JPH0533938B2 - - Google Patents
Info
- Publication number
- JPH0533938B2 JPH0533938B2 JP61189831A JP18983186A JPH0533938B2 JP H0533938 B2 JPH0533938 B2 JP H0533938B2 JP 61189831 A JP61189831 A JP 61189831A JP 18983186 A JP18983186 A JP 18983186A JP H0533938 B2 JPH0533938 B2 JP H0533938B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- water
- reaction
- substituted
- mol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- BTNMPGBKDVTSJY-UHFFFAOYSA-N keto-phenylpyruvic acid Chemical class OC(=O)C(=O)CC1=CC=CC=C1 BTNMPGBKDVTSJY-UHFFFAOYSA-N 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 28
- -1 cobalt carbonyl compound Chemical class 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 229910017052 cobalt Inorganic materials 0.000 claims description 18
- 239000010941 cobalt Substances 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000001903 2-oxo-3-phenylpropanoic acid Substances 0.000 claims description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 15
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 15
- DEDGUGJNLNLJSR-UHFFFAOYSA-N alpha-hydroxycinnamic acid Natural products OC(=O)C(O)=CC1=CC=CC=C1 DEDGUGJNLNLJSR-UHFFFAOYSA-N 0.000 claims description 15
- 229940073608 benzyl chloride Drugs 0.000 claims description 15
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 15
- 150000005524 benzylchlorides Chemical class 0.000 claims description 13
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical group CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 11
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 11
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical group [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 10
- 239000000920 calcium hydroxide Substances 0.000 claims description 10
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- MQIKJSYMMJWAMP-UHFFFAOYSA-N dicobalt octacarbonyl Chemical group [Co+2].[Co+2].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] MQIKJSYMMJWAMP-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 7
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 6
- 239000003021 water soluble solvent Substances 0.000 claims description 5
- 150000002576 ketones Chemical group 0.000 claims description 3
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N phenyl propionaldehyde Natural products CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 33
- 239000010410 layer Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- WLJVXDMOQOGPHL-UHFFFAOYSA-N benzyl-alpha-carboxylic acid Natural products OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 229960003424 phenylacetic acid Drugs 0.000 description 4
- 239000003279 phenylacetic acid Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- CYAKWEQUWJAHLW-UHFFFAOYSA-N 1-(chloromethyl)-4-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C(CCl)C=C1 CYAKWEQUWJAHLW-UHFFFAOYSA-N 0.000 description 2
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 description 2
- MGKPFALCNDRSQD-UHFFFAOYSA-N 2-(4-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=C(F)C=C1 MGKPFALCNDRSQD-UHFFFAOYSA-N 0.000 description 2
- QKSGIGXOKHZCQZ-UHFFFAOYSA-N 2-chloro-2-phenylacetic acid Chemical compound OC(=O)C(Cl)C1=CC=CC=C1 QKSGIGXOKHZCQZ-UHFFFAOYSA-N 0.000 description 2
- ARBYLMGHSUQHSN-UHFFFAOYSA-N 2-oxo-3-(4-propan-2-ylphenyl)propanoic acid Chemical compound CC(C)C1=CC=C(CC(=O)C(O)=O)C=C1 ARBYLMGHSUQHSN-UHFFFAOYSA-N 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- UBQRAAXAHIKWRI-UHFFFAOYSA-N 4-(chloromethyl)-1,2-dimethylbenzene Chemical compound CC1=CC=C(CCl)C=C1C UBQRAAXAHIKWRI-UHFFFAOYSA-N 0.000 description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- PQQDWLYOSCOOSW-UHFFFAOYSA-N (4-fluorophenyl) hydrogen sulfate Chemical compound OS(=O)(=O)OC1=CC=C(F)C=C1 PQQDWLYOSCOOSW-UHFFFAOYSA-N 0.000 description 1
- BETNPSBTDMBHCZ-UHFFFAOYSA-N 1-(chloromethyl)-2,4-dimethylbenzene Chemical compound CC1=CC=C(CCl)C(C)=C1 BETNPSBTDMBHCZ-UHFFFAOYSA-N 0.000 description 1
- UAWVMPOAIVZWFQ-UHFFFAOYSA-N 1-(chloromethyl)-2-methoxybenzene Chemical compound COC1=CC=CC=C1CCl UAWVMPOAIVZWFQ-UHFFFAOYSA-N 0.000 description 1
- VQRBXYBBGHOGFT-UHFFFAOYSA-N 1-(chloromethyl)-2-methylbenzene Chemical compound CC1=CC=CC=C1CCl VQRBXYBBGHOGFT-UHFFFAOYSA-N 0.000 description 1
- OFFXBUAZOPRAJX-UHFFFAOYSA-N 1-(chloromethyl)-2-phenylmethoxybenzene Chemical compound ClCC1=CC=CC=C1OCC1=CC=CC=C1 OFFXBUAZOPRAJX-UHFFFAOYSA-N 0.000 description 1
- ABJGYUSFOIMJPT-UHFFFAOYSA-N 1-(chloromethyl)-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1CCl ABJGYUSFOIMJPT-UHFFFAOYSA-N 0.000 description 1
- FYNVRRYQTHUESZ-UHFFFAOYSA-N 1-(chloromethyl)-3,5-dimethylbenzene Chemical compound CC1=CC(C)=CC(CCl)=C1 FYNVRRYQTHUESZ-UHFFFAOYSA-N 0.000 description 1
- VGISFWWEOGVMED-UHFFFAOYSA-N 1-(chloromethyl)-3-methoxybenzene Chemical compound COC1=CC=CC(CCl)=C1 VGISFWWEOGVMED-UHFFFAOYSA-N 0.000 description 1
- LZBOHNCMCCSTJX-UHFFFAOYSA-N 1-(chloromethyl)-3-methylbenzene Chemical compound CC1=CC=CC(CCl)=C1 LZBOHNCMCCSTJX-UHFFFAOYSA-N 0.000 description 1
- MKXVKELDRLNWGV-UHFFFAOYSA-N 1-(chloromethyl)-3-phenylmethoxybenzene Chemical compound ClCC1=CC=CC(OCC=2C=CC=CC=2)=C1 MKXVKELDRLNWGV-UHFFFAOYSA-N 0.000 description 1
- OCFXNUNCMJFLML-UHFFFAOYSA-N 1-(chloromethyl)-3-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC(CCl)=C1 OCFXNUNCMJFLML-UHFFFAOYSA-N 0.000 description 1
- MOHYOXXOKFQHDC-UHFFFAOYSA-N 1-(chloromethyl)-4-methoxybenzene Chemical compound COC1=CC=C(CCl)C=C1 MOHYOXXOKFQHDC-UHFFFAOYSA-N 0.000 description 1
- DMHZDOTYAVHSEH-UHFFFAOYSA-N 1-(chloromethyl)-4-methylbenzene Chemical compound CC1=CC=C(CCl)C=C1 DMHZDOTYAVHSEH-UHFFFAOYSA-N 0.000 description 1
- HLQZCRVEEQKNMS-UHFFFAOYSA-N 1-(chloromethyl)-4-phenylbenzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=CC=C1 HLQZCRVEEQKNMS-UHFFFAOYSA-N 0.000 description 1
- WAXIFMGAKWIFDQ-UHFFFAOYSA-N 1-tert-butyl-4-(chloromethyl)benzene Chemical compound CC(C)(C)C1=CC=C(CCl)C=C1 WAXIFMGAKWIFDQ-UHFFFAOYSA-N 0.000 description 1
- MWBXCWLRASBZFB-UHFFFAOYSA-N 2-(2,4-dimethylphenyl)acetic acid Chemical compound CC1=CC=C(CC(O)=O)C(C)=C1 MWBXCWLRASBZFB-UHFFFAOYSA-N 0.000 description 1
- OTTPBKINJOYJGW-UHFFFAOYSA-N 2-(3,4-dimethylphenyl)acetic acid Chemical compound CC1=CC=C(CC(O)=O)C=C1C OTTPBKINJOYJGW-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- ATPPNMLQNZHDOG-UHFFFAOYSA-N 2-fluoro-2-phenylacetic acid Chemical compound OC(=O)C(F)C1=CC=CC=C1 ATPPNMLQNZHDOG-UHFFFAOYSA-N 0.000 description 1
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical class O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 description 1
- LVOQCQHGSGURKK-UHFFFAOYSA-N 3-(3,4-dimethylphenyl)-2-oxopropanoic acid Chemical compound CC1=CC=C(CC(=O)C(O)=O)C=C1C LVOQCQHGSGURKK-UHFFFAOYSA-N 0.000 description 1
- UTTDJAPJOSBBIO-UHFFFAOYSA-N 3-(4-fluorophenyl)-2-oxopropanoic acid Chemical compound OC(=O)C(=O)CC1=CC=C(F)C=C1 UTTDJAPJOSBBIO-UHFFFAOYSA-N 0.000 description 1
- OEBIVOHKFYSBPE-UHFFFAOYSA-N 4-Benzyloxybenzyl alcohol Chemical compound C1=CC(CO)=CC=C1OCC1=CC=CC=C1 OEBIVOHKFYSBPE-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 229940049953 phenylacetate Drugs 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- 150000002993 phenylalanine derivatives Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002982 water resistant material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—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)
Description
【発明の詳細な説明】
(イ) 産業上の利用分野
本発明は、コバルトカルボニル化合物触媒の存
在下、置換ベンジルクロライドと一酸化炭素及び
アルカリ土類金属塩基とを反応させる際に、溶媒
として水と水に難溶性の溶媒を存在させ反応させ
ることを特徴とする置換フエニルピルビン酸の製
造法に関するものである。Detailed Description of the Invention (a) Industrial Application Field The present invention provides a method for reacting substituted benzyl chloride with carbon monoxide and an alkaline earth metal base in the presence of a cobalt carbonyl compound catalyst, using water as a solvent. The present invention relates to a method for producing substituted phenylpyruvic acid, which is characterized in that the reaction is carried out in the presence of a poorly soluble solvent in water.
置換フエニルピルビン酸は、例えば置換フエニ
ルアラニンとして医薬品等として利用される物質
である。 Substituted phenylpyruvic acid is a substance used as a pharmaceutical product, for example, as substituted phenylalanine.
(ロ) 従来の技術
置換ベンジルクロライドと一酸化炭素との反応
による置換フエニルピルビン酸の製造法は公知で
あり、例えば特公昭56−18587号公報等が挙げら
れる。(b) Prior Art A method for producing substituted phenylpyruvic acid by reacting substituted benzyl chloride with carbon monoxide is known, and for example, Japanese Patent Publication No. 18587/1987 is cited.
特公昭56−18587号公報では、触媒として金属
カルボニル化合物、特にコバルトカルボニル化合
物を使用して、アルカリ土類金属塩基の存在下、
置換ベンジルクロライドと一酸化炭素とを水／ア
ルコール混合溶媒中で反応させ置換フエニルピル
ビン酸を製造する方法が提案されている。 In Japanese Patent Publication No. 56-18587, a metal carbonyl compound, especially a cobalt carbonyl compound, is used as a catalyst, and in the presence of an alkaline earth metal base,
A method has been proposed for producing substituted phenylpyruvic acid by reacting substituted benzyl chloride and carbon monoxide in a water/alcohol mixed solvent.
(ハ) 発明が解決しようとする問題点
しかし、上述の特公昭56−18587号公報をはじ
めとする既存の置換フエニルピルビン酸の製造法
では、置換フエニルピルビン酸は反応中に固体と
して析出する置換フエニルピルビン酸のアルカリ
金属塩又はアルカリ土類金属塩を濾過後酸処理す
ることにより簡単に得ることができるが、副生置
換フエニル酢酸のアルカリ金属塩又はアルカリ土
類金属塩とコバルトカルボニル触媒が反応濾液中
に溶解しており、これら副生置換フエニル酢酸ア
ルカリ金属塩又はアルカリ土類金属塩とコバルト
カルボニル触媒の相互分離並びにコバルトカルボ
ニル触媒の再生には煩雑な工程を必要とする。(c) Problems to be Solved by the Invention However, in existing methods for producing substituted phenylpyruvic acid, including the above-mentioned Japanese Patent Publication No. 56-18587, substituted phenylpyruvic acid precipitates as a solid during the reaction. The alkali metal salt or alkaline earth metal salt of substituted phenylpyruvic acid can be easily obtained by acid treatment after filtration. The catalyst is dissolved in the reaction filtrate, and complicated steps are required to separate the by-product substituted phenyl acetic acid alkali metal salt or alkaline earth metal salt from the cobalt carbonyl catalyst and to regenerate the cobalt carbonyl catalyst.
又、コバルトカルボニル触媒の再生は、反応濾
液より水／アルコール溶媒等を除去し、鉱酸で処
理して副生置換フエニル酢散を回収後、生成した
コバルトの鉱酸塩を、例えば水酸化アルカリ等で
処理して水酸化コバルトとした後、更に水酸化コ
バルトを高温、高圧の水性ガスと反応させてコバ
ルトカルボニル化合物とするものである。 In addition, to regenerate the cobalt carbonyl catalyst, water/alcohol solvent etc. are removed from the reaction filtrate, treated with mineral acid to recover by-product substituted phenyl acetate powder, and then the produced cobalt mineral acid salt is treated with alkali hydroxide, for example. After processing to produce cobalt hydroxide, the cobalt hydroxide is further reacted with high-temperature, high-pressure water gas to produce a cobalt carbonyl compound.
又、特公昭56−18587号公報の方法は、５〜200
バールの圧力下で反応が行われ、置換フエニルビ
ルビン酸を実用的な収率で得るためには40バール
以上の圧力が必要な常圧下では好ましい収率で置
換フエニルビルビン酸を得ることができない。 In addition, the method of Japanese Patent Publication No. 56-18587 is 5 to 200
The reaction is carried out under a pressure of 1 bar, and substituted phenyl biruvic acid cannot be obtained in a preferred yield under normal pressure, where a pressure of 40 bar or more is required to obtain a practical yield of substituted phenyl biruvic acid.
本発明者らは、これらの欠点を改良すべく鋭意
努力検討した結果本発明を完成したものである。 The present inventors have completed the present invention as a result of their earnest efforts and studies to improve these drawbacks.
(ニ) 問題点を解決するための手段
本発明は、コバルトカルボニル化合物触媒の存
在下、置換ベンジルクロライドと一酸化炭素及び
アルカリ土類金属塩基とを反応させる際に、溶媒
として水と水に難溶性の溶媒を存在させ反応させ
ることを特徴とする置換フエニルピルビン酸の製
造法に関するものである。(d) Means for Solving the Problems The present invention uses water as a solvent and water-resistant materials when reacting a substituted benzyl chloride with carbon monoxide and an alkaline earth metal base in the presence of a cobalt carbonyl compound catalyst. The present invention relates to a method for producing substituted phenylpyruvic acid characterized by carrying out the reaction in the presence of a soluble solvent.
本発明の置換ベンジルクロライドとしては、ｏ
−弗化ベンジルクロライド、ｍ−弗化ベンジルク
ロライド、ｐ−弗化ベンジルクロライド、ｏ−メ
チルベンジルクロライド、ｍ−メチルベンジルク
ロライド、ｐ−メチルベンジルクロライド、ｏ−
イソプロピルベンジルクロライド、ｍ−イソプロ
ピルベンジルクロライド、ｐ−イソプロピルベン
ジルクロライド、ｏ−塩化ベンジルクロライド、
ｍ−塩化ベンジルクロライド、ｐ−塩化ベンジル
クロライド、２，４−ジメチルベンジルクロライ
ド、３，４−ジメチルベンジルクロライド、３，
５−ジメチルベンジルクロライド、ｏ−メトキシ
ベジルクロライド、ｍ−メトキシベジルクロライ
ド、ｐ−メトキシベンジルクロライド、ｏ−ベン
ジロキシベジルクロライド、ｍ−ベンジロキシベ
ジルクロライド、ｐ−ベンジロキシベンジルクロ
ライド、ｍ，ｐ−メチレンジオキシシベンジルク
ロライド、ｐ−フエニルベンジルクロライド、ｐ
−ｔ−ブチルベンジルクロライド等が挙げられ
る。 The substituted benzyl chloride of the present invention includes o
-Fluorinated benzyl chloride, m-fluorinated benzyl chloride, p-fluorinated benzyl chloride, o-methylbenzyl chloride, m-methylbenzyl chloride, p-methylbenzyl chloride, o-
Isopropylbenzyl chloride, m-isopropylbenzyl chloride, p-isopropylbenzyl chloride, o-benzyl chloride,
m-benzyl chloride, p-benzyl chloride, 2,4-dimethylbenzyl chloride, 3,4-dimethylbenzyl chloride, 3,
5-dimethylbenzyl chloride, o-methoxybenzyl chloride, m-methoxybenzyl chloride, p-methoxybenzyl chloride, o-benzyloxybenzyl chloride, m-benzyloxybenzyl chloride, p-benzyloxybenzyl chloride, m , p-methylenedioxybenzyl chloride, p-phenylbenzyl chloride, p
-t-butylbenzyl chloride and the like.
本発明における水に難溶性の溶媒としては、ベ
ンゼン、トルエン等の芳香族炭化水素類、ヘキサ
ン、ヘプタン等の脂肪族炭化水素類、ジエチルエ
ーテル、ジイソプロピルエーテル、ジフエニルエ
ーテル等の脂肪族及び芳香族エーテル類、メチル
イソブチルケトン、アセトフエノン、ジイソプロ
ピルケトン、メチルイソプロピルケトン、ジブチ
ルケトン、ジイソブチルケトン、シクロペンタノ
ン等の脂肪族及び芳香族ケトン類が選ばれ、特に
メチルイソブチルケトン、アセトフエノン等のケ
トン類が好ましい。 In the present invention, the poorly water-soluble solvents include aromatic hydrocarbons such as benzene and toluene, aliphatic hydrocarbons such as hexane and heptane, and aliphatic and aromatic hydrocarbons such as diethyl ether, diisopropyl ether, and diphenyl ether. Ethers, aliphatic and aromatic ketones such as methyl isobutyl ketone, acetophenone, diisopropyl ketone, methyl isopropyl ketone, dibutyl ketone, diisobutyl ketone, and cyclopentanone are selected, and ketones such as methyl isobutyl ketone and acetophenone are particularly preferred. .
反応溶媒中の置換ベンジルクロライドの濃度は
特に制限はないが、水に難溶性の溶媒に対して一
般に１〜50重量％使用される。 The concentration of substituted benzyl chloride in the reaction solvent is not particularly limited, but it is generally used in an amount of 1 to 50% by weight based on the slightly water-soluble solvent.
水の量は、一般に水に難溶性の溶媒に対し10〜
200重量％使用される。 The amount of water is generally 10 to 10% for a solvent that is poorly soluble in water.
200% by weight used.
本発明で使用されるアルカリ土類金属塩基は、
一般にアルカリ土類金属水酸化物、アルカリ土類
金属酸化物及びアルカリ土類金属炭酸塩から選ば
れるが、特にアルカリ土類金属水酸化物が使用さ
れ、なかでも水酸化カルシウムが好ましい。 The alkaline earth metal base used in the present invention is
Generally selected from alkaline earth metal hydroxides, alkaline earth metal oxides and alkaline earth metal carbonates, particularly alkaline earth metal hydroxides are used, with calcium hydroxide being preferred.
アルカリ土類金属塩基の使用量は、一般に置換
ベンジルクロライド１モル当たり少なくとも１モ
ル使用するする必要があり、置換ベンジルクロラ
イド１モル当たり少なくとも1.0〜2.5モルの使用
が好ましい。 The alkaline earth metal base should generally be used in an amount of at least 1 mol per mol of substituted benzyl chloride, preferably at least 1.0 to 2.5 mol per mol of substituted benzyl chloride.
触媒としては、コバルトカルボニル化合物、特
にジコバルトオクタカルボニルが好ましい。 As the catalyst, cobalt carbonyl compounds, especially dicobalt octacarbonyl, are preferred.
触媒は、コバルトカルボニル化合物／塩化ベン
ジル（モル比）として一般に１／１〜１／1000の
範囲で使用されるが、１／30〜１／200の範囲が
特に好ましい。 The cobalt carbonyl compound/benzyl chloride (molar ratio) of the catalyst is generally used in a range of 1/1 to 1/1000, but a range of 1/30 to 1/200 is particularly preferred.
一酸化炭素は、高純度である必要はなく水性ガ
ス等も使用できる。一酸化炭素圧力は、一般に常
圧〜200Kg／cm2の範囲が採用される。 Carbon monoxide does not need to be of high purity, and water gas or the like can also be used. The carbon monoxide pressure generally ranges from normal pressure to 200 kg/cm 2 .
反応温度は、20〜150℃が好ましくは40〜100℃
が良い。 The reaction temperature is 20-150℃, preferably 40-100℃
is good.
一般に、反応は一酸化炭素の吸収が停止するま
で行い、反応溶液は目的物である置換フエニルピ
ルビン酸、副生物である置換フエニル酢酸及びコ
バルトカルボニル触媒を回収する為に次のように
処理される。 Generally, the reaction is carried out until the absorption of carbon monoxide stops, and the reaction solution is treated as follows to recover the target product, substituted phenylpyruvic acid, by-products, substituted phenylacetic acid, and cobalt carbonyl catalyst. Ru.
即ち、反応溶液を濾過することにより、反応中
に固体として析出した置換フエニルピルビン酸の
アルカリ土類金属塩よりなる固体部分、置換フエ
ニル酢酸のアルカリ土類金属塩を含有する水層部
分及びコバルトカルボニル触媒を含有する水に難
溶性の溶媒層部分に分離することができる。 That is, by filtering the reaction solution, a solid portion consisting of the alkaline earth metal salt of substituted phenylpyruvic acid precipitated as a solid during the reaction, an aqueous layer portion containing the alkaline earth metal salt of substituted phenylpyruvic acid, and cobalt. It can be separated into a slightly water-soluble solvent layer containing the carbonyl catalyst.
続いて、濾過操作により分取された置換フエニ
ルピルビン酸のアルカリ土類金属塩は、鉱酸水溶
液、例えば希塩酸水溶液で酸性とし、得られた水
溶液を適当な有機溶媒、例えばジエチルエーテル
等で抽出後、有機溶媒を除去することにより置換
フエニルピルビン酸を得ることができる。同様
に、置換フエニル酢酸のアルカリ土類金属塩を含
有する水層部分は、鉱酸水溶液、例えば希塩酸水
溶液で酸性とし、得られた水溶液を適当な有機溶
媒、例えばジエチルエーテル等で抽出後、有機溶
媒を除去することにより副生置換フエニル酢酸を
回収することができる。 Subsequently, the alkaline earth metal salt of substituted phenylpyruvic acid separated by filtration is made acidic with an aqueous mineral acid solution, for example, a dilute aqueous hydrochloric acid solution, and the resulting aqueous solution is extracted with a suitable organic solvent, such as diethyl ether. Thereafter, substituted phenylpyruvic acid can be obtained by removing the organic solvent. Similarly, the aqueous layer containing the alkaline earth metal salt of substituted phenylacetic acid is made acidic with a mineral acid aqueous solution, for example, dilute hydrochloric acid aqueous solution, and the resulting aqueous solution is extracted with a suitable organic solvent, such as diethyl ether. By-product substituted phenylacetic acid can be recovered by removing the solvent.
又、コバルトカルボニル触媒を含有する水に難
溶生の溶媒層部分は何等処理を行うことなくその
まま反応系にリサイクルし、再使用することがで
きる。 Further, the solvent layer portion containing the cobalt carbonyl catalyst and hardly soluble in water can be recycled to the reaction system as it is without any treatment and can be reused.
(ホ) 発明の効果
本発明によれば、置換フエニルビルピン酸收率
が高く、副生置換フエニル酢酸のアルカリ土類金
属塩とコバルトカルボニル触媒の相互分離が容易
で且つコバルトカルボニル触媒はそのまま反応系
にリサイクルして再使用することができる。(E) Effects of the Invention According to the present invention, the yield of substituted phenylbilpic acid is high, the alkaline earth metal salt of the by-product substituted phenylacetic acid and the cobalt carbonyl catalyst can be easily separated from each other, and the cobalt carbonyl catalyst can be directly added to the reaction system. Can be recycled and reused.
従つて、経済的に置換フエニルピルビン酸を製
造することが可能となつた。 Therefore, it has become possible to economically produce substituted phenylpyruvic acid.
以下に本発明を実施例を挙げて詳細に説明する
が、本発明はこれらに限定されるものではない。 The present invention will be described in detail below with reference to Examples, but the present invention is not limited thereto.
(ヘ) 実施例
実施例 １
500mlのステンレス製オートクレーブに、メチ
ルイソブチルケトン100ml、水50ml、水酸化カル
シウム9.3ｇ（0.126モル）、ｐ−弗化ベンジルク
ロライド8.8ｇ（0.061モル）、及びジコバルトオ
クタカルボニル1.2ｇ（0.0035モル）を仕込んだ。(f) Examples Example 1 In a 500 ml stainless steel autoclave, 100 ml of methyl isobutyl ketone, 50 ml of water, 9.3 g (0.126 mol) of calcium hydroxide, 8.8 g (0.061 mol) of p-benzyl fluoride, and dicobalt octave. 1.2 g (0.0035 mol) of carbonyl was charged.
オートクレーブ内を一酸化炭素で洗浄し、一酸
化炭素加圧下で撹拌しながら昇温後、一酸化炭素
圧力１Kg／cm2、温度50℃で一酸化炭素の吸収が停
止するまで10時間反応を行つた。 The inside of the autoclave was washed with carbon monoxide, and the temperature was raised with stirring under carbon monoxide pressure. The reaction was then carried out at a carbon monoxide pressure of 1 Kg/cm 2 and a temperature of 50°C for 10 hours until carbon monoxide absorption stopped. Ivy.
反応後、反応混合物は一酸化炭素圧力を利用し
てオートクレーブから加圧濾過器を介して固体と
有機層及び水層に分離した。 After the reaction, the reaction mixture was separated from the autoclave into a solid, an organic layer, and an aqueous layer through a pressure filter using carbon monoxide pressure.
得られた固体を500mlのフラスコに移し、10％
塩酸水溶液270mlとジエチルエーテル150mlを加え
固体が完全に溶解するまで撹拌した。ジエチルエ
ーテル層を分離後、水層を更にジエチルエーテル
100mlで２回抽出した。これらジエチルエーテル
層を併せ、水洗後硫酸ナトリウムで乾燥した。乾
燥後ジエチルエーテルを留去するとｐ−弗化フエ
ニルピンルビン酸8.1ｇが得られ、收率は73.0％
であつた。 Transfer the resulting solid to a 500 ml flask and add 10%
270 ml of an aqueous hydrochloric acid solution and 150 ml of diethyl ether were added and stirred until the solid was completely dissolved. After separating the diethyl ether layer, the aqueous layer is further diluted with diethyl ether.
Extracted twice with 100 ml. These diethyl ether layers were combined, washed with water, and then dried over sodium sulfate. After drying, diethyl ether was distilled off to obtain 8.1 g of p-fluorinated phenylpine rubic acid, with a yield of 73.0%.
It was hot.
反応濾液の水層は、10％塩酸水溶液70mlで酸性
としジエチルエーテル100mlで３回抽出した。こ
れらジエチルエーテル層を併せ、硫酸ナトリウム
で乾燥後、ジエチルエーテルを留去するとｐ−弗
化フエニル酢酸が1.0ｇ得られ、收率は10.7％で
あつた。 The aqueous layer of the reaction filtrate was acidified with 70 ml of a 10% aqueous hydrochloric acid solution and extracted three times with 100 ml of diethyl ether. These diethyl ether layers were combined, dried over sodium sulfate, and then diethyl ether was distilled off to obtain 1.0 g of p-fluorophenyl acetic acid, with a yield of 10.7%.
反応濾液の有機層には、コバルトカルボニル触
媒が存在した。 A cobalt carbonyl catalyst was present in the organic layer of the reaction filtrate.
実施例 ２
水に難溶性の溶媒としてアセトフエノンを使用
した他は、実施例１と同様に反応及び処理を行つ
た。ｐ−弗化フエニルピルビン酸の收率は72.0
％、ｐ−弗化フエニル酢酸の收率は10.5％であつ
た。Example 2 The reaction and treatment were carried out in the same manner as in Example 1, except that acetophenone was used as a poorly water-soluble solvent. The yield of p-fluorinated phenylpyruvic acid is 72.0
%, the yield of p-fluorophenyl acetic acid was 10.5%.
実施例 ３
常圧下一酸化炭素を吹込みながら、反応温度を
50℃、反応時間を20時間とした他は、実施例１と
同様に反応及び処理を行つた。ｐ−弗化フエニル
ピルビン酸の收率は71.5％、ｐ−弗化フエニル硫
酸の收率は9.2％であつた。Example 3 While blowing in carbon monoxide under normal pressure, the reaction temperature was increased.
The reaction and treatment were carried out in the same manner as in Example 1, except that the temperature was 50°C and the reaction time was 20 hours. The yield of p-fluorophenylpyruvic acid was 71.5%, and the yield of p-fluorophenylsulfuric acid was 9.2%.
実施例 ４
メチルイソブチルケトン100ml、水50ml、水酸
化カルシウム9.3ｇ（0.126モル）、ｏ−弗化ベン
ジルクロライド8.8ｇ（0.061モル）、及びジコバ
ルトオクタカルボニル1.2ｇ（0.0035モル）を仕
込み、実施例１と同様に反応及び処理を行つた。
ｏ−弗化フエニルピルビン酸の収率は68.0％、ｏ
−弗化フエニル酢酸の收率は5.9％であつた。Example 4 100 ml of methyl isobutyl ketone, 50 ml of water, 9.3 g (0.126 mol) of calcium hydroxide, 8.8 g (0.061 mol) of o-fluorinated benzyl chloride, and 1.2 g (0.0035 mol) of dicobalt octacarbonyl were prepared. The reaction and treatment were carried out in the same manner as in Example 1.
The yield of o-fluorinated phenylpyruvic acid was 68.0%, o
-The yield of fluorinated phenylacetic acid was 5.9%.
実施例 ５
メチルイソブチルケトン100ml、水50ml、水酸
化カルシウム9.3ｇ（0.126モル）、ｍ−弗化ベン
ジルクロライド8.8ｇ（0.061モル）、及びジコバ
ルトオクタカルボニル1.2ｇ（0.0035モル）を仕
込み、実施例１と同様に反応及び処理を行つた。
ｍ−弗化フエニルピルビン酸の収率は71.4％、ｍ
−弗化フエニル酢酸の收率は3.5％であつた。Example 5 100 ml of methyl isobutyl ketone, 50 ml of water, 9.3 g (0.126 mol) of calcium hydroxide, 8.8 g (0.061 mol) of m-benzyl fluoride, and 1.2 g (0.0035 mol) of dicobalt octacarbonyl were charged. The reaction and treatment were carried out in the same manner as in Example 1.
The yield of m-fluorinated phenylpyruvic acid was 71.4%, m
-The yield of fluorophenyl acetic acid was 3.5%.
実施例 ６
メチルイソブチルケトン100ml、水50ml、水酸
化カルシウム9.3ｇ（0.126モル）、ｐ−塩化ベン
ジルクロライド9.8ｇ（0.061モル）、及びジコバ
ルトオクタカルボニル1.2ｇ（0.0035モル）を仕
込み、実施例１と同様に反応及び処理を行つた。
ｐ−塩化フエニルピルビン酸の収率は77.4％、ｐ
−塩化フエニル酢酸の収酸の收率は2.4％であつ
た。Example 6 100 ml of methyl isobutyl ketone, 50 ml of water, 9.3 g (0.126 mol) of calcium hydroxide, 9.8 g (0.061 mol) of p-benzyl chloride, and 1.2 g (0.0035 mol) of dicobalt octacarbonyl were prepared. The reaction and treatment were carried out in the same manner as above.
The yield of p-chlorinated phenylpyruvic acid was 77.4%, p
-The acid yield of chlorophenylacetic acid was 2.4%.
実施例 ７
メチルイソブチルケトン100ml、水50ml、水酸
化カルシウム9.3ｇ（0.126モル）、ｐ−塩化ベン
ジルクロライド9.8ｇ（0.061モル）、及びジコバ
ルトオクタカルボニル1.2ｇ（0.0035モル）を仕
込み、実施例１と同様に反応及び処理を行つた。
ｐ−塩化フエニルピルビン酸の収率は77.4％、ｐ
−塩化フエニル酢酸の收率は10.3％であつた。Example 7 100 ml of methyl isobutyl ketone, 50 ml of water, 9.3 g (0.126 mol) of calcium hydroxide, 9.8 g (0.061 mol) of p-benzyl chloride, and 1.2 g (0.0035 mol) of dicobalt octacarbonyl were charged. The reaction and treatment were carried out in the same manner as above.
The yield of p-chlorinated phenylpyruvic acid was 77.4%, p
-The yield of chlorophenylacetic acid was 10.3%.
実施例 ８
メチルイソブチルケトン100ml、水50ml、水酸
化カルシウム9.3ｇ（0.126モル）、２，４−ジメ
チルベンジクロライド9.4ｇ（0.061モル）、及び
ジコバルトオクタカルボニル1.2ｇ（0.0035モル）
を仕込み、実施例１と同様に反応及び処理を行つ
た。２，４−ジメチルフエニルピルビン酸の収率
は81.0％、２，４−ジメチルフエニル酢酸の收率
は1.7％であつた。Example 8 100 ml of methyl isobutyl ketone, 50 ml of water, 9.3 g (0.126 mol) of calcium hydroxide, 9.4 g (0.061 mol) of 2,4-dimethylbendichloride, and 1.2 g (0.0035 mol) of dicobalt octacarbonyl.
The reaction and treatment were carried out in the same manner as in Example 1. The yield of 2,4-dimethylphenylpyruvic acid was 81.0%, and the yield of 2,4-dimethylphenylacetic acid was 1.7%.
実施例 ９
メチルイソブチルケトン100ml、水50ml、水酸
化カルシウム9.3ｇ（0.126モル）、３，４−ジメ
チルベンジルクロライド9.4ｇ（0.061モル）、及
びジコバルトオクタカルボニル1.2ｇ（0.0035モ
ル）を仕込み、実施例１と同様に反応及び処理を
行つた。３，４−ジメチルフエニルピルビン酸の
収率は73.5％、３，４−ジメチルフエニル酢酸の
收率は2.0％であつた。Example 9 100 ml of methyl isobutyl ketone, 50 ml of water, 9.3 g (0.126 mol) of calcium hydroxide, 9.4 g (0.061 mol) of 3,4-dimethylbenzyl chloride, and 1.2 g (0.0035 mol) of dicobalt octacarbonyl were charged and carried out. The reaction and treatment were carried out in the same manner as in Example 1. The yield of 3,4-dimethylphenylpyruvic acid was 73.5%, and the yield of 3,4-dimethylphenylacetic acid was 2.0%.
実施例 10
メチルイソブチルケトン100ml、水50ml、水酸
化カルシウム9.3ｇ（0.126モル）、ｐ−イソプロ
ピルベンジルクロライド10.3ｇ（0.061モル）、及
びジコバルトオクタカルボニル1.2ｇ（0.0035モ
ル）を仕込み、実施例１と同様に反応及び処理を
行つた。ｐ−イソプロピルフエニルピルビン酸の
収率は72.1％、ｐ−イソプロピルフエニル酢酸の
收率は6.8％であつた。Example 10 100 ml of methyl isobutyl ketone, 50 ml of water, 9.3 g (0.126 mol) of calcium hydroxide, 10.3 g (0.061 mol) of p-isopropylbenzyl chloride, and 1.2 g (0.0035 mol) of dicobalt octacarbonyl were prepared. The reaction and treatment were carried out in the same manner as above. The yield of p-isopropylphenylpyruvic acid was 72.1%, and the yield of p-isopropylphenylpyruvic acid was 6.8%.
Claims (1)
換ベンジルクロライドと一酸化炭素及びアルカリ
土類金属塩基とを反応させる際に、溶媒として水
と水に難溶性の溶媒を存在させ反応させることを
特徴とする置換フエニルピルビン酸の製造法。 ２ 水に難溶性の溶媒がケトンであることを特徴
とする特許請求の範囲第１項の製造法。 ３ ケトンがメチルイソブチルケトン又はアセト
フエノンであることを特徴とする特許請求の範囲
第１項の製造法。 ４ アルカリ土類金属塩基が水酸化カルシウムで
あることを特徴とする特許請求の範囲第１項の製
造法。 ５ コバルトカルボニル化合物がジコバルトオク
タカルボニルであることを特徴とする特許請求の
範囲第１項の製造法。 ６ 一酸化炭素圧力が常圧〜100Kg／cm2であるこ
とを特徴とする特許請求の範囲第１項の製造法。[Claims] 1. When reacting a substituted benzyl chloride with carbon monoxide and an alkaline earth metal base in the presence of a cobalt carbonyl compound catalyst, the reaction is carried out in the presence of water and a poorly water-soluble solvent as a solvent. A method for producing substituted phenylpyruvic acid, characterized by: 2. The production method according to claim 1, wherein the solvent that is poorly soluble in water is a ketone. 3. The manufacturing method according to claim 1, wherein the ketone is methyl isobutyl ketone or acetophenone. 4. The manufacturing method according to claim 1, wherein the alkaline earth metal base is calcium hydroxide. 5. The manufacturing method according to claim 1, wherein the cobalt carbonyl compound is dicobalt octacarbonyl. 6. The manufacturing method according to claim 1, wherein the carbon monoxide pressure is normal pressure to 100 Kg/cm 2 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61189831A JPS6348244A (en) | 1986-08-13 | 1986-08-13 | Production of substituted phenylpyruvic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61189831A JPS6348244A (en) | 1986-08-13 | 1986-08-13 | Production of substituted phenylpyruvic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6348244A JPS6348244A (en) | 1988-02-29 |
| JPH0533938B2 true JPH0533938B2 (en) | 1993-05-20 |
Family
ID=16247939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61189831A Granted JPS6348244A (en) | 1986-08-13 | 1986-08-13 | Production of substituted phenylpyruvic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6348244A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003014057A1 (en) * | 2001-08-08 | 2003-02-20 | Tanabe Seiyaku Co., Ltd. | Processes for producing halogenophenylpyruvic acid and optically active halogenophenylalanine |
-
1986
- 1986-08-13 JP JP61189831A patent/JPS6348244A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6348244A (en) | 1988-02-29 |
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