JPH03284654A - Production of 7-bromo-9,10-dihydrophenanthrene-2-carboxylic acid ester - Google Patents
Production of 7-bromo-9,10-dihydrophenanthrene-2-carboxylic acid esterInfo
- Publication number
- JPH03284654A JPH03284654A JP2083898A JP8389890A JPH03284654A JP H03284654 A JPH03284654 A JP H03284654A JP 2083898 A JP2083898 A JP 2083898A JP 8389890 A JP8389890 A JP 8389890A JP H03284654 A JPH03284654 A JP H03284654A
- Authority
- JP
- Japan
- Prior art keywords
- dihydrophenanthrene
- carboxylic acid
- bromo
- palladium
- dibromo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- QXEZLMVQNMVYRX-UHFFFAOYSA-N 7-bromo-9,10-dihydrophenanthrene-2-carboxylic acid Chemical compound BrC1=CC=C2C3=CC=C(C(=O)O)C=C3CCC2=C1 QXEZLMVQNMVYRX-UHFFFAOYSA-N 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 10
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- CZFAGVNUIFJWGE-UHFFFAOYSA-N 2,7-dibromo-9,10-dihydrophenanthrene Chemical compound BrC1=CC=C2C3=CC=C(Br)C=C3CCC2=C1 CZFAGVNUIFJWGE-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZOUWOGOTHLRRLS-UHFFFAOYSA-N palladium;phosphane Chemical compound P.[Pd] ZOUWOGOTHLRRLS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000002430 hydrocarbons Chemical group 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 abstract description 14
- 229910000030 sodium bicarbonate Inorganic materials 0.000 abstract description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 abstract description 7
- HEAZVVTVISIFPP-UHFFFAOYSA-N 1,1-dibromo-2h-phenanthrene Chemical compound C1=CC2=CC=CC=C2C2=C1C(Br)(Br)CC=C2 HEAZVVTVISIFPP-UHFFFAOYSA-N 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 229920000106 Liquid crystal polymer Polymers 0.000 abstract description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- QDTCBEZXBDUOCR-UHFFFAOYSA-N n,n-dibutylbutan-1-amine oxide Chemical compound CCCC[N+]([O-])(CCCC)CCCC QDTCBEZXBDUOCR-UHFFFAOYSA-N 0.000 abstract 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 12
- 229910002090 carbon oxide Inorganic materials 0.000 description 9
- -1 hydroxy aromatic carboxylic acid Chemical compound 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- ILYSAKHOYBPSPC-UHFFFAOYSA-N 2-phenylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1 ILYSAKHOYBPSPC-UHFFFAOYSA-N 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000005810 carbonylation reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- JBCLQODDDRVTSV-UHFFFAOYSA-N ethyl 7-bromo-9,10-dihydrophenanthrene-2-carboxylate Chemical compound BrC1=CC=C2C3=CC=C(C(=O)OCC)C=C3CCC2=C1 JBCLQODDDRVTSV-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 150000003003 phosphines Chemical class 0.000 description 3
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- XXPBFNVKTVJZKF-UHFFFAOYSA-N dihydrophenanthrene Natural products C1=CC=C2CCC3=CC=CC=C3C2=C1 XXPBFNVKTVJZKF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002941 palladium compounds Chemical class 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 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 2
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 2
- XGCDBGRZEKYHNV-UHFFFAOYSA-N 1,1-bis(diphenylphosphino)methane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CP(C=1C=CC=CC=1)C1=CC=CC=C1 XGCDBGRZEKYHNV-UHFFFAOYSA-N 0.000 description 1
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 1
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- KURIKJUBIDNKAU-UHFFFAOYSA-N 2-bromo-9,10-dihydrophenanthrene Chemical compound C1=CC=C2C3=CC=C(Br)C=C3CCC2=C1 KURIKJUBIDNKAU-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BKDMERPASJRHDJ-UHFFFAOYSA-N 3-diphenylphosphanylprop-1-enyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CC=CP(C=1C=CC=CC=1)C1=CC=CC=C1 BKDMERPASJRHDJ-UHFFFAOYSA-N 0.000 description 1
- JCLFHZLOKITRCE-UHFFFAOYSA-N 4-pentoxyphenol Chemical compound CCCCCOC1=CC=C(O)C=C1 JCLFHZLOKITRCE-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- WRDIOOMOLDUFQA-UHFFFAOYSA-N diethyl 9,10-dihydrophenanthrene-2,7-dicarboxylate Chemical compound CCOC(=O)C1=CC=C2C3=CC=C(C(=O)OCC)C=C3CCC2=C1 WRDIOOMOLDUFQA-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- IBOBFGGLRNWLIL-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine oxide Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)[O-] IBOBFGGLRNWLIL-UHFFFAOYSA-N 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 125000001792 phenanthrenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 1
- IGNTWNVBGLNYDV-UHFFFAOYSA-N triisopropylphosphine Chemical compound CC(C)P(C(C)C)C(C)C IGNTWNVBGLNYDV-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- KCTAHLRCZMOTKM-UHFFFAOYSA-N tripropylphosphane Chemical compound CCCP(CCC)CCC KCTAHLRCZMOTKM-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の利用分野〕
本発明は、耐熱性あるいは液晶高分子等の中間原料とし
て利用可能な７−ブロモ−９，１０−ジヒドロフェナン
スレン−２−カルボン酸エステルの製造方法に関する。Detailed Description of the Invention [Field of Application of the Invention] The present invention is directed to the use of 7-bromo-9,10-dihydrophenanthrene-2-carboxylic acid ester which can be used as an intermediate raw material for heat-resistant or liquid crystal polymers, etc. Regarding the manufacturing method.
詳しくは、２，７−ジブロモ−９．１０−ジヒドロフェ
ナンスレンをパラジウム−ホスフィン系触媒及び塩基性
物質の存在下で一酸化炭素及びアルコールと反応させ、
その際、相間移動触媒を添加することにより反応性を制
御することを特徴とする７−ブロモ−９，１０−ジヒド
ロフェナンスレン−２−カルボン酸エステルを選択的に
合成する方法である。Specifically, 2,7-dibromo-9.10-dihydrophenanthrene is reacted with carbon monoxide and alcohol in the presence of a palladium-phosphine catalyst and a basic substance,
This is a method for selectively synthesizing 7-bromo-9,10-dihydrophenanthrene-2-carboxylic acid ester, which is characterized in that the reactivity is controlled by adding a phase transfer catalyst.
従来、芳香族化合物のカルボニル化反応について各種の
方法が１Ｒ案されている。例えばヨウ素化または臭素化
ビフェニルに水性溶媒中触媒の存在下、−酸化炭素を反
応させてビフェニルカルボン酸を製造する方法（特開昭
６２−１８５０５５号）、ハロゲン化方香族ヒドロキン
化合物にアルコール溶媒中、触媒の存在下に一酸化炭素
を反応させてヒドロキシ芳香族カルボン酸エステルを製
造する方法（特開昭６２−１８７４３５号）、塩基及び
水の存在下に触媒を使用せずに芳香族ヨウ素化合物を一
酸化炭素と反応させて芳香族カルボン酸を製造する方法
（特開昭６３−５０５２号）、あるいはハロゲン化芳香
族化合物を高温、高圧下に触媒の存在下、−酸化炭素と
反応させて芳香族カルボン酸エステルを製造する方法（
米国特許第３６３６０８２号）￥が知られている。Conventionally, various 1R methods have been proposed for the carbonylation reaction of aromatic compounds. For example, a method for producing biphenylcarboxylic acid by reacting iodinated or brominated biphenyl with -carbon oxide in the presence of a catalyst in an aqueous solvent (Japanese Unexamined Patent Application Publication No. 185055/1982), a method for producing biphenylcarboxylic acid by reacting iodinated or brominated biphenyl with carbon oxide in the presence of a catalyst in an aqueous solvent, and a method for producing biphenylcarboxylic acid by reacting iodinated or brominated biphenyl with carbon oxide in the presence of a catalyst in an aqueous solvent. Among them, a method for producing hydroxy aromatic carboxylic acid ester by reacting carbon monoxide in the presence of a catalyst (Japanese Patent Application Laid-Open No. 187435/1982), and a method for producing aromatic iodine in the presence of a base and water without using a catalyst. A method of producing an aromatic carboxylic acid by reacting a compound with carbon monoxide (Japanese Unexamined Patent Publication No. 63-5052), or a method of reacting a halogenated aromatic compound with -carbon oxide at high temperature and pressure in the presence of a catalyst. Method for producing aromatic carboxylic acid ester (
US Pat. No. 3,636,082) is known.
しかし、これまでにフェナンスレン化合物にこれらの方
法を適応して選択的に７−ブロモ−９゜１０−ジヒドロ
フェナンスレン−２−カルボン酸エステルを合成した例
は報告されていない。また、本発明者らは上記方法で２
．７−ジブロモ−９゜１０−ジヒドロフェナンスレンの
カルボニル化反応を試みたが、７−ブロモ−９，１０−
ジヒドロフェナンスレン−２−カルボン酸エステルを選
択的に（ワることは出来ず、いずれも７−ブロモ−９゜
１０−ジヒドロフェナンスレン−２−カルボン酸エステ
ル及び９．１０−ジヒドロフェナンスレン−２，７−ジ
カルボン酸ジエステルの混合物を生成した。ここから７
−ブロモ−９，１０−ジヒドロフェナンスレン−２−カ
ルボン酸エステルを得るにはさらに煩雑な分ｌ１ｌｔｆ
ｉ！ｉ製行程を必要とすることから、７−ブロモ−９，
１０−ジヒドロフェナンスレン−２−カルボン酸エステ
ルを１段で選択的に合成する方法が求められていた。However, there have been no reports of selectively synthesizing 7-bromo-9°10-dihydrophenanthrene-2-carboxylic acid ester by applying these methods to phenanthrene compounds. In addition, the present inventors used the above method to
．． Attempts were made to carbonylate 7-dibromo-9゜10-dihydrophenanthrene, but 7-bromo-9,10-
Selectively dihydrophenanthrene-2-carboxylic acid ester (cannot be removed, both 7-bromo-9゜10-dihydrophenanthrene-2-carboxylic acid ester and 9.10-dihydrophenanthrene A mixture of lene-2,7-dicarboxylic acid diesters was produced, from which 7
-Bromo-9,10-dihydrophenanthrene-2-carboxylic acid ester requires more complicated steps.
i! 7-bromo-9,
There has been a need for a method for selectively synthesizing 10-dihydrophenanthrene-2-carboxylic acid ester in one step.
本発明者らはかねてより芳香族化合物のカルボニル化反
応について種々研究を重ね、特に原？１、触媒、反応条
件等が生成物の収率や選択率に及はす影響について広範
かつ綿密な検討を行ってきた。The present inventors have been conducting various studies on the carbonylation reaction of aromatic compounds for some time. 1. Extensive and detailed studies have been conducted on the effects of catalysts, reaction conditions, etc. on product yield and selectivity.
この中で特に塩基性物質とパラジウム−ホスフィン系触
媒の存在下におけるジブロモジヒドロフェナンスレンの
カルボニル化反応について詳細に検討したところ、更に
相間移動触媒を添加することによって、７−ブロモ−９
，１０−ジヒドロフェナンスレン−２−カルボン酸エス
テルを高選択率で合成する方法を見出して本発明に至っ
たものである。Among these, we specifically investigated the carbonylation reaction of dibromodihydrophenanthrene in the presence of a basic substance and a palladium-phosphine catalyst, and found that by further adding a phase transfer catalyst, 7-bromo-9
, 10-dihydrophenanthrene-2-carboxylic acid ester was discovered with high selectivity, leading to the present invention.
本発明は２，７−ジブロモ−９．１０−ジヒドロフェナ
ンスレンを相間移動触媒、パラジウム−ポスフィン系触
媒及び塩基性物ｎのＴ１在下で一酸化炭素及び一般式（
Ｉ）Ｒ−ＯＨを有するアルコールと反応させ、一般式（
ｎ）て表される７−ブロモ・９，１０−ジヒドロフェナ
ンスレン−２カルボン駿エステルを；ｙ、択的に合成す
る方法に関イＺ１゜
一般式（ＩＩ）
〔発明の詳細な説明〕
以ド、本発明について詳細に説明する。The present invention deals with the treatment of 2,7-dibromo-9,10-dihydrophenanthrene in the presence of T1 of a phase transfer catalyst, a palladium-phosphine catalyst, and a basic substance n, with carbon monoxide and the general formula (
I) React with an alcohol having R-OH to form the general formula (
General formula (II) [Detailed description of the invention] The present invention will now be described in detail.
本発明の原電４として使用する２、７−ジブロモ−９，
１０−ジヒドロフェナンスレンは、次の式％式％
種々の方法で容易に得るこたが出来る。例えば、９ １
０−ジヒドロフェナンスレンをトリメチルホスフェイト
溶媒中、Ｊ２素存在Ｆて反応させることにより高収率で
ｉすられる（Ｉ）、Ｅ、Ｐｃａｒｓｏｎ、Ｕ、Ｓ、ｌ”
ａｔ。2,7-dibromo-9, used as the power source 4 of the present invention,
10-Dihydrophenanthrene can be easily obtained by various methods. For example, 9 1
By reacting 0-dihydrophenanthrene in a trimethyl phosphate solvent in the presence of J2 element, it can be obtained in high yield (I), E, Pcarson, U, S, l"
at.
３．９８８．３６９（Ｉ９７６））。3.988.369 (I976)).
本発明で用いる相間移動触媒としＣは、例えばヨウ化テ
！・クーｎ−ブチルアンモニウム、４化ベンジルトリエ
チルアンモニウム、塩化テトラ−ｎブチルホスホニウム
、塩化セチルトリーｎ−ブチルホスホニウム等のアルキ
ル基あるいはアリル基をもつ４級アンモニウｌ、塩類ま
たは４級ホスホニウム塩類、あるいはトリー〇・ブチル
アミンオキシド、セチルジメチルアミンオキシド等のア
ミンオキンド類、あるいは１８−クラウン−６等のクラ
ウンエーテル類が挙げられる。相間移動触媒の添加量に
は特に制限はないが、通常は反応させるジブロモジヒド
ロフェナンスレンに対して、１１５０〜１／１０００モ
ル当量、好ましくは、コ／２０〜１ ／ ２００モル当
量が適当である。C as the phase transfer catalyst used in the present invention is, for example, iodide!・Quaternary ammonium salts or quaternary phosphonium salts having an alkyl or allyl group such as n-butylammonium, benzyltriethylammonium tetrachloride, tetra-n-butylphosphonium chloride, cetyltri-n-butylphosphonium chloride, or tri- - Examples include amine oxides such as butylamine oxide and cetyldimethylamine oxide, and crown ethers such as 18-crown-6. There is no particular limit to the amount of the phase transfer catalyst added, but usually 1150 to 1/1000 molar equivalents, preferably co/20 to 1/200 molar equivalents, based on the dibromodihydrophenanthrene to be reacted. be.
本発明で用いるパラジウム−ポスフィン系触媒において
、例えばパラジウム化合物と１．では塩化パラジウム、
硫酸パラジウム、酢酸パラジウムなどがあり、これらに
ホスフィン類を添加するかあるいはパラジウム−ホスフ
ィン錯体を用いることができる。In the palladium-posphine catalyst used in the present invention, for example, a palladium compound and 1. So palladium chloride,
Examples include palladium sulfate and palladium acetate, to which phosphines can be added or a palladium-phosphine complex can be used.
ホスフィンとしては、トリフェニルホスフィン、トリト
リルホスフィン、ドリアニシルホスフィン等の芳香族ホ
スフィン類、トリトリルホスフィン、トリプロピルホス
フィン、トリイソプロピルホスフィン等のアルキルホス
フィン類、１，１−ビス（ジフェニルホスフィノ）メタ
ン、１．２−ビス（ジフェニルホスフィノ）エタン、］
、］３−ビスジフェニルホスフィノ）プロパン等のジホ
スフィン類等が挙げられる。これらのホスフィン類はパ
ラジウム錯体として反応系中に加えられても良いし、ま
た例えば塩化パラジウム等の塩類とホスフィンとを一定
の割合で反応器中に充填しても良い。Examples of phosphines include aromatic phosphines such as triphenylphosphine, tritolylphosphine, and dorianisylphosphine, alkylphosphines such as tritolylphosphine, tripropylphosphine, and triisopropylphosphine, and 1,1-bis(diphenylphosphino)methane. , 1,2-bis(diphenylphosphino)ethane,]
, ]3-bisdiphenylphosphino)propane and other diphosphines. These phosphines may be added to the reaction system as a palladium complex, or a salt such as palladium chloride and phosphine may be charged into the reactor at a fixed ratio.
パラジウム化合物の使用量は反応させるジブロモジヒド
ロフェナンスレンに対して、１／１０〜１／１０００モ
ル当量、好ましくは１／２０〜１／２００モル当量が適
当である。ホスフィン化合物の添加量はパラジウムの量
に対して０．０５〜１０モル当量、好ましくは１〜５モ
ル当量が適当である。The appropriate amount of the palladium compound to be used is 1/10 to 1/1000 molar equivalent, preferably 1/20 to 1/200 molar equivalent, relative to dibromodihydrophenanthrene to be reacted. The appropriate amount of the phosphine compound added is 0.05 to 10 molar equivalents, preferably 1 to 5 molar equivalents, relative to the amount of palladium.
本発明で用いる塩基性物質は、例えばアルカリ金属水酸
化物、アルカリ金属炭酸塩、アルカリ金属炭酸水素塩、
アルカリ土類金属水酸化物等が挙げられる。特に炭酸水
素ナトリウムが好んで用いられる。使用量は、反応させ
るジブロモジヒドロフェナンスレンのハロゲン量に対し
て０．１〜３．０モル当量、好ましくはＱ、 ３〜２
．０モル当量である。The basic substances used in the present invention include, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates,
Examples include alkaline earth metal hydroxides. Particularly preferred is sodium hydrogen carbonate. The amount used is 0.1 to 3.0 molar equivalent based on the amount of halogen in dibromodihydrophenanthrene to be reacted, preferably Q, 3 to 2.
．． 0 molar equivalent.
一般式（Ｉ）Ｒ−ＯＨで表されるアルコール類としてＲ
が炭素数１〜２０を有する炭化水素基を有するものが挙
げられる。例えばメチル、エチル等のアルキル基、シク
ロペンチル、シクロｔ＼キシル等のシクロアルギル基、
フェニル、ベンジル基等のアリール基をａむ脂肪族、脂
環族、または芳香族の炭化水素基である。従って一般式
（ＩＮ）で表される化合物と１−１では、代表的には７
−ブロモ９、】Ｏ−ジヒドロフェナンスレン−２−カル
ボン酸メチルニスデル、７−ブロモ−９，１０ジヒドロ
フェナンスレン−２−カルボ〉酸エチルエステル等が挙
げられる。As alcohols represented by general formula (I) R-OH, R
Examples include those having a hydrocarbon group having 1 to 20 carbon atoms. For example, alkyl groups such as methyl and ethyl, cycloargyl groups such as cyclopentyl and cyclot\xyl,
It is an aliphatic, alicyclic, or aromatic hydrocarbon group including an aryl group such as phenyl or benzyl group. Therefore, in the compound represented by the general formula (IN) and 1-1, typically 7
-bromo9, ]O-dihydrophenanthrene-2-carboxylic acid methyl nisder, 7-bromo-9,10 dihydrophenanthrene-2-carboxylic acid ethyl ester, and the like.
反応装置としては、通常用いられる流通式あるいは四分
式高圧反応装置か適当であるか、これらに限定されるも
のではない。反応は一酸化炭素存在下で行う。−酸化炭
素ガスの圧力は、ケージ圧１〜１５０隊／ ｃｄ 、好
ま（−＜は］〜７０ｋｇ／ｅ−か適当である。反応温度
は、反応速度の点て５０〜・１５０℃、好ましくは５０
〜１００℃が適当であり、１５０℃以上では副反応が多
くなる。The reaction apparatus may be a commonly used flow type or four-section high pressure reaction apparatus, but is not limited thereto. The reaction is carried out in the presence of carbon monoxide. - The pressure of the carbon oxide gas is a cage pressure of 1 to 150 units/cd, preferably -70 kg/e-, or appropriate.The reaction temperature is 50 to 150°C, preferably from the viewpoint of reaction rate. 50
A temperature of 100°C to 100°C is suitable, and a temperature of 150°C or higher causes many side reactions.
（実施例）
次に、実施例と比較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 and Comparative Examples.
〔実施例１〕
２．７−ジブロモ−９，１０−ジヒドロフェナンスレン
０． ７８ｚ （２，３ｓｉｏｌ） 、ヨウ化テトラ−
ｎ−ブチルアンモニウム０． ９ｇ （０，２３ｍｗｏ
ｌ） 、塩化パラジウムＯ１００４ｇ（０，０２３■ｏ
ｆ）、１．３−ビス（ジフェニルホスフィノ）プロペン
０． １（’）ｇ （０，０２３ｉｍｏｌ） 、炭酸水
素ナトリウム０． ３ｇ （３，４ｇｍｏｌ） 、エタ
ノール２５ｍ１を５ＩＪＳ３１６！！１００ｍ１オート
クレーブに仕込み、次いて一酸化炭素５０ｋｇ／ｃｄを
仕込み、９０℃に昇温させて６時間反応させた。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。その
結果、仕込んだ２，７−ジブロモ−９１０−ジヒドロツ
ユ。[Example 1] 2.7-dibromo-9,10-dihydrophenanthrene 0. 78z (2,3siol), tetra-iodide
n-butylammonium 0. 9g (0.23mwo
l), palladium chloride O1004g (0,023■o
f), 1,3-bis(diphenylphosphino)propene 0. 1(')g (0,023 imol), sodium hydrogen carbonate 0. 3g (3.4gmol), ethanol 25ml 5IJS316! ! The mixture was charged into a 100 ml autoclave, and then 50 kg/cd of carbon monoxide was charged, the temperature was raised to 90°C, and the reaction was carried out for 6 hours. After the reaction, unreacted carbon monoxide was purged, and the reaction solution was taken out and analyzed by gas chromatography. As a result, 2,7-dibromo-910-dihydrotsuyu was prepared.
ナンスレンのうち７〕９ｏか反応し、主生成物とし。Of the nanthrenes, 7]9o reacted and became the main product.
て７−ブロモ−９，１０−ジヒドロフェナンスレン−２
−カルボン酸エチルエステルが０．４３ｇ（Ｉ，’３＋
ｓｏｌ、選択率８０％）得られた。その他、主な副生成
物と１７で９．］Ｏ−ジヒドロフエナンスレン−２，７
−ジカルボン酸ジエチルエステルが０，０３■（Ｑ、
］ｓｍｏｌ、選択率６％）得られた。7-Bromo-9,10-dihydrophenanthrene-2
-0.43 g of carboxylic acid ethyl ester (I, '3+
sol, selectivity 80%) was obtained. Other main by-products and 17 and 9. ]O-dihydrophenanthrene-2,7
-Dicarboxylic acid diethyl ester is 0.03■ (Q,
] smol, selectivity 6%) was obtained.
〔実施例２〕
２．７−ジブロモ−９．１０−ジヒドロフェナンスレン
０．７８ｇ （２，３ｍ５ｏｌ） 、１ｇ−クラウン−
６０，０６ｇ （０，２３ｓｎｏｌ） 、塩化パラジウ
ム０． ００４ｇ （０，０２３ｇ＋ｍｏｌ） 、１゜
３−ビス（ジフェニルホスフィノ）プロパン０．１０ｇ
（０，０２３ｍ５ｏｌ） 、炭酸水素ナトリウム０．
３ｇ （３，４ｓｓｏｌ） 、エタノール２５ｍ１を
オートクレーブに仕込み、温度９０℃、−酸化炭素５０
ｋｇ／ｃｊで実施例１と同様の方法で６時間反応させた
。その結果、仕込んだ２．７−ジブロモ−９．１０−ジ
ヒドロフェナンスレンのうち８３％が反応し、主生成物
として７−ブロモ−９゜１０−ジヒドロフェナンスレン
−２−カルボン酸エチルエステルが０． ５ｇ （Ｉ，
４ｍｇ＋ｏｌ、選択率７３％）得られた。その他、主な
副生成物として９．１０−ジヒドロフェナンスレン−２
，７−ジカルボン酸ジエチルエステルが０．０５ｍｇ（
０，１５ｇ１＋ｏｌ、選択率８％）得られた。[Example 2] 2,7-dibromo-9,10-dihydrophenanthrene 0.78g (2,3m5ol), 1g-crown-
60,06g (0,23snol), palladium chloride 0. 004g (0,023g+mol), 1°3-bis(diphenylphosphino)propane 0.10g
(0,023m5ol), sodium bicarbonate 0.
3 g (3,4 ssol) and 25 ml of ethanol were placed in an autoclave, the temperature was 90°C, and -carbon oxide 50
kg/cj and reacted for 6 hours in the same manner as in Example 1. As a result, 83% of the charged 2,7-dibromo-9,10-dihydrophenanthrene was reacted, and the main product was 7-bromo-9,10-dihydrophenanthrene-2-carboxylic acid ethyl ester. is 0. 5g (I,
4 mg+ol, selectivity 73%) was obtained. Other main by-products include 9.10-dihydrophenanthrene-2
, 0.05 mg of 7-dicarboxylic acid diethyl ester (
0.15g1+ol, selectivity 8%) was obtained.
〔実施例３〕
２．７−ジブロモ−９．１０−ジヒドロフェナンスレン
０． ７８ｇ （２，３ｓｓｏｌ） 、ジベンゾ−１８
−クラウン−６０，０８ｇ （０，２３１１ｏ１）、塩
化パラジウム０．００４ｇ（０，０２３ｓｎｏｌ） 、
１．３−ビス（ジフェニルホスフィノ）プロパン０．１
０ｇ （０，０２３−■ｏ１）、炭酸水素ナトリウム０
． ３ｇ （３，４１ｍｏｌ） 、エタノール２５ｍ１
をオートクレーブに仕込み、温度９０℃、−酸化炭素圧
力５０ｋｇ／ｃ−で実施例１と同様の方法で５時間反応
させた。その結果、仕込んだ２，７−ジブロモ−９，１
０−ジヒドロフェナンスレンのうち７１％が反応し、主
生成物として７−ブロモ−９，１０−ジヒドロフェナン
スレン−２−カルボン酸エチルエステルか０、４ｇ （
Ｉ，２ｍ５ｏｌ、選択率７２％）得られた。[Example 3] 2.7-dibromo-9.10-dihydrophenanthrene 0. 78g (2,3ssol), dibenzo-18
-Crown-60,08g (0,2311o1), palladium chloride 0.004g (0,023snol),
1.3-bis(diphenylphosphino)propane 0.1
0g (0,023-■o1), sodium hydrogen carbonate 0
．． 3g (3.41mol), ethanol 25ml
was charged into an autoclave and reacted for 5 hours in the same manner as in Example 1 at a temperature of 90° C. and a carbon oxide pressure of 50 kg/c. As a result, the charged 2,7-dibromo-9,1
71% of 0-dihydrophenanthrene reacted, and the main product was 0.4 g of 7-bromo-9,10-dihydrophenanthrene-2-carboxylic acid ethyl ester (
I, 2 m5 ol, selectivity 72%) was obtained.
その他、主な副生成物として９．１０−ジヒドロフェナ
ンスレン−２，７−ジカルボン酸ジエチルエステルが０
． Ｏｌｇ （０，０３ｓｎｏｌ、選択率２％）得ら
れた。In addition, the main by-product is 9.10-dihydrophenanthrene-2,7-dicarboxylic acid diethyl ester.
．． Olg (0.03 snol, selectivity 2%) was obtained.
〔比較例１〕
２７−ジブロモ−９，１０−ジヒドロフェナンスレン０
． ７８ｇ （２，：３＋ｎｏｌ） 、塩化パラジウム
０．００４ｇ （０，０２３ｓｎｏｌ） 、１．３−ビ
ス（ジフェニルホスフィノ）プロパン０，１０ｇ （０
，０２３ｓ■０１）、炭酸水素ナトリウム０、 ３ｇ
（３，４＋ｎｏｌ） 、エタノール２５ｍ１をオートク
レーブに仕込ろ、温度９０℃、−酸化炭素圧力５０ｋｇ
１ｃｄで実施例１と同様の方法で５時間反応させた。そ
の結果、仕込んだ２．７−ジブロモ−９，１０−ジヒド
ロフェナンスレンのうち３１％が反応し、７−ブロモ−
９，１０−ジヒドロフェナンスレン−２−カルボン酸エ
チルエステルおよび９，１０−ジヒドロフェナンスレン
−２゜７−ジカルボン酸ジエチルエステルがそれぞれ０
、 １． ＜０． ３厘」０１、選択率３７％）および
０、 ０１ ｇ （０，０４＋ｎｏｌ、選択率６％）生
成した。[Comparative Example 1] 27-dibromo-9,10-dihydrophenanthrene 0
．． 78g (2,:3+nol), palladium chloride 0.004g (0,023snol), 1,3-bis(diphenylphosphino)propane 0.10g (0
,023s■01), Sodium hydrogen carbonate 0.3g
(3,4+nol), charge 25ml of ethanol into an autoclave, temperature 90℃, -carbon oxide pressure 50kg
The reaction was carried out in the same manner as in Example 1 at 1 cd for 5 hours. As a result, 31% of the 2,7-dibromo-9,10-dihydrophenanthrene charged reacted, and 7-bromo-9,10-dihydrophenanthrene was reacted.
9,10-dihydrophenanthrene-2-carboxylic acid ethyl ester and 9,10-dihydrophenanthrene-2゜7-dicarboxylic acid diethyl ester are each 0
, 1. <0. 3 g (0.01 g, selectivity 37%) and 0.01 g (0.04+nol, selectivity 6%) were produced.
〔比較例２〕
２．７−ジブロモ−９，１０−ジヒドロフェナンスレン
０． ７８ｇ （２，３釦ｍｏｌ） 、ジクロロビス（
トリフェニルホスフィン）パラジウム０、 ０１７ｇ
（０，０２３ａｍｏｌ） 、炭酸水素ナトリウム０．
３ｇ （３，４ｓｓｏｌ） 、エタノール２５ｍ１をオ
ートクレーブに仕込み、温度７０℃、−酸化炭素圧力３
０ｋｇ／ｃシで実施例１と同様の方法で５時間反応させ
た。その結果、仕込んだ２．７ジ−ブロモ−９，１０−
ジヒドロフェナンスレンのうち６９％が反応し、７−ブ
ロモ−９１０−ジヒドロフェナンスレン−２−カルボン
酸エチルエステルおよび９，１０−ジヒドロフェナンス
レン−２，７−ジカルボン酸ジエチルエステルがそれぞ
れ０． ２ｇ （０，５Ｉｉｓｏｌ、選択率３２％）お
よび０． Ｏｌｇ （０，０２ｓｎｏｌ、選択率１％
）生成した。[Comparative Example 2] 2.7-dibromo-9,10-dihydrophenanthrene 0. 78g (2,3 mol), dichlorobis(
Triphenylphosphine) Palladium 0.017g
(0,023 amol), sodium hydrogen carbonate 0.
3 g (3,4 ssol) and 25 ml of ethanol were placed in an autoclave at a temperature of 70°C and a carbon oxide pressure of 3.
The reaction was carried out in the same manner as in Example 1 at 0 kg/c for 5 hours. As a result, the charged 2.7 di-bromo-9,10-
69% of dihydrophenanthrene was reacted, and 0% of 7-bromo-910-dihydrophenanthrene-2-carboxylic acid ethyl ester and 9,10-dihydrophenanthrene-2,7-dicarboxylic acid diethyl ester were reacted. ．． 2g (0,5Iisol, selectivity 32%) and 0.2g (0.5Iisol, selectivity 32%). Olg (0.02 snol, selectivity 1%
) generated.
上述のところから明らかなように本発明に従って塩基性
物質とパラジウム−ホスフィン系触媒とともに相間移動
触媒を用いることによって２．７ジ−ブロモ−９，１０
−ジヒドロフェナンスレンから７−ブロモ−９，１０−
ジヒドロフェナンスレン−２−カルボン酸エステルを高
い選択率で製造することができる。As is clear from the above, by using a phase transfer catalyst together with a basic substance and a palladium-phosphine catalyst according to the present invention, 2.7di-bromo-9,10
-dihydrophenanthrene to 7-bromo-9,10-
Dihydrophenanthrene-2-carboxylic acid ester can be produced with high selectivity.
Claims (1)
を相間移動触媒、パラジウム−ホスフィン系触媒及び塩
基性物質の存在下で一酸化炭素及び一般式（ I ）Ｒ−
ＯＨ（式中Ｒは炭素数１〜２０を有する炭化水素基を表
す）を有するアルコールと反応させ、一般式（II）で表
わされる７−ブロモ−９，１０−ジヒドロフェナンスレ
ン−２−カルボン酸エステルを選択的に合成する方法。 一般式（II） ▲数式、化学式、表等があります▼[Claims] 2,7-dibromo-9,10-dihydrophenanthrene is reacted with carbon monoxide and the general formula (I) R- in the presence of a phase transfer catalyst, a palladium-phosphine catalyst, and a basic substance.
7-bromo-9,10-dihydrophenanthrene-2-carboxylic acid represented by general formula (II) by reacting with an alcohol having OH (in the formula, R represents a hydrocarbon group having 1 to 20 carbon atoms) A method for selectively synthesizing acid esters. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2083898A JPH078836B2 (en) | 1990-03-30 | 1990-03-30 | Process for producing 7-bromo-9,10-dihydrophenanthrene-2-carboxylic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2083898A JPH078836B2 (en) | 1990-03-30 | 1990-03-30 | Process for producing 7-bromo-9,10-dihydrophenanthrene-2-carboxylic acid ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03284654A true JPH03284654A (en) | 1991-12-16 |
| JPH078836B2 JPH078836B2 (en) | 1995-02-01 |
Family
ID=13815452
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2083898A Expired - Lifetime JPH078836B2 (en) | 1990-03-30 | 1990-03-30 | Process for producing 7-bromo-9,10-dihydrophenanthrene-2-carboxylic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH078836B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7803953B2 (en) * | 2006-06-06 | 2010-09-28 | Tosoh Corporation | Catalyst for producing arylamine and process for producing arylamine by means thereof |
-
1990
- 1990-03-30 JP JP2083898A patent/JPH078836B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7803953B2 (en) * | 2006-06-06 | 2010-09-28 | Tosoh Corporation | Catalyst for producing arylamine and process for producing arylamine by means thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH078836B2 (en) | 1995-02-01 |
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