JPH083103A - Method for producing β-naphthoic acid - Google Patents
Method for producing β-naphthoic acidInfo
- Publication number
- JPH083103A JPH083103A JP6164570A JP16457094A JPH083103A JP H083103 A JPH083103 A JP H083103A JP 6164570 A JP6164570 A JP 6164570A JP 16457094 A JP16457094 A JP 16457094A JP H083103 A JPH083103 A JP H083103A
- Authority
- JP
- Japan
- Prior art keywords
- naphthoic acid
- naphthalene
- rhodium
- carbon monoxide
- 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.)
- Withdrawn
Links
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 65
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 19
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims abstract description 14
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010948 rhodium Substances 0.000 claims description 27
- 229910052703 rhodium Inorganic materials 0.000 claims description 26
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 25
- 239000010949 copper Substances 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 150000001735 carboxylic acids Chemical class 0.000 claims description 9
- 239000005749 Copper compound Substances 0.000 claims description 5
- 150000001880 copper compounds Chemical class 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 abstract description 8
- 229940076286 cupric acetate Drugs 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
- -1 palladium carboxylate Chemical class 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 229910052763 palladium Inorganic materials 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 150000005209 naphthoic acids Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VOCNMTIGMYPFPY-UHFFFAOYSA-N 6-methylnaphthalene-2-carboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C)=CC=C21 VOCNMTIGMYPFPY-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000001116 FEMA 4028 Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910002567 K2S2O8 Inorganic materials 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 1
- 229960004853 betadex Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Inorganic materials [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- 229910003450 rhodium oxide Inorganic materials 0.000 description 1
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 description 1
- MMRXYMKDBFSWJR-UHFFFAOYSA-K rhodium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Rh+3] MMRXYMKDBFSWJR-UHFFFAOYSA-K 0.000 description 1
- KXAHUXSHRWNTOD-UHFFFAOYSA-K rhodium(3+);triiodide Chemical compound [Rh+3].[I-].[I-].[I-] KXAHUXSHRWNTOD-UHFFFAOYSA-K 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- YWFDDXXMOPZFFM-UHFFFAOYSA-H rhodium(3+);trisulfate Chemical compound [Rh+3].[Rh+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YWFDDXXMOPZFFM-UHFFFAOYSA-H 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- TXUZMGFRPPRPQA-UHFFFAOYSA-K trifluororhodium Chemical compound F[Rh](F)F TXUZMGFRPPRPQA-UHFFFAOYSA-K 0.000 description 1
- 239000000341 volatile oil Substances 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
(57)【要約】
【目的】 ナフタレンおよび一酸化炭素から特定の触媒
を用いてβ−ナフトエ酸を一段階でかつ極めて高い選択
率で得ることのできる工業的な製造方法を提供すること
を目的とする。
【構成】 塩化ロジウム、酢酸第二銅、１，１０−フェ
ナントロリンおよびトリフルオロ酢酸の存在下に、温度
１００℃、圧力２０気圧の条件でナフタレンと一酸化炭
素とを反応させることにより、ほぼ選択率１００％でβ
−ナフトエ酸を製造する。(57) [Abstract] [Purpose] An object of the present invention is to provide an industrial production method capable of obtaining β-naphthoic acid from naphthalene and carbon monoxide in a single step and with extremely high selectivity by using a specific catalyst. And [Structure] By reacting naphthalene with carbon monoxide in the presence of rhodium chloride, cupric acetate, 1,10-phenanthroline, and trifluoroacetic acid under the conditions of a temperature of 100 ° C. and a pressure of 20 atm, it is possible to obtain an almost selective selectivity. Β at 100%
Produce naphthoic acid.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ナフタレンおよび一酸
化炭素からロジウム系触媒を用いてβ−ナフトエ酸を高
選択率で製造する方法に関するものである。FIELD OF THE INVENTION The present invention relates to a method for producing β-naphthoic acid from naphthalene and carbon monoxide with a rhodium catalyst at a high selectivity.
【０００２】[0002]
【従来の技術】ナフトエ酸にはα−ナフトエ酸とβ−ナ
フトエ酸とがあり、このうちβ−ナフトエ酸はポリエス
テルなどの原料として有用性が高い。2. Description of the Related Art There are α-naphthoic acid and β-naphthoic acid in naphthoic acid, of which β-naphthoic acid is highly useful as a raw material for polyesters and the like.
【０００３】β−ナフトエ酸の製造法としては種々の方
法が知られているが、このうちナフタレンおよび一酸化
炭素を出発原料とするβ−ナフトエ酸の製造法に関する
文献としては、次に述べる特公昭５６−２６６５０号公
報（特開昭４９−３６６４５号公報）、特開昭６３−１
１５８４７号公報および特開平２−１６４８４３号公報
がある。Various methods are known as a method for producing β-naphthoic acid. Among them, as a literature relating to the method for producing β-naphthoic acid using naphthalene and carbon monoxide as starting materials, JP-A-56-26650 (JP-A-49-36645), JP-A-63-1
There are JP 15847 and JP 2-164843.
【０００４】特公昭５６−２６６５０号公報には、核炭
素原子に直結した少なくとも１個の水素原子を有する芳
香族化合物を、パラジウムカルボキシレートの存在下に
一酸化炭素および分子状酸素含有ガスと接触せしめて芳
香族カルボン酸を得る方法が示されている。その実施例
においては、ナフタレン、パラジウム系触媒およびカル
ボン酸の存在下に酸素および一酸化炭素を反応させるこ
とにより、ナフタレン転化率 0.1〜１６％でナフトエ酸
を得ており、ナフトエ酸の選択率は３０〜９７％、ナフ
トエ酸のうちβ−ナフトエ酸の選択率は５０〜８９％で
ある。JP-B-56-26650 discloses that an aromatic compound having at least one hydrogen atom directly connected to a nuclear carbon atom is contacted with carbon monoxide and a gas containing molecular oxygen in the presence of palladium carboxylate. At most, a method of obtaining an aromatic carboxylic acid is shown. In that example, naphthoic acid was obtained at a naphthalene conversion rate of 0.1 to 16% by reacting oxygen and carbon monoxide in the presence of naphthalene, a palladium-based catalyst, and a carboxylic acid. 30-97%, and the selectivity of β-naphthoic acid among naphthoic acids is 50-89%.
【０００５】特開昭６３−１１５８４７号公報には、パ
ラジウム系触媒および１，１０−フェナントロリンの存
在下で、ナフタレンと、一酸化炭素ならびに酸素および
／またはカルボン酸とを接触させることによりナフトエ
酸を製造する方法が示されている。実施例の結果は第１
表にまとめられており、その結果によれば、ナフタレン
７８ミリモル（全実施例）を用いてナフトエ酸を0.21〜
0.84ミリモルの収量で得ており、生成したナフトエ酸の
うちβ−ナフトエ酸の選択率は８０〜９８モル％であ
る。なお、最も高いβ−ナフトエ酸の選択率（９８モル
％）が得られた実施例１３のナフトエ酸収量は0.68ミリ
モル、最も高いナフトエ酸収量（0.84ミリモル）が得ら
れた実施例３のβ−ナフトエ酸の選択率は９４モル％で
ある。In Japanese Patent Laid-Open No. 63-115847, naphthoic acid is obtained by contacting naphthalene with carbon monoxide and oxygen and / or carboxylic acid in the presence of a palladium catalyst and 1,10-phenanthroline. The method of manufacture is shown. The result of the example is the first
The results are summarized in the table and the results show that 78 mmol of naphthalene (all examples) were used to add naphthoic acid from 0.21 to
The yield was 0.84 mmol, and the selectivity of β-naphthoic acid in the naphthoic acid produced was 80 to 98 mol%. In addition, the naphthoic acid yield of Example 13 in which the highest β-naphthoic acid selectivity (98 mol%) was obtained was 0.68 mmol, and the β-naphthoic acid yield of Example 3 in which the highest naphthoic acid yield (0.84 mmol) was obtained. The selectivity of naphthoic acid is 94 mol%.
【０００６】特開平２−１６４８４３号公報には、ナフ
タレンまたはメチルナフタレンと酸素と一酸化炭素とを
反応させてカルボン酸類を合成する方法において、パラ
ジウムおよび／またはパラジウム化合物を触媒として用
い、酢酸および／またはトリフルオロ酢酸の共存下で反
応を行うナフタレンカルボン酸類の合成法が示されてい
る。しかしながらその実施例においては、β−メチルナ
フタレンを原料として用いて２−メチル−６−ナフトエ
酸を得ている例があげられているのみであり、ナフタレ
ンを用いた例は記載されていない。なおこの公報には、
従来方法としてパラジウム触媒を用いてナフタレンを一
酸化炭素の共存下で反応させてナフトエ酸（またはその
エステル）を合成する方法があるとしているが、従来方
法におけるβ−ナフトエ酸の選択率は２０〜８０％とい
うように低いものであることが述べられている。JP-A-2-164843 discloses a method for synthesizing carboxylic acids by reacting naphthalene or methylnaphthalene with oxygen and carbon monoxide, using palladium and / or a palladium compound as a catalyst, and acetic acid and / or Alternatively, a method for synthesizing naphthalene carboxylic acids which reacts in the presence of trifluoroacetic acid is disclosed. However, in the examples, only an example in which β-methylnaphthalene is used as a raw material to obtain 2-methyl-6-naphthoic acid, and an example using naphthalene is not described. In this publication,
As a conventional method, there is a method of synthesizing naphthoic acid (or an ester thereof) by reacting naphthalene in the presence of carbon monoxide using a palladium catalyst, but the selectivity of β-naphthoic acid in the conventional method is 20 to It is stated to be as low as 80%.
【０００７】[0007]
【発明が解決しようとする課題】β−ナフトエ酸の製造
法としては種々の方法が知られているが、このうちナフ
タレンおよび一酸化炭素を出発原料とするβ−ナフトエ
酸の製造法に関する上述の３つの文献は、いずれも触媒
としてパラジウム系触媒を用いるものである。Various methods are known as a method for producing β-naphthoic acid. Among them, the above-mentioned method for producing β-naphthoic acid using naphthalene and carbon monoxide as starting materials is mentioned above. All three references use a palladium-based catalyst as a catalyst.
【０００８】しかしながら、パラジウム系触媒を用いた
上述の方法においては、生成したナフトエ酸のうちβ−
ナフトエ酸の選択率の最高のものは、特公昭５６−２６
６５０号公報では８９％（実施例２）、特開昭６３−１
１５８４７号公報では９８％（実施例１３）であり、β
−ナフトエ酸を事実上１００％の選択率で得た例はな
い。However, in the above-mentioned method using a palladium-based catalyst, among the naphthoic acids produced, β-
The highest naphthoic acid selectivity is found in Japanese Examined Patent Publication No. 56-26.
In 650 publication, 89% (Example 2), JP-A-63-1
In 15847, it is 98% (Example 13), and β
No naphthoic acid was obtained with virtually 100% selectivity.
【０００９】生成ナフトエ酸に副生物であるα−ナフト
エ酸が混じることは、β−ナフトエ酸の収率の点で不利
となるのみならず、生成物ナフトエ酸からのβ−ナフト
エ酸の単離操作が複雑になるという不利がある。The mixing of the by-product α-naphthoic acid with the produced naphthoic acid is not only disadvantageous in terms of the yield of β-naphthoic acid, but also the isolation of β-naphthoic acid from the product naphthoic acid. It has the disadvantage that the operation becomes complicated.
【００１０】本発明は、このような背景下において、ナ
フタレンおよび一酸化炭素から特定の触媒を用いてβ−
ナフトエ酸を一段階でかつ極めて高い選択率で得ること
のできる工業的な製造方法を提供することを目的とする
ものである。Under the above circumstances, the present invention uses a specific catalyst from naphthalene and carbon monoxide to form β-
It is an object of the present invention to provide an industrial production method capable of obtaining naphthoic acid in one step and with extremely high selectivity.
【００１１】[0011]
【課題を解決するための手段】ナフタレンと一酸化炭素
とを反応させるにあたり、ロジウム系触媒を用いること
自体が新規であると信じられる。すなわち、本発明のβ
−ナフトエ酸の製造法は、ロジウム系触媒の存在下に、
ナフタレンと一酸化炭素とを反応させることを特徴とす
るものである。It is believed that the use of a rhodium-based catalyst in the reaction of naphthalene with carbon monoxide is novel in itself. That is, β of the present invention
-The process for the production of naphthoic acid is carried out in the presence of a rhodium catalyst,
It is characterized in that naphthalene is reacted with carbon monoxide.
【００１２】本発明のβ−ナフトエ酸のより具体的な製
造法は、ロジウム系触媒、銅系化合物、１，１０−フェ
ナントロリンおよびカルボン酸類の存在下に、ナフタレ
ンと一酸化炭素とを反応させることを特徴とするもので
ある。A more specific method for producing β-naphthoic acid of the present invention is to react naphthalene with carbon monoxide in the presence of a rhodium catalyst, a copper compound, 1,10-phenanthroline and carboxylic acids. It is characterized by.
【００１３】以下本発明を詳細に説明する。The present invention will be described in detail below.
【００１４】出発原料としてはナフタレンと一酸化炭素
とが用いられる。ナフタレンは、工業的には石炭乾留に
おける精製工程、石油精製工程、植物精油分離工程をは
じめとする諸工程から得られるが、本発明の原料として
はできるだけ精製したナフタレンを用いることが望まし
い。一酸化炭素は、コークス炉ガス、水性ガスをはじめ
とする諸工程から得られるが、本発明の原料としてはで
きるだけ精製した一酸化炭素を用いることが望ましい。Naphthalene and carbon monoxide are used as starting materials. Although naphthalene is industrially obtained from various steps including a coal carbonization refining step, a petroleum refining step, and a plant essential oil separation step, it is desirable to use purified naphthalene as a raw material of the present invention. Although carbon monoxide can be obtained from various processes including coke oven gas and water gas, it is desirable to use as purified carbon monoxide as the raw material of the present invention.
【００１５】ロジウム系触媒としては、ハロゲン化ロジ
ウム（塩化ロジウム、臭化ロジウム、フッ化ロジウム、
ヨウ化ロジウム）、ハロゲン化物以外のロジウムの無機
酸塩（硫酸ロジウム、硝酸ロジウム等）、ロジウムの有
機酸塩（酢酸ロジウム等）、ロジウムの錯化合物、ロジ
ウムのカルボニル錯体、ロジウムと他の金属との錯塩、
ロジウムの酸化物などがあげられる、これらの中では、
ＲｈＣｌ3 ・３Ｈ2 Ｏ、［ＲｈＣｌ（ＣＯ）2 ］2 、
［Ｒｈ3 Ｏ（ＯＣＯＣＨ3 ）6 （ＣＨ3 ＣＯ2 Ｈ）3 ］
ＯＣＯＣＨ3 などを用いることが多い。ロジウム系触媒
は、適当な担体に担持された状態のものであってもよ
い。Rhodium catalysts include rhodium halides (rhodium chloride, rhodium bromide, rhodium fluoride,
Rhodium iodide), inorganic acid salts of rhodium other than halides (rhodium sulfate, rhodium nitrate, etc.), organic acid salts of rhodium (rhodium acetate, etc.), complex compounds of rhodium, carbonyl complexes of rhodium, rhodium and other metals Complex salt of
Rhodium oxide, etc. can be mentioned. Among these,
RhCl 3 .3H 2 O, [RhCl (CO) 2 ] 2 ,
[Rh 3 O (OCOCH 3 ) 6 (CH 3 CO 2 H) 3 ]
OCOCH 3 is often used. The rhodium-based catalyst may be supported on a suitable carrier.
【００１６】銅系化合物としては、銅の有機酸塩（酢酸
塩等）、銅のハロゲン化物（塩化物、臭化物等）、ハロ
ゲン化物以外の銅の無機酸塩、銅の酸化物などがあげら
れる。銅系化合物は酸化剤としての役割を果たすので、
第二銅化合物を用いる。なお銅系化合物と共にあるいは
銅系化合物に代えて酸素を用いることもできる。Examples of the copper-based compound include organic acid salts of copper (such as acetate), halides of copper (such as chloride and bromide), inorganic acid salts of copper other than halides, oxides of copper and the like. . Since the copper compound acts as an oxidant,
A cupric compound is used. Oxygen may be used together with the copper-based compound or in place of the copper-based compound.
【００１７】１，１０−フェナントロリンは、市販の一
水塩や塩酸塩を必要に応じて精製して用いる。銅系化合
物のＣｕは、この１，１０−フェナントロリンのＮに配
位して、安定で酸化力の強い錯体を形成するものと考え
られる。As the 1,10-phenanthroline, a commercially available monohydrate or hydrochloride may be purified and used as necessary. It is considered that Cu, which is a copper-based compound, coordinates with N of the 1,10-phenanthroline to form a stable complex having strong oxidizing power.
【００１８】カルボン酸類としては、脂肪族カルボン酸
（酢酸、プロピオン酸、酪酸等）、脂環式カルボン酸、
芳香族カルボン酸のうち炭素数が２〜１０程度のモノま
たはポリカルボン酸またはそれらの無水物あるいはアル
キルエステルが用いられ、たとえばＲＣＯＯＨで表わさ
れる脂肪族モノカルボン酸の場合、Ｒ（アルキル基）の
Ｈがハロゲンで置換されたものであってもよい。カルボ
ン酸類の中では、トリフルオロ酢酸が本発明の目的に特
に好適である。The carboxylic acids include aliphatic carboxylic acids (acetic acid, propionic acid, butyric acid, etc.), alicyclic carboxylic acids,
Of the aromatic carboxylic acids, mono- or polycarboxylic acids having about 2 to 10 carbon atoms or their anhydrides or alkyl esters are used. For example, in the case of an aliphatic monocarboxylic acid represented by RCOOH, R (alkyl group) H may be replaced with halogen. Among the carboxylic acids, trifluoroacetic acid is particularly suitable for the purposes of the invention.
【００１９】カルボン酸類は溶媒の役割を果たす。カル
ボン酸類と共に、系に不活性な他の溶媒（飽和炭化水
素、アルコール、ケトン、エステル、エーテル、ニトリ
ル、含ハロゲン溶剤、含窒素溶剤等）を併用してもよ
い。The carboxylic acids act as a solvent. Other solvents inert to the system (saturated hydrocarbon, alcohol, ketone, ester, ether, nitrile, halogen-containing solvent, nitrogen-containing solvent, etc.) may be used together with the carboxylic acid.
【００２０】上記のうちロジウム系触媒は、ナフタレン
１モルに対して 0.001〜１０モル、好ましくは 0.002〜
５モル、殊に 0.002〜１モル用いるようにする。ロジウ
ム系触媒の使用量が余りに少ないときはナフトエ酸への
反応速度が小さく、ロジウム化合物の使用量を余りに多
くすることは経済的に不利となる。Of the above, the rhodium-based catalyst is 0.001 to 10 mol, preferably 0.002 to 1 mol, relative to 1 mol of naphthalene.
5 mol, especially 0.002-1 mol should be used. When the amount of the rhodium-based catalyst used is too small, the reaction rate to naphthoic acid is low, and it is economically disadvantageous to use the amount of the rhodium compound used too much.
【００２１】銅系化合物の添加はナフトエ酸の収率向上
に貢献し、またその添加量を多くするとβ−ナフトエ酸
の選択率の向上に有利に作用する。銅系化合物は、ロジ
ウム系触媒１モルに対して0.01〜１００モル、好ましく
は 0.1〜８０モル、殊に１〜５０モル用いるようにす
る。銅系化合物の添加量が余りに少ないときはナフトエ
酸への反応が円滑に進まず、一方銅系化合物の限度を越
えた過多は、β−ナフトエ酸の選択率ばかりでなくナフ
トエ酸自身の収率を低下させることとなる。The addition of the copper-based compound contributes to the improvement of the yield of naphthoic acid, and the increase of the addition amount advantageously acts on the improvement of the selectivity of β-naphthoic acid. The copper-based compound is used in an amount of 0.01 to 100 mol, preferably 0.1 to 80 mol, and particularly 1 to 50 mol, per 1 mol of the rhodium catalyst. When the addition amount of the copper-based compound is too small, the reaction to naphthoic acid does not proceed smoothly, while the excess exceeding the limit of the copper-based compound is not only the selectivity of β-naphthoic acid but also the yield of naphthoic acid itself. Will be reduced.
【００２２】１，１０−フェナントロリンの併用は、β
−ナフトエ酸の選択率を極限（１００％）にまで高める
ことができる上、１，１０−フェナントロリンの併用量
を多くするとβ−ナフトエ酸の収率も向上する。１，１
０−フェナントロリンは、ロジウム系触媒１モルに対し
て 0.1〜１００モル、好ましくは 0.5〜９０モル、殊に
１〜８０モル用いることが望ましい。The combined use of 1,10-phenanthroline is β
-The selectivity of naphthoic acid can be increased to the limit (100%), and the amount of 1,10-phenanthroline used in combination also increases the yield of β-naphthoic acid. 1,1
0-phenanthroline is used in an amount of 0.1 to 100 mol, preferably 0.5 to 90 mol, and more preferably 1 to 80 mol, per 1 mol of the rhodium-based catalyst.
【００２３】カルボン酸類またはその他の溶媒の使用量
は、系の均一化、反応熱の除去、撹拌の容易性などを考
慮して適宜に設定される。The amount of the carboxylic acid or other solvent used is appropriately set in consideration of homogenization of the system, removal of reaction heat, ease of stirring, and the like.
【００２４】本発明においては、上に述べたロジウム系
触媒、銅系化合物、１，１０−フェナントロリンおよび
カルボン酸類の存在下に、ナフタレンと一酸化炭素とを
反応させる。In the present invention, naphthalene is reacted with carbon monoxide in the presence of the above-mentioned rhodium catalyst, copper compound, 1,10-phenanthroline and carboxylic acids.
【００２５】反応温度は、常温〜３００℃程度、好まし
くは３０〜２５０℃、殊に５０〜２００℃とすることが
望ましい。反応温度が余りに低いときはナフタレンの転
化率が小さく、一方反応温度を余りに高くするとナフト
エ酸への転化率が低くなる傾向がある。The reaction temperature is usually room temperature to 300 ° C., preferably 30 to 250 ° C., and particularly 50 to 200 ° C. If the reaction temperature is too low, the conversion of naphthalene will be low, while if the reaction temperature is too high, the conversion to naphthoic acid will tend to be low.
【００２６】反応圧力は常圧〜５０気圧、好ましくは２
〜４０気圧、殊に５〜３０気圧とすることが望ましい。
反応圧力を余りに高くすることは、装置上不利になる
上、ナフトエ酸の収率が低くなるおそれがある。反応圧
力は主として一酸化炭素の供給量によって定まるが、反
応温度におけるナフタレンや溶媒の蒸気圧も加わる。な
お場合によっては、一酸化炭素と共に不活性ガスを供給
することもできる。The reaction pressure is from atmospheric pressure to 50 atm, preferably 2
It is desirable to set the pressure to -40 atm, especially 5 to 30 atm.
If the reaction pressure is too high, it is disadvantageous in terms of equipment and the yield of naphthoic acid may be low. The reaction pressure is mainly determined by the amount of carbon monoxide supplied, but the vapor pressures of naphthalene and the solvent at the reaction temperature are also added. In some cases, an inert gas may be supplied together with carbon monoxide.
【００２７】反応時間には特に限定はないが、１〜１０
０時間程度あるいはそれ以上とすることが多い。The reaction time is not particularly limited, but it is from 1 to 10
It is often 0 hours or more.
【００２８】反応系において、触媒成分はスラリー状態
にあるようにすることが多いが、固定床、流動床などの
方式を採用することも可能である。In the reaction system, the catalyst component is often in a slurry state, but it is also possible to adopt a system such as a fixed bed or a fluidized bed.
【００２９】反応終了後は、反応物からβ−ナフトエ酸
を分離、精製する。未反応のナフタレンは再使用に供す
るようにする。触媒やその他の添加剤も、必要に応じて
再生した後、再使用に供することができる。After the reaction is completed, β-naphthoic acid is separated and purified from the reaction product. Unreacted naphthalene should be reused. The catalyst and other additives can be reused after being regenerated if necessary.
【００３０】[0030]
【作用】本発明においては、ロジウム系触媒の存在下に
（殊にロジウム系触媒、銅系化合物、１，１０−フェナ
ントロリンおよびカルボン酸類の存在下に）、ナフタレ
ンと一酸化炭素とを反応させる方法を採用している。In the present invention, a method of reacting naphthalene with carbon monoxide in the presence of a rhodium catalyst (particularly in the presence of a rhodium catalyst, a copper compound, 1,10-phenanthroline and carboxylic acids) Has been adopted.
【００３１】そのため、ナフタレンからのナフトエ酸の
収率を向上させることができる上、β−ナフトエ酸の選
択率をほぼ１００％にまで向上させることができる。Therefore, the yield of naphthoic acid from naphthalene can be improved, and the selectivity of β-naphthoic acid can be improved to almost 100%.
【００３２】[0032]
【実施例】次に実施例をあげて本発明をさらに説明す
る。EXAMPLES The present invention will be further described with reference to examples.
【００３３】〈反応〉 実施例１ ５０mlのオートクレーブに、ナフタレン１０ mmol 、Ｒ
ｈＣｌ3 ・３Ｈ2 Ｏ0.2 mmol、酢酸第二銅 4.0mmol、ト
リフルオロ酢酸 3.0 ml 、１，１０−フェナントロリン
0.5 mmol をそれぞれ仕込み、一酸化炭素を供給して２
０気圧とした。系の温度を１００℃まで高め、この温度
で撹拌下に７２時間反応させた後、室温にまで冷却し、
解圧した。<Reaction> Example 1 Into a 50 ml autoclave, 10 mmol of naphthalene and R were added.
hCl 3 · 3H 2 O0.2 mmol, cupric acetate 4.0 mmol, trifluoroacetic acid 3.0 ml, 1,10-phenanthroline
Charge 0.5 mmol each and supply carbon monoxide to 2
It was set to 0 atm. The temperature of the system was raised to 100 ° C., reacted at this temperature for 72 hours with stirring, and then cooled to room temperature,
Decompressed.
【００３４】反応物にＮａＣｌ水を加えてからエーテル
で抽出し、ＣＨ2 Ｎ2 を加えて−ＣＯＯＨ基を−ＣＯＯ
ＣＨ3 に変えてから、ＧＬＣ分析に供して定量した。Aqueous NaCl was added to the reaction product, which was then extracted with ether. CH 2 N 2 was added to remove --COOH groups from --COO.
After changing to CH 3 , it was subjected to GLC analysis for quantification.
【００３５】実施例２ ナフタレンの仕込み量を1.0 mmol、ＲｈＣｌ3 ・３Ｈ2
Ｏの仕込み量を 0.02mmol、酢酸第二銅の仕込み量を0.4
mmol、トリフルオロ酢酸の仕込み量を3.0 ml、１，１
０−フェナントロリンの仕込み量を1.0 mmol、圧力を２
０気圧、温度を１００℃、反応時間を２４時間としたほ
かは実施例１を繰り返した。Example 2 The amount of naphthalene charged was 1.0 mmol, and RhCl 3 · 3H 2 was added.
The amount of O charged was 0.02 mmol, and the amount of cupric acetate charged was 0.4.
mmol, trifluoroacetic acid charge of 3.0 ml, 1,1
The amount of 0-phenanthroline charged was 1.0 mmol, and the pressure was 2
Example 1 was repeated except that the pressure was 0 atm, the temperature was 100 ° C., and the reaction time was 24 hours.
【００３６】比較例または参考例 各成分の仕込み量、反応条件を種々変更したほかは実施
例１を繰り返した。Comparative Example or Reference Example Example 1 was repeated except that the charged amount of each component and the reaction conditions were variously changed.
【００３７】〈条件および結果〉条件および結果を表１
に示す。表１中、No. 1 は実施例１、No. 2 は実施例２
に相当する。No. 3 〜No. 11は比較例ないし参考例であ
る。Cu(OAc)2は酢酸第二銅、αはα−ナフトエ酸、βは
β−ナフトエ酸、1,10-Pは１，１０−フェナントロリ
ン、β-CD はβ−シクロデキストリンである。<Conditions and Results> Table 1 shows the conditions and results.
Shown in In Table 1, No. 1 is Example 1 and No. 2 is Example 2
Equivalent to. No. 3 to No. 11 are comparative examples or reference examples. Cu (OAc) 2 is cupric acetate, α is α-naphthoic acid, β is β-naphthoic acid, 1,10-P is 1,10-phenanthroline, and β-CD is β-cyclodextrin.
【００３８】[0038]
【表１】 RhCl3・3H2O Cu(OAc)2 添加物 反応時間 α収率 β収率 β選択 No. (mmol) (mmol) (mmol) (hr) (%) (%) 率 (%) 1 0.2 4.0 1,10-P 0.5 72 trace 96 100 2 0.02 0.4 1,10-P 1.0 24 trace 100 100 3 0.3 - - 24 0 0 - 4 0.2 2.0 - 72 7 122 95 5 0.2 4.0 - 24 25 35 58 6 0.01 0.2 - 24 trace trace - 7 - 2.0 - 24 trace trace - 8 0.2 2.0 K2S2O8 5.0 72 - - - 9 0.2 2.0 β-CD 5.0 72 - - - 10 0.2 - LiBr 1.0 24 trace trace - 11 0.2 - SbCl3 0.2 24 7 12 62 （注）α−およびβ−ナフトエ酸の収率はロジウム系触媒ベースで算出した。 No. 3 においては溶媒として酢酸 3.0 ml を使用した。 No. 8, 9においてはポリマーが生成した。 No. 10においては、ナフタレンのα位に-OCOCF3 がついた化合物とβ位に -OCOCF3 がついた化合物とが得られた。[Table 1] RhCl3・ 3H2O Cu (OAc)2 Additive Reaction time α Yield β Yield β Selection No. (mmol) (mmol) (mmol) (hr) (%) (%) Rate (%) 1 0.2 4.0 1,10-P 0.5 72 trace 96 1002 0.02 0.4 1,10-P 1.0 24 trace 100 100 3 0.3--24 0 0-4 0.2 2.0-72 7 122 95 5 0.2 4.0-24 25 35 58 6 0.01 0.2-24 trace trace-7-2.0-24 trace trace-8 0.2 2.0 K2S2O8 5.0 72---9 0.2 2.0 β-CD 5.0 72---10 0.2-LiBr 1.0 24 trace trace-11 0.2-SbCl 3 0.2 24 7 12 62 (Note) The yields of α- and β-naphthoic acid were calculated based on the rhodium catalyst. In No. 3, 3.0 ml of acetic acid was used as a solvent. In Nos. 8 and 9, polymers were formed. In No. 10, at the α-position of naphthalene, -OCOCF3 Compound with a mark and -OCOCF at the β position3 And a compound marked with were obtained.
【００３９】[0039]
【発明の効果】本発明の方法によれば、ナフタレンおよ
び一酸化炭素からロジウム系触媒を用いてβ−ナフトエ
酸を一段階でかつ極めて高い選択率で得ることができ
る。よって本発明は工業的なβ−ナフトエ酸の生産に適
している。According to the method of the present invention, β-naphthoic acid can be obtained from naphthalene and carbon monoxide using a rhodium catalyst in one step and with extremely high selectivity. Therefore, the present invention is suitable for industrial production of β-naphthoic acid.
Claims (7)
一酸化炭素とを反応させることを特徴とするβ−ナフト
エ酸の製造法。1. A method for producing β-naphthoic acid, which comprises reacting naphthalene with carbon monoxide in the presence of a rhodium catalyst.
フェナントロリンおよびカルボン酸類の存在下に、ナフ
タレンと一酸化炭素とを反応させることを特徴とするβ
−ナフトエ酸の製造法。2. A rhodium-based catalyst, a copper-based compound, 1,10-
Β characterized by reacting naphthalene with carbon monoxide in the presence of phenanthroline and carboxylic acids
-Method for producing naphthoic acid.
の製造法。3. The method according to claim 2, wherein the copper-based compound is a cupric salt.
求項２記載の製造法。4. The method according to claim 2, wherein the carboxylic acid is trifluoroacetic acid.
て 0.001〜１０モル用いることを特徴とする請求項１ま
たは２記載の製造法。5. The method according to claim 1, wherein the rhodium-based catalyst is used in an amount of 0.001 to 10 mol with respect to 1 mol of naphthalene.
て0.01〜１００モル用いることを特徴とする請求項２記
載の製造法。6. The method according to claim 2, wherein the copper compound is used in an amount of 0.01 to 100 mol per mol of the rhodium catalyst.
触媒１モルに対して 0.1〜１００モル用いることを特徴
とする請求項２記載の製造法。7. The method according to claim 2, wherein 1,10-phenanthroline is used in an amount of 0.1 to 100 mol per mol of the rhodium catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6164570A JPH083103A (en) | 1994-06-22 | 1994-06-22 | Method for producing β-naphthoic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6164570A JPH083103A (en) | 1994-06-22 | 1994-06-22 | Method for producing β-naphthoic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH083103A true JPH083103A (en) | 1996-01-09 |
Family
ID=15795685
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6164570A Withdrawn JPH083103A (en) | 1994-06-22 | 1994-06-22 | Method for producing β-naphthoic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH083103A (en) |
-
1994
- 1994-06-22 JP JP6164570A patent/JPH083103A/en not_active Withdrawn
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20010904 |