましい。The basic substance used in the present invention can be either an organic base or an inorganic base, as long as it can capture hydrogen iodide etc. generated in the reaction. , quaternary ammonium hydroxide, alkali metal alcoholades, alkali metal hydroxides, alkali metal carbonates, and the like. Preferably aliphatic amines, quaternary ammonium hydroxides, alkali metal hydroxides,
Alkali metal carbonates can be used. The amount used is
The amount of organic amines such as aliphatic amines and aromatic amines should be at least equivalent to the halogen of the iodinated diphenyl or brominated diphenyl to be reacted.On the other hand, when using a strong base such as an alkali metal hydroxide, From the viewpoint of yield, it is preferable to use an amount equivalent to the halogen of the iodinated diphenyl or brominated diphenyl to be reacted.
本発明で用いられる遷・移金属としては、一般にカルボ
ニル化反応に活性なものが用いられ、■、■族の遷移金
属、例えばパラジウム、白金、ニッケル、コバルト、鉄
、マンガン等が挙げられるが、収率の点から好ましくは
パラジウム、ニッケル、コバルト、鉄が用いられる。こ
れらの遷移金属は、これら自身か、これらの□ハロゲン
化物、硫酸塩、硝酸塩、有機酸塩等を用いることが出来
る。また、これら遷移金属化合物は、一酸化炭素の錯体
、トリフェニルホスフィン等のホスフィン類の錯体とし
て用いることも出来る。遷移金属化合物の使用量は反応
させるヨウ素化ジフェニル又は臭素化ジフェニルの０．
０１−１０モル％であれば良い。The transition/transition metals used in the present invention are generally those active in carbonylation reactions, and include transition metals of groups 1 and 2, such as palladium, platinum, nickel, cobalt, iron, and manganese. From the viewpoint of yield, palladium, nickel, cobalt, and iron are preferably used. These transition metals themselves can be used, or their halides, sulfates, nitrates, organic acid salts, etc. can be used. Further, these transition metal compounds can also be used as a complex of carbon monoxide or a complex of phosphines such as triphenylphosphine. The amount of the transition metal compound to be used is 0.00% of the iodinated diphenyl or brominated diphenyl to be reacted.
It is sufficient if it is 01-10 mol%.
反応はオートクレーブ内で一酸化炭素加圧下で行うこと
が出来、圧力は、ゲージ圧１〜２００ ｋｇ／ｃ−２、
好ましくは５〜１００ ｋｇ／ｃｍ”である。１ ｋｇ
／ｃ＋ａ２より低いと反応速度が遅＜ 、２００ ｋｇ
／ｃ■２より高いと分解等の副反応が多くなる。The reaction can be carried out in an autoclave under pressure of carbon monoxide, with a gauge pressure of 1 to 200 kg/c-2,
Preferably 5 to 100 kg/cm". 1 kg
If it is lower than /c+a2, the reaction rate is slow < , 200 kg
If it is higher than /c2, side reactions such as decomposition will increase.
反応温度は、反応速度の点で５０’Ｃ以上であれば良く
、２００°Ｃ以上でＬよ副反応が多くなる。好ましくは
、１００°Ｃ〜２００°Ｃである。The reaction temperature may be 50'C or higher in terms of reaction rate, and side reactions will occur more frequently if it is 200°C or higher. Preferably it is 100°C to 200°C.
本発明では水が単独で用いられるか又は水を含有する溶
媒系として用いられる。溶剤としては、原料であるヨウ
素化ジフェニル又は臭素化ジフェニルを溶解する溶媒又
は水との両方に溶解性のある溶媒を用いることができる
。例えばメタノール、゛エタノール、プロパツール等の
脂肪族アルコール、ベンジルアルコール、フェノール等
の芳香性アルコール類、ヘキサン、オクタン、ベンゼン
、トルエン等の炭化水素、ジメチルホルムアミド、ジメ
チルスルホキシド等の極性溶媒、ジオキサン等のエーテ
ル類等がある。また、塩基性物質として用いる脂肪族ア
ミン、芳香族アミンを用いることもできる。Water is used in the present invention either alone or as a solvent system containing water. As the solvent, a solvent that dissolves the raw material iodinated diphenyl or brominated diphenyl or a solvent that is soluble in both water can be used. For example, aliphatic alcohols such as methanol, ethanol, and propatool; aromatic alcohols such as benzyl alcohol and phenol; hydrocarbons such as hexane, octane, benzene, and toluene; polar solvents such as dimethylformamide and dimethyl sulfoxide; There are ethers, etc. Furthermore, aliphatic amines and aromatic amines used as basic substances can also be used.
反応に用いる水の使用量は水単独で用いる場合、ヨウ素
化ジフェニル又は臭素化ジフェニルに対して少なくとも
当量以上用いる必要がある。溶媒として量を多く用いる
ことはもちろん差し支えはない。水を含有する溶媒系と
して用いた場合も水単独の場合と同様の量を用いること
が必要であり、他の溶媒系と混合することにより、反応
系を均一にする等の効果が期待できる。When using water alone in the reaction, it is necessary to use at least an equivalent amount to the iodinated diphenyl or brominated diphenyl. Of course, there is no problem in using a large amount as a solvent. When used as a solvent system containing water, it is necessary to use the same amount as in the case of water alone, and by mixing it with other solvent systems, effects such as making the reaction system uniform can be expected.
（発明の効果）
上述の様に、本発明は、人手容易な安価な原料を用い、
簡単な工程により新規なジフェニルカルボン酸の製造方
法を提供するものであり、工業的価値は高い。この化合
物は、耐熱性、高強度に優れた繊維や樹脂などの原料と
して利用される。(Effect of the invention) As described above, the present invention uses inexpensive raw materials that are easy to handle,
The present invention provides a novel method for producing diphenylcarboxylic acid using simple steps, and has high industrial value. This compound is used as a raw material for fibers and resins that have excellent heat resistance and high strength.
（実施例） 次に、実施例により本発明をさらに詳細に説明する。(Example) Next, the present invention will be explained in more detail with reference to Examples.
実施例１
４．４′−ジヨードジフェニル４０．６ｇ（０，１モル
）、ｎ−）リブチルアミン２７．８ ｇ （０，１５モ
ル）、塩化パラジウム０．１８ ｇ （０，００１モル
）、トリフェニルホスフィン ０．７９ｇ （０，００
３モル）、水ｓｏ３ （２，８モル）、エタノール５ｏ
８（１，１モル）を電磁攪１ｆ−機付きオートクレーブ
に仕込み、次いで一酸化炭素３０ ｋｇ／ｃｍ２仕込ん
だ。次に、１５０＠Ｃに昇温させて２蒔間反応させた。Example 1 40.6 g (0.1 mol) of 4.4'-diiododiphenyl, 27.8 g (0.15 mol) of n-)butylamine, 0.18 g (0.001 mol) of palladium chloride, Triphenylphosphine 0.79g (0,00
3 mol), water SO3 (2.8 mol), ethanol 5o
8 (1.1 mol) was charged into an autoclave equipped with a 1F electromagnetic stirrer, and then 30 kg/cm2 of carbon monoxide was charged. Next, the temperature was raised to 150@C to carry out a reaction between the two solubilizers.
反応中一酸化炭素の圧力を３０に８１Ｃ１１２に一定に
保った。The pressure of carbon monoxide was kept constant at 30.8C112 during the reaction.
反応後、未反応の一酸化炭素をパージした後、反応液を
取り出し液体クロマトグラフィーにより分析を行った。After the reaction, unreacted carbon monoxide was purged, and the reaction solution was taken out and analyzed by liquid chromatography.
その結果、４，４ξジフエニルジカルボン酸が１４．５
ｇ（０，０６モル）生成していた。未反応の４，４′
−ジヨードジフェニルは検出されなかった。As a result, 4,4ξ diphenyl dicarboxylic acid was 14.5
g (0.06 mol) was produced. Unreacted 4,4'
-Diiododiphenyl was not detected.
実施例２
４−ヨードジフェニル２８．０ｇ（０，１モル）、ｎ−
）リブチルアミン２０．２ｇ （０，２モル）、酢酸ニ
ッケル０．３５ｇ （０，００２モル）、トリフェニル
ホスフィン１．５７ｇ （０，００６モル）、水５０
ｇ （２，８モル）を仕込み、温度１８０°Ｃ，１時間
、一酸化炭素圧力５０ ｋｇ／ｃａｂ２で実施例１と同
様な装置、方法で実施した。その結果トジフェニルカル
ボン酸が１０．９ｇ（０，０５５モル）生成していた。Example 2 4-iododiphenyl 28.0 g (0.1 mol), n-
) butylamine 20.2g (0.2 mol), nickel acetate 0.35g (0,002 mol), triphenylphosphine 1.57g (0,006 mol), water 50
The experiment was carried out using the same apparatus and method as in Example 1, using the same method as in Example 1, at a temperature of 180° C. for 1 hour and a carbon monoxide pressure of 50 kg/cab2. As a result, 10.9 g (0,055 mol) of todiphenylcarboxylic acid was produced.
未反応の４−ヨードジフェニルは検出されなかった。No unreacted 4-iododiphenyl was detected.
実施例３
４．４′−ジブロムジフェニル３１．２ｇ（０，１モル
）、ｎ−トリブチルアミン２７．８ ｇ （０，１５モ
ル）、塩化コバルト０．６５ｇ （０，００５モル）、
トリフェニルホスフィン１．５８ｇ （０，００６モル
）、水５０ｇ （２，８モル）、フェノール５０ｇ （
０，５５モル）を仕込み、温度１５０＠Ｃ，３時間、一
酸化炭素圧力３０ｋｇ／ｃａ＋”で実施例１と同様な装
置、方法で実施した。その結果４．４′−ジフェニルジ
カルボン酸がｓ、ｓｇ（ｏ、ｏ３ｓ３ｇ）生成していた
。Example 3 4.4′-dibromidiphenyl 31.2 g (0.1 mol), n-tributylamine 27.8 g (0.15 mol), cobalt chloride 0.65 g (0.005 mol),
Triphenylphosphine 1.58g (0,006 mol), water 50g (2.8 mol), phenol 50g (
The experiment was carried out using the same apparatus and method as in Example 1 at a temperature of 150@C for 3 hours and a carbon monoxide pressure of 30 kg/ca+''.As a result, 4,4'-diphenyldicarboxylic acid was , sg(o, o3s3g) was generated.
実施例４
４−ブロムジフェニル２３．３ｇ（０，１モル）、ｎ−
）リブチルアミン２７．８ｇ （０，１５モル）、塩化
鉄０．２５ｇ （０，００２モル）、トリフェニルホス
フィン０．５２ｇ （０，００２モル）、水５０ｇ （
２，８モル）、エタノール５０ｇ（１，１モル）を仕込
み、温度１５０”ｃ 、 １時間、一酸化炭素圧力３０
ｋｇ／ｃｍ”で実施例１と同様な装置、方法で実施した
。その結果へ一ジフェニルカルボン酸が５−９ｇ（０，
０３モル）生成していた。Example 4 23.3 g (0.1 mol) of 4-bromidiphenyl, n-
) butylamine 27.8 g (0.15 mol), iron chloride 0.25 g (0.002 mol), triphenylphosphine 0.52 g (0.002 mol), water 50 g (
2.8 mol) and 50 g (1.1 mol) of ethanol, temperature 150"C, 1 hour, carbon monoxide pressure 30
kg/cm" using the same equipment and method as in Example 1. As a result, 5-9 g of monodiphenyl carboxylic acid (0,
03 mol) was produced.
実施例５
４．４′−ジヨードジフェニル４０．６ｇ（０，１モル
）、ｎ−）リブチルアミン２７．８ｇ （０，１５モル
）、塩化パラジウム０．９０ｇ（０，００５モル）、水
５０ｇ （２，８ｔル）、エタノール５０ｇ（１，１モ
ル）を仕込み、温度ｔｓｏ”ｃ 。Example 5 40.6 g (0.1 mol) of 4.4'-diiododiphenyl, 27.8 g (0.15 mol) of n-)butylamine, 0.90 g (0.005 mol) of palladium chloride, 50 g of water. (2.8 tons) and 50 g (1.1 mol) of ethanol were charged at a temperature of tso"c.
１時間、一酸化炭素圧力４０ｋｇ／ｃｍ２で実施例１と
同様な装置、方法で実施した。その結果、４，４′−ジ
フェニルジカルボン酸が１３．３ｇ（０，０６モル）生
成していた。The experiment was carried out using the same apparatus and method as in Example 1 at a carbon monoxide pressure of 40 kg/cm2 for 1 hour. As a result, 13.3 g (0.06 mol) of 4,4'-diphenyldicarboxylic acid was produced.
Claims (4)
性物質、遷移金属化合物を含有する触媒の存在下、水単
独又は水を含有する溶媒系として、水を該ヨウ素化ジフ
ェニル又は臭素化ジフェニルのハロゲンに対して当量以
上用い、一酸化炭素と反応させることを特徴とするジフ
ェニルカルボン酸の製造方法。(1) Iodinated diphenyl or brominated diphenyl is converted into halogen of the iodinated diphenyl or brominated diphenyl by water alone or in a solvent system containing water in the presence of a catalyst containing a basic substance and a transition metal compound. 1. A method for producing diphenylcarboxylic acid, which comprises using an equivalent or more amount of diphenylcarboxylic acid and reacting it with carbon monoxide.
は４，４′−ジヨードジフェニルである特許請求の範囲
第（１）項記載の方法。 方法。(2) The method according to claim (1), wherein the iodinated diphenyl is 4-iododiphenyl or 4,4'-diiododiphenyl. Method.
４，４′−ジブロムジフェニルである特許請求の範囲第
（１）項記載の方法。 方法。(3) The method according to claim (1), wherein the brominated diphenyl is 4-bromodiphenyl or 4,4'-dibromodiphenyl. Method.
ト、鉄化合物である特許請求の範囲第（１）項記載の方
法。(4) The method according to claim (1), wherein the transition metal compound is a palladium, nickel, cobalt, or iron compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61026911A JPS62185055A (en) | 1986-02-12 | 1986-02-12 | Production of diphenylcarboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61026911A JPS62185055A (en) | 1986-02-12 | 1986-02-12 | Production of diphenylcarboxylic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62185055A true JPS62185055A (en) | 1987-08-13 |
Family
ID=12206397
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61026911A Pending JPS62185055A (en) | 1986-02-12 | 1986-02-12 | Production of diphenylcarboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62185055A (en) |
-
1986
- 1986-02-12 JP JP61026911A patent/JPS62185055A/en active Pending
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