JPS62187434A - Production of diphenylcarboxylic acid ester - Google Patents
Production of diphenylcarboxylic acid esterInfo
- Publication number
- JPS62187434A JPS62187434A JP61026912A JP2691286A JPS62187434A JP S62187434 A JPS62187434 A JP S62187434A JP 61026912 A JP61026912 A JP 61026912A JP 2691286 A JP2691286 A JP 2691286A JP S62187434 A JPS62187434 A JP S62187434A
- Authority
- JP
- Japan
- Prior art keywords
- mol
- diphenyl
- carbon monoxide
- alcohol
- reaction
- 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
- -1 diphenylcarboxylic acid ester Chemical class 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 125000006267 biphenyl group Chemical group 0.000 claims abstract description 25
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 8
- 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 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- 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
- 239000000126 substance Substances 0.000 claims description 5
- 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
- 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 description 2
- 150000002506 iron compounds Chemical class 0.000 claims 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 abstract description 10
- 235000010290 biphenyl Nutrition 0.000 abstract description 7
- 239000004305 biphenyl Substances 0.000 abstract description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 235000019445 benzyl alcohol Nutrition 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 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 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 5
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 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
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens 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
- 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
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 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 1
- 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
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000005810 carbonylation reaction Methods 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
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004820 halides 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
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 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エステルの製造
法に関す、る。詳しくはヨウ素化ジフェニル、または臭
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、一酸化炭素、アルコールと反応させる
ことを特徴とするジフェニルカルボン酸エステルを製造
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 ester. Specifically, it is a method for producing diphenyl carboxylic acid ester, which is characterized by reacting iodinated diphenyl or brominated diphenyl with carbon monoxide and alcohol in the presence of a catalyst containing a basic substance and a transition metal compound.
（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
ロル安息香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。ジフェニルカルボン酸エステルを得るために
は公知の方法でエステル化する。(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. In order to obtain diphenylcarboxylic acid ester, esterification is carried out by a known method.
（発明が解決しようとする問題点）
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ったり、工業的に実施する場合は有
利な方法とは言えない。(Problems to be Solved by the Invention) However, in these methods, the reaction steps are long, the raw materials used are expensive, and these methods cannot be said to be advantageous when implemented industrially.
（問題点を解決するための手段、及び作用）本発明者等
は安価な原料を用い、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、また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、一
酸化炭素、アルコールと反応させることによって高収率
で、ジフェニルカルボン酸エステル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、また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、一
酸化炭素、アルコールと反応させることを特徴とするジ
フェニルカルボン酸エステルの製造法である。(Means and effects for solving the problems) The present inventors have studied various reaction methods that use inexpensive raw materials and have simple reaction steps, and have found that iodinated diphenyl, which can be easily synthesized from inexpensive diphenyl, Alternatively, it was discovered that diphenyl carboxylic acid ester can be obtained in high yield by reacting brominated diphenyl with carbon monoxide and alcohol in the presence of a catalyst containing a basic substance and a transition metal compound. I ended up completing it. That is, the present invention is a method for producing diphenyl carboxylic acid ester, which is characterized by reacting iodinated diphenyl or brominated diphenyl with carbon monoxide and alcohol in the presence of a catalyst containing a basic substance and a transition metal compound. be.
本発明の原料として使用するヨウ素化ジフェニル、また
は臭素化ジフェニルは、４−ヨードジフェニル、４．４
’−ジヨードジフェニル、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０例えばヨウ素化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 or brominated diphenyl used as a raw material in the present invention is 4-iododiphenyl, 4.4
'-diiododiphenyl, 4-bromidiphenyl, 4,
For example, iodinated diphenyl can be obtained in high yield by reacting diphenyl with iodine in the presence of nitric acid, and the amount of iodine to be reacted is Each can be selectively obtained by changing .
本発明で用いる塩基性物質は、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を捕
捉出来るものであれば良い。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、アルカ
リ金属アルコラード、水酸化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、反応させるヨウ素化ジフェニル、臭素
化ジフェニルのハロゲンに対して当量以上であれば良い
。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 produced in the reaction. Examples include aliphatic amines, aromatic amines, quaternary ammonium hydroxides, alkali metal alcoholades, alkali metal hydroxides, alkali metal carbonates, and the like. Preferably, aliphatic amines, alkali metal alcolades, quaternary ammonium hydroxides, alkali metal hydroxides, and alkali metal carbonates can be used. The amount used may be at least equivalent to the halogen of the iodinated diphenyl or brominated diphenyl to be reacted.
本発明で用い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、有機酸塩またはアセチルアセトン等の錯
塩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、臭素化ジ
フェニルの０．０１〜１０モル％であれば良い。As the transition metal used in the present invention, those active in carbonylation reactions are generally used, and examples include transition metals of groups 1 and 2, such as palladium, platinum, nickel, cobalt, iron, and manganese. From this point of view, palladium, nickel, cobalt, and iron are preferably used. These transition metals can be used themselves or in the form of their halides, sulfates, nitrates, organic acid salts, or complex salts such as acetylacetone. Further, these transition metal compounds can also be used as carbon monoxide complexes and complexes of phosphines such as triphenylphosphine. The amount of the transition metal compound to be used may be 0.01 to 10 mol% of the iodinated diphenyl or brominated diphenyl to be reacted.
本発明で用いるアルコールは、目的に応じて使用出来る
。脂肪族アルコール、芳香族アルコール類等いずれも使
用できる。好ましくは、脂肪族アルコールでは、メタノ
ール、エタノール、プロパツール、芳香族アルコール類
では、ベンジルアルコール、フェノールである２、アル
コールの使用量は、反応させるヨウ素化ジフェニル、臭
素化ジフェニルのハロゲンに対して当量以上であれば良
い。The alcohol used in the present invention can be used depending on the purpose. Both aliphatic alcohols and aromatic alcohols can be used. Preferably, the aliphatic alcohol is methanol, ethanol, propatool, and the aromatic alcohol is benzyl alcohol or phenol2. The amount of alcohol used is equivalent to the halogen of the iodinated diphenyl or brominated diphenyl to be reacted. Anything above that is fine.
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１〜１００ ｋｇ／ｃＩ２で
あることが好ましい。１ ｋｇ／ｃｍ’より低いと反応
速度が遅く、１００ ｋｇ／ｃｍ”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 carbon monoxide pressure, and the pressure is preferably 1 to 100 kg/cI2 gauge. If it is lower than 1 kg/cm', the reaction rate will be slow, and if it is higher than 100 kg/cm', 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＜
、２００＠Ｃ以上では副反応が多くなる。好ましくは
、１００°Ｃ〜２００°Ｃである。The reaction temperature should be 50°C or higher in terms of reaction rate.
, 200@C or more, side reactions increase. Preferably it is 100°C to 200°C.
（発明の効果）
上述の様に、本発明は、入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エステル
の製造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の原料
として利用される。(Effect of the invention) As mentioned above, the present invention uses easily available and inexpensive raw materials,
The present invention provides a new method for producing diphenylcarboxylic acid esters through 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
４．４ξショートジフェニル４０．６ｇ（０，１モル）
、ｎ−トリブチルアミン２７．８ｇ （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 （０，００３モ
ル）、エタノール１００ｇ （２，２モル）を電磁攪１
牢機付きオートクレーブに仕込み、次いで一酸化炭素を
３０ｋｇ／ｃｍ２仕込んだ。Example 1 40.6 g (0.1 mol) of 4.4ξ short diphenyl
, n-tributylamine 27.8g (0.15 mol)
, palladium chloride 0.18 g (0,001 mol),
0.79 g (0,003 mol) of triphenylphosphine and 100 g (2.2 mol) of ethanol were stirred magnetically.
The mixture was placed in an autoclave equipped with a cell, and then carbon monoxide was added at 30 kg/cm2.
次に、１５０°Ｃに昇温させて２時間反応させた。反応
中一酸化炭素の圧力を３０ｋｇ／ｃｍ２に一定に保った
。Next, the temperature was raised to 150°C and a reaction was carried out for 2 hours. The pressure of carbon monoxide was kept constant at 30 kg/cm2 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
取り出しガス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 gas chromatography.
その結果、４，４′−ジフェニルジカルボン酸ジエチル
エステルが２６．８ ｇ（０，０９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, 26.8 g (0.09 mol) of 4,4'-diphenyldicarboxylic acid diethyl ester was produced. No unreacted 4,4'-diiododiphenyl was detected.
実施例２
４−ヨードジフェニル２８．０ｇ（０，１モル）、ｎ−
）リエチルアミン２０．２ｇ（０，２モル）、硝酸パラ
ジウム０．４６ｇ（０，００２モル）、トリフェニルホ
スフィン１．５７ ｇ （０，００６モル）、メタール
１５０ ｇ （４，６９モル）を仕込み、温度１２０°
Ｃ１３時間、一酸化炭素圧力２０ｋｇ／ｃｍ２で実施例
１と同様な装置、方法で実施した。その結果４−ジフェ
ニルカルボン酸メチルエステルが１９．５ｇ（０，０９
２モル）生成していた。Example 2 4-iododiphenyl 28.0 g (0.1 mol), n-
) 20.2 g (0.2 mol) of ethylamine, 0.46 g (0,002 mol) of palladium nitrate, 1.57 g (0,006 mol) of triphenylphosphine, and 150 g (4.69 mol) of metal were prepared. , temperature 120°
The experiment was carried out using the same apparatus and method as in Example 1 at a carbon monoxide pressure of 20 kg/cm2 for 13 hours. As a result, 19.5 g (0,09
2 mol) was produced.
実施例３
４．４′−ジヨードジフェニル ４０．６ｇ（０，１モ
ル）、ｎ −Ｉ−リブチルアミン２７．８ｇ（０，１５
モル）、塩化パラジウム０．１８ｇ （０，００１モル
）、トリフェニルホスフィン０．７９ｇ （０，００３
モル）、フェノール３７．６ｇ （０，４モル）を仕込
み、温度１２０°Ｃ１３時間、一酸化炭素圧力２０ｋｇ
／ｃｍ２て実施例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ジフェノール
エステルが３７．４ｇ（０，０９５モル）生成していた
。Example 3 40.6 g (0.1 mol) of 4.4'-diiododiphenyl, 27.8 g (0.15 mol) of n-I-butylamine
mol), palladium chloride 0.18g (0,001 mol), triphenylphosphine 0.79g (0,003
mol), phenol 37.6g (0.4 mol), temperature 120°C 13 hours, carbon monoxide pressure 20kg
/cm2 using the same apparatus and method as in Example 1. As a result, 37.4 g (0,095 mol) of 4.4'-diphenyldicarboxylic acid diphenol ester was produced.
実施例４
４−ヨードジフェニル２８．０ｇ（０，１モル）、ｎ−
）リエチルアミン２０．２ ｇ （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）、ベンジル
アルコール１６゜２ｇ （０，１５モル）を仕込み、温
度１３０°Ｃ１３時間、一酸化炭素圧力３０ｋｇ／ｃｎ
＋２で実施例１と同様な装置、方法で実施した。その結
果４−ジフェニルカルボン酸ベンジルエステルが２４．
５ｇ（０，０８５モル）生成していた。Example 4 28.0 g (0.1 mol) of 4-iododiphenyl, n-
) 20.2 g (0,2 mol) of ethylamine, 0.35 g (0,002 mol) of nickel acetate, 1.57 g (0,006 mol) of triphenylphosphine, 16°2 g (0,15 mol) of benzyl alcohol temperature 130°C for 13 hours, carbon monoxide pressure 30kg/cn
+2 using the same equipment and method as in Example 1. As a result, 4-diphenylcarboxylic acid benzyl ester was 24.
5g (0,085 mol) was produced.
実施例５
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０．１３ 、ｇ （０，００１モル
）、トリフェニルホスフィン０．７９ｇ （０，００３
モル）、フェノール１００ｇ （１，１モル）を仕込み
、温度１５０°Ｃ，３時間、一酸化炭素圧力３０ｋｇ／
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ジフェノールエ
ステルが２１．７ｇ（０，０５５モル）生成していた。Example 5 4.4'-Dibromidiphenyl 31.2 g (0.1 mol), n-tributylamine 27.8 g (0.15 mol), cobalt chloride 0.13 g (0.001 mol), Triphenylphosphine 0.79g (0,003
mol), phenol 100g (1.1 mol) was charged, temperature was 150°C, 3 hours, carbon monoxide pressure was 30kg/
cm2 using the same equipment and method as in Example 1. As a result, 21.7 g (0,055 mol) of 4.4''-diphenyldicarboxylic acid diphenol ester was produced.
実施例６
トブロムジフエニル２３．３ｇ（０，１モル）、ｎ−）
リブチルアミン２７．８ ｇ （０，１５モル）、塩化
鉄０．２５ｇ （０，００２モル）、トリフェニルホス
フィン０．５２ ｇ （０，００２モル）、フェノール
５０ｇ （０，５３モル）を仕込み、温度１５０°Ｃ１
１時間、一酸化炭素圧力２０ｋｇ／ｃｍ’で実施例１と
同様な装置、方法で実施した。その結果４−ジフェニル
カルボン酸フェノールエステルが９．０ｇ（０，０３５
モル）生成していた。Example 6 Tobromidiphenyl 23.3 g (0.1 mol), n-)
27.8 g (0.15 mol) of butylamine, 0.25 g (0.002 mol) of iron chloride, 0.52 g (0.002 mol) of triphenylphosphine, and 50 g (0.53 mol) of phenol were charged. Temperature 150°C1
It was carried out using the same apparatus and method as in Example 1 at a carbon monoxide pressure of 20 kg/cm' for 1 hour. As a result, 9.0g (0,035g of 4-diphenylcarboxylic acid phenol ester)
mole) was produced.
実施例７
４−ヨードジフェニル２８．０ｇ（０，１モル）、ｎ−
トリエチルアミン２０．２ ｇ （０，２モル）、ニッ
ケルアセチルアセトネート０．５１ｇ （０，００２モ
ル）、トリフェニルホスフィン１．５７ｇ（０，００６
モル）、フェノール１４．１ｇ （０，１５モル）を仕
込み、温度１５０°Ｃ１３時間、一酸化炭素圧力３０ｋ
ｇ／ｃｍ２で実施例１と同様な装置、方法で実施した。Example 7 28.0 g (0.1 mol) 4-iododiphenyl, n-
20.2 g (0.2 mol) of triethylamine, 0.51 g (0.002 mol) of nickel acetylacetonate, 1.57 g (0.006 mol) of triphenylphosphine.
mol), phenol 14.1g (0.15 mol), temperature 150°C 13 hours, carbon monoxide pressure 30k
g/cm2 using the same apparatus and method as in Example 1.
その結果４−ジフェニルカルボン酸フェノールエステル
が２４．７ｇ（０，０９モル）生成していた。As a result, 24.7 g (0.09 mol) of 4-diphenylcarboxylic acid phenol ester was produced.
実施例８
４．４′−ジヨードジフェニル ４０．６ｇ（０，１モ
ル）、ｎ−トリブチルアミン２７．８ｇ（０，１５モル
）、塩化パラジウム０．１８ｇ （０，００１モル）、
フェノール３７．６ｇ （０，４モル）を仕込み、温度
１５０＠Ｃ，１時間、一酸化炭素圧力５０ｋｇ／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ジフェノールエステル
が３５．４３（０，０９モル）生成していた。Example 8 40.6 g (0.1 mol) of 4.4'-diiododiphenyl, 27.8 g (0.15 mol) of n-tributylamine, 0.18 g (0.001 mol) of palladium chloride,
Phenol 37.6g (0.4 mol) was charged, temperature 150@C, 1 hour, carbon monoxide pressure 50kg/cm2
The experiment was carried out using the same apparatus and method as in Example 1. Result 4
．． 35.43 (0.09 mol) of 4'-diphenyldicarboxylic acid diphenol ester was produced.
Claims (4)
塩基性物質、遷移金属化合物を含有する触媒の存在下、
一酸化炭素、アルコールと反応させることを特徴とする
ジフェニルカルボン酸エステルの製造法。(1) Iodinated diphenyl or brominated diphenyl in the presence of a basic substance and a catalyst containing a transition metal compound,
A method for producing diphenylcarboxylic acid ester, which is characterized by reaction with carbon monoxide and alcohol.
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。(2) The method according to claim (1), wherein the iodinated diphenyl is 4-iododiphenyl or 4,4'-diiododiphenyl.
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。(3) The method according to claim (1), wherein the brominated diphenyl is 4-bromodiphenyl or 4,4'-dibromidiphenyl.
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 |
|---|---|---|---|
| JP61026912A JPS62187434A (en) | 1986-02-12 | 1986-02-12 | Production of diphenylcarboxylic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61026912A JPS62187434A (en) | 1986-02-12 | 1986-02-12 | Production of diphenylcarboxylic acid ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62187434A true JPS62187434A (en) | 1987-08-15 |
Family
ID=12206425
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61026912A Pending JPS62187434A (en) | 1986-02-12 | 1986-02-12 | Production of diphenylcarboxylic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62187434A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02295949A (en) * | 1989-05-10 | 1990-12-06 | Agency Of Ind Science & Technol | 9,10-dihydrophenanthrene-2,7-dicarboxylic acid diester, 7-bromo-9,10-dihydrophenanthrene-2-carboxylic acid ester and production thereof |
| JPH03258752A (en) * | 1990-03-07 | 1991-11-19 | Agency Of Ind Science & Technol | Production of 4,4'-biphenyldicarboxylic acid diester |
| JPH04169556A (en) * | 1990-11-02 | 1992-06-17 | Agency Of Ind Science & Technol | Production of biphenyl-4-4'-dicarboxylic acid dieser |
| JPH0812623A (en) * | 1994-06-23 | 1996-01-16 | Agency Of Ind Science & Technol | Production of ester of biphenyl-4-carboxylic acid and phenol compound |
| JP2019500209A (en) * | 2015-12-18 | 2019-01-10 | イエフペ エネルジ ヌヴェルＩｆｐ Ｅｎｅｒｇｉｅｓ Ｎｏｕｖｅｌｌｅｓ | Catalyst composition comprising nickel, phosphine-type ligand and Lewis base and its use in olefin oligomerization process |
-
1986
- 1986-02-12 JP JP61026912A patent/JPS62187434A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02295949A (en) * | 1989-05-10 | 1990-12-06 | Agency Of Ind Science & Technol | 9,10-dihydrophenanthrene-2,7-dicarboxylic acid diester, 7-bromo-9,10-dihydrophenanthrene-2-carboxylic acid ester and production thereof |
| JPH03258752A (en) * | 1990-03-07 | 1991-11-19 | Agency Of Ind Science & Technol | Production of 4,4'-biphenyldicarboxylic acid diester |
| JPH04169556A (en) * | 1990-11-02 | 1992-06-17 | Agency Of Ind Science & Technol | Production of biphenyl-4-4'-dicarboxylic acid dieser |
| JPH0812623A (en) * | 1994-06-23 | 1996-01-16 | Agency Of Ind Science & Technol | Production of ester of biphenyl-4-carboxylic acid and phenol compound |
| JP2019500209A (en) * | 2015-12-18 | 2019-01-10 | イエフペ エネルジ ヌヴェルＩｆｐ Ｅｎｅｒｇｉｅｓ Ｎｏｕｖｅｌｌｅｓ | Catalyst composition comprising nickel, phosphine-type ligand and Lewis base and its use in olefin oligomerization process |
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