JPS6326745B2 - - Google Patents
Info
- Publication number
- JPS6326745B2 JPS6326745B2 JP636881A JP636881A JPS6326745B2 JP S6326745 B2 JPS6326745 B2 JP S6326745B2 JP 636881 A JP636881 A JP 636881A JP 636881 A JP636881 A JP 636881A JP S6326745 B2 JPS6326745 B2 JP S6326745B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- acid
- palladium
- catalyst
- compound
- 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
Links
- 239000003054 catalyst Substances 0.000 claims description 26
- -1 aromatic nitro compound Chemical class 0.000 claims description 21
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 11
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 5
- 150000002611 lead compounds Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 229910052763 palladium Inorganic materials 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- WDAXFOBOLVPGLV-UHFFFAOYSA-N ethyl isobutyrate Chemical compound CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VYWYYJYRVSBHJQ-UHFFFAOYSA-N 3,5-dinitrobenzoic acid Chemical compound OC(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 VYWYYJYRVSBHJQ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- PUOIRWDPECROBN-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3,5-dinitrobenzoate Chemical compound CC(=C)C(=O)OCCOC(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 PUOIRWDPECROBN-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229940046892 lead acetate Drugs 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- BZRAULNYWZRKMB-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3,5-diaminobenzoate Chemical compound CC(=C)C(=O)OCCOC(=O)C1=CC(N)=CC(N)=C1 BZRAULNYWZRKMB-UHFFFAOYSA-N 0.000 description 1
- SFMIOOLDTVYJLM-UHFFFAOYSA-N 2-(2-methylpropanoyloxy)ethyl 3,5-diaminobenzoate Chemical compound CC(C)C(=O)OCCOC(=O)C1=CC(N)=CC(N)=C1 SFMIOOLDTVYJLM-UHFFFAOYSA-N 0.000 description 1
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 description 1
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 description 1
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- KQNKJJBFUFKYFX-UHFFFAOYSA-N acetic acid;trihydrate Chemical compound O.O.O.CC(O)=O KQNKJJBFUFKYFX-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- ILUJQPXNXACGAN-UHFFFAOYSA-N ortho-methoxybenzoic acid Natural products COC1=CC=CC=C1C(O)=O ILUJQPXNXACGAN-UHFFFAOYSA-N 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 235000019260 propionic acid Nutrition 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
- 239000012266 salt solution Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Pyrrole Compounds (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、側鎖に炭素−炭素二重結合を有する
各種の芳香族ニトロ化合物のニトロ基を選択的に
還元して側鎖に炭素−炭素二重結合を有する各種
の芳香族アミン化合物を製造する方法を提供する
にある。
従来、側鎖に炭素−炭素二重結合を有する芳香
族ニトロ化合物のニトロ基のみを選択的に還元す
る方法は少なく、わずかに以下(1)〜(3)に示す４，
4′−ジニトロスチルベンゼン−２，2′−ジスルホ
ン酸又はその塩を選択的に還元方法が提案されて
いるのみである。
(1) ジシアンジアミドの存在下でラネ−ニツケル
を用いて水素化する方法。
(2) ヨウ素、臭素又はこれらのイオンを共存さ
せ、パラジウム系触媒を用いて水素化する方
法。
(3) PH４〜5.5もしくはPH7.5〜9.5の４，4′−ジニ
トロスチルベンゼン−２，2′−ジスルホン酸の
ナトリウム塩溶液に、パラジウムもしくは白金
又はこれらの混合物をカーボンブラツクに挾持
させた触媒加えて水素化する方法。
しかし、上記(1)〜(3)の方法では、上記のニトロ
化合物以外ものをニトロ基を選択的に還元できな
かつた。
本発明の目的は、上述した従来技術の欠点をな
くし、側鎖に炭素一炭素二重結合を有する芳香族
ニトロ化合物ならば如何様なものでもニトロ基を
選択的に還元して側鎖に炭素一炭素二重結合を有
する芳香族アミン化合物を得るにある。
上記目的は、
一般式
（但し、式中、Ｒは
The present invention produces various aromatic amine compounds having a carbon-carbon double bond in the side chain by selectively reducing the nitro group of various aromatic nitro compounds having a carbon-carbon double bond in the side chain. This is to provide a way to do so. Conventionally, there are few methods for selectively reducing only the nitro group of an aromatic nitro compound having a carbon-carbon double bond in the side chain, and there are only a few methods shown in (1) to (3) below.
Only a method for selectively reducing 4'-dinitrostilbenzene-2,2'-disulfonic acid or a salt thereof has been proposed. (1) Hydrogenation using Raney-nickel in the presence of dicyandiamide. (2) A method of hydrogenation using a palladium-based catalyst in the coexistence of iodine, bromine, or these ions. (3) A catalyst in which palladium, platinum, or a mixture thereof is sandwiched between carbon black in a sodium salt solution of 4,4'-dinitrostilbenzene-2,2'-disulfonic acid with a pH of 4 to 5.5 or 7.5 to 9.5. In addition, a method of hydrogenation. However, in the methods (1) to (3) above, it was not possible to selectively reduce the nitro group of compounds other than the above-mentioned nitro compounds. The purpose of the present invention is to eliminate the above-mentioned drawbacks of the prior art, and to selectively reduce the nitro group of any aromatic nitro compound having a carbon-carbon double bond in the side chain. The object of the present invention is to obtain an aromatic amine compound having a one-carbon double bond. For the above purpose, the general formula (However, in the formula, R is
【式】【formula】
【式】Ｘは−Ｏ−、[Formula] X is -O-,
【式】であり、ｍ、ｎは０又は
１で表わす。）で表わされる化合物の中から選ば
れる１種又は２種以上の芳香族ニトロ化合物を、
(イ)鉛化合物によつて被毒されたパラジウム一炭酸
カルシウム触媒と、有機カルボン酸存在下に有機
溶剤中で水素化反応させ、ニトロ基のみを選択的
に還元するか、あるいは、(ロ)上記一般式で示され
る芳香族ニトロ化合物をあらかじめ有機カルボン
酸で処理した鉛化合物で被毒されたパラジウム一
炭酸カルシウム触媒存在下に有機溶剤中で水素化
反応を行ない、ニトロ基のみを選択的に還元する
ことで達成される。
以下、本発明で使用する材料について説明す
る。側鎖に炭素一炭素二重結合を有する芳香族ニ
トロ化合物は特に限定されるものではないが、
（但し、式中Ｘは−Ｏ−、
[Formula], where m and n are represented by 0 or 1. ) one or more aromatic nitro compounds selected from the compounds represented by
(a) A hydrogenation reaction is carried out with a palladium monocalcium carbonate catalyst poisoned by a lead compound in an organic solvent in the presence of an organic carboxylic acid to selectively reduce only nitro groups, or (b) The aromatic nitro compound represented by the above general formula is hydrogenated in an organic solvent in the presence of a palladium monocalcium carbonate catalyst poisoned with a lead compound that has been previously treated with an organic carboxylic acid to selectively remove only the nitro group. This is achieved by giving back. The materials used in the present invention will be explained below. Aromatic nitro compounds having a carbon-carbon double bond in the side chain are not particularly limited, but (However, in the formula, X is -O-,
【式】Ｚはハロゲン原子、ｍ、
ｎは０又は１である。）で表わされる化合物の中
から選ばれる少なくとも１種の芳香族ニトロ化合
物を不活性有機溶媒に溶解した溶液を不活性有機
溶媒に溶解した[Formula] Z is a halogen atom, m and n are 0 or 1. ) A solution of at least one aromatic nitro compound selected from the compounds represented by () dissolved in an inert organic solvent is dissolved in an inert organic solvent.
【式】又 は【Formula】Also teeth
【式】で表
わされる化合物の中から選ばれる少なくとも１種
および必要に応じて第３級アミン、又は水酸化ナ
トリウム等の中和剤を用いて低温で反応させて得
たもの、
（但し、式中、Ｘは−Ｏ−、
A product obtained by reacting at a low temperature with at least one compound selected from the compounds represented by the formula and optionally a tertiary amine or a neutralizing agent such as sodium hydroxide; (However, in the formula, X is -O-,
【式】ｍ、ｎは０又は１であ
る。）で表わされる化合物の中から選ばれる少な
くとも１種の芳香族ニトロ化合物を不活性有機溶
媒に溶解した溶液に、不活性有機溶媒に溶解した
[Formula] m and n are 0 or 1. ) in a solution of at least one aromatic nitro compound selected from the compounds represented by
【式】又は[Formula] or
【式】
（但し、Ｚはハロゲン原子である。）で表わされ
る化合物の中から選ばれる少なくとも１種および
必要に応じて第３級アミン又は水酸化ナトリウム
等の中和剤を用いて低温で反応させて得たもので
ある。
具体的には、以下に示すものである。
一般式[Formula] (However, Z is a halogen atom.) React at low temperature using at least one compound selected from the compounds represented by the formula and, if necessary, a neutralizing agent such as a tertiary amine or sodium hydroxide. This is what I got by doing it. Specifically, it is shown below. general formula
【式】【formula】
（但し式中、Ｒは (However, in the formula, R is
【式】又は、[Formula] or
【式】である。）
鉛化合物で被毒したパラジウム一炭酸カルシウ
ム触媒は、例えば炭酸カルシウムの水懸濁液に塩
化パラジウム水溶液を加えて暫次撹拌してから、
水素ガス又はホルマリンのような還元剤で還元
し、得られた沈澱物を別する。別した沈澱物
はそのまま又は乾燥して酢酸鉛のような鉛塩水溶
液中に加え、撹拌しながら加熱し、得られた沈澱
物を水洗別し、これを乾燥したものである。こ
れはいわゆるリンドラー型触媒といわれる触媒に
代表されるものである。〔H.Lindler：Helv，
Chem Acta.，35 446（1952）〕。
上記触媒は前記した芳香族ニトロ化合物に対し
て0.5〜20重量％好ましくは３〜10重量％加える。
なお0.5重量％より少ないと長時間反応させても
未反応物が残り、20重量％より多いと選択性が低
下し炭素一炭素二重結合が飽和したアミン化合物
の生成率が多くなる。
上記触媒と共に用いるが、又は上記触媒を処理
するのに用いる有機カルボン酸としては、種々あ
るが、例えば酢酸、プロピオン酸、カプリン酸、
カプロン酸、カプリル酸等のような脂肪酸類、マ
ロン酸、コハク酸、クエン酸、アジピン酸などの
多塩基性脂肪酸類、乳酸、リンゴ酸、酒石酸など
のオキシ酸、安息香酸、メチル安息香酸、サルチ
ル酸、ニトロ安息香酸、ジニトロ安息香酸、メト
キシ安息香酸、フエニル酢酸などの芳香族カルボ
ン酸類などであり、その添加量は前記芳香族ニト
ロ化合物に対して0.5〜20重量％、好ましくは３
〜10重量％が良い。0.5重量％より少ないとニト
ロ基の選択還元性が低下し、炭素一炭素二重結合
が飽和した化合物が多く生成する。又20重量％以
上の優位性はない。触媒を処理するのに用いる有
機カルボン酸の添加量は、前記の触媒に対して10
〜150重量％、好ましくは30〜100重量である。10
重量％より少ないとニトロ基の選択還元性が低下
し、150重量％より多いと有意性がない。
有機溶媒の最も好ましい代表例は、低級アルコ
ール類又はこれを主成分とするものがあげられる
が、前記した芳香族ニトロ化合物を溶解するもの
であればとくに限定されない。
反応条件は、水素圧が常圧ないし、150Kg／cm2、
好ましくは10〜70Kg／cm2、反応温度が常温ないし
100℃好ましくは40〜80℃である。
次に本発明を実施例により具体的に説明する。
実施例 １
(イ) 被毒したパラジウム触媒の調整
炭酸カルシウム50ｇを水400mlに懸濁させ、
この懸濁液を撹拌しながらパラジウム金属2.5
ｇを含む塩化パラジウム水溶液50mlを30分かか
つて加えた。この液にホルマリン100mlを滴下
し、30分間撹拌してから10％水酸化ナトリウム
水溶液を加えてPH12とし、さらに30分間撹拌し
沈澱物を得た。その後沈澱物を過し、水洗を
３回行なつた後、過物を乾燥してパラジウム
炭酸カルシウム触媒を得た。つぎに酢酸鉛三水
塩５ｇを水100mlに溶解した溶液に、上記パラ
ジウム一炭酸カルシウム触媒を加え、室温で30
分間撹拌してから80℃に40分保ち、これを過
乾燥して被毒したパラジウム触媒51.5ｇを得
た。
(ロ) 水素化反応
500ml容量の反応器（オートクレーブ）中に
２−（3′，5′−ジニトロベンゾイルオキシ）エ
チルメタクリレート25ｇ（0.0771モル）、前記
の(イ)で得た被毒したパラジウム触媒2.5ｇ、ジ
ニトロ安息香酸1.25ｇ、メタノール250mlを仕
込み水素ガスで３回置換したのち水素圧50Kg／
cm2とした。反応器を徐々に加熱し、内温が70℃
になつた時点で撹拌を開始し、水素の吸収がな
くなつてから（約３時間後）さらに30分間撹拌
を行なつた。内温を室温まで冷却し、反応生成
物をオートクレープから取り出し、触媒を別
してからメタノールを減圧下で留去し、残留物
を５％塩酸水溶液150〜200mlに溶解して活性炭
処理を行なつた。その後、５％水酸化ナトリウ
ム溶液でPHを9.0とし、黄色の結晶を得た。生
成物を乾燥してから、イソプロピルエーテルで
再結晶し18.3ｇの黄色針状結晶を得た。これを
NMRで分析したところ、目的物の２−（3′，
5′−ジアミノベンゾイルオキシ）エチルメタク
リレートは17.4ｇ（収率85.5％）であり、残部
は２−（3′，5′−ジアミノベンゾイルオキシ）
エチルイソブチレートであつた。
実施例 ２〜７
第１表の実施例２〜７のような原料を用い、実
施例１と同様に操作し、第１表の結果を得た。
実施例 ８〜11
第２表の実施例８〜11のような原料を用い実施
例１と同様に操作し第２表の結果を得た。
実施例 12
(イ) 被毒したパラジウム触媒の調整
200mlオートクレーブ中に、３，５−ジニト
ロ安息香酸1.25ｇ、被毒したパラジウム触媒
2.5ｇメタノール100mlを仕込み、水素で３回置
換した後、水素圧を50〜60Kg／cm3とした。加温
して内温が70℃となつたら撹拌を開始し、２時
間撹拌した後室温まで冷却し触媒を別した。
メタノールにて洗浄後乾燥し、2.4ｇの修飾触
媒を得た。
(ロ) 水素化反応
200mlオートクレーブ中に２−（3′，5′−ジニ[Formula]. ) A palladium monocarbonate catalyst poisoned with a lead compound can be prepared by, for example, adding a palladium chloride aqueous solution to an aqueous suspension of calcium carbonate and stirring the mixture for a while.
Reduction is performed with a reducing agent such as hydrogen gas or formalin, and the resulting precipitate is separated. The separated precipitate is added as it is or dried to an aqueous solution of a lead salt such as lead acetate, heated while stirring, and the obtained precipitate is washed with water and dried. This is typified by the so-called Lindlar type catalyst. [H. Lindler: Helv,
Chem Acta., 35 446 (1952)]. The above catalyst is added in an amount of 0.5 to 20% by weight, preferably 3 to 10% by weight, based on the aromatic nitro compound described above.
If it is less than 0.5% by weight, unreacted substances will remain even if the reaction is carried out for a long time, and if it is more than 20% by weight, the selectivity will decrease and the production rate of amine compounds with saturated carbon-carbon double bonds will increase. There are various organic carboxylic acids that can be used with or to treat the catalyst, such as acetic acid, propionic acid, capric acid,
Fatty acids such as caproic acid and caprylic acid, polybasic fatty acids such as malonic acid, succinic acid, citric acid, and adipic acid, oxyacids such as lactic acid, malic acid, and tartaric acid, benzoic acid, methylbenzoic acid, and salutyl. acid, aromatic carboxylic acids such as nitrobenzoic acid, dinitrobenzoic acid, methoxybenzoic acid, phenyl acetic acid, etc., and the amount added is 0.5 to 20% by weight, preferably 3% by weight based on the aromatic nitro compound.
~10% by weight is good. When the amount is less than 0.5% by weight, the selective reduction of nitro groups decreases, and many compounds with saturated carbon-carbon double bonds are produced. Moreover, there is no superiority of 20% by weight or more. The amount of organic carboxylic acid used to treat the catalyst is 10
~150% by weight, preferably 30-100% by weight. Ten
When it is less than 150% by weight, the selective reduction of nitro groups decreases, and when it is more than 150% by weight, there is no significance. The most preferred representative example of the organic solvent is lower alcohols or those containing lower alcohols as a main component, but there is no particular limitation as long as it dissolves the above-mentioned aromatic nitro compound. The reaction conditions are hydrogen pressure at normal pressure, 150Kg/cm 2 ,
Preferably 10 to 70Kg/cm 2 , reaction temperature is room temperature to
The temperature is 100°C, preferably 40-80°C. Next, the present invention will be specifically explained using examples. Example 1 (a) Preparation of poisoned palladium catalyst 50 g of calcium carbonate was suspended in 400 ml of water,
2.5% palladium metal while stirring this suspension.
50 ml of an aqueous palladium chloride solution containing g was added over 30 minutes. 100 ml of formalin was added dropwise to this liquid, and after stirring for 30 minutes, a 10% aqueous sodium hydroxide solution was added to adjust the pH to 12, and the mixture was further stirred for 30 minutes to obtain a precipitate. Thereafter, the precipitate was filtered, washed three times with water, and then dried to obtain a palladium calcium carbonate catalyst. Next, the above palladium monocalcium carbonate catalyst was added to a solution of 5 g of lead acetate trihydrate dissolved in 100 ml of water, and the mixture was heated at room temperature for 30 min.
After stirring for a minute, the mixture was kept at 80° C. for 40 minutes and overdried to obtain 51.5 g of a poisoned palladium catalyst. (b) Hydrogenation reaction In a 500 ml reactor (autoclave), 25 g (0.0771 mol) of 2-(3',5'-dinitrobenzoyloxy)ethyl methacrylate and the poisoned palladium catalyst obtained in (a) above were added. After charging 2.5g, dinitrobenzoic acid 1.25g, and methanol 250ml and purging with hydrogen gas three times, the hydrogen pressure was 50kg/
cm2 . Gradually heat the reactor until the internal temperature reaches 70℃
Stirring was started when the temperature reached 100 ml, and stirring was continued for an additional 30 minutes after hydrogen absorption had ceased (about 3 hours later). The internal temperature was cooled to room temperature, the reaction product was taken out from the autoclave, the catalyst was separated, the methanol was distilled off under reduced pressure, and the residue was dissolved in 150 to 200 ml of a 5% aqueous hydrochloric acid solution and treated with activated carbon. . Thereafter, the pH was adjusted to 9.0 with 5% sodium hydroxide solution to obtain yellow crystals. The product was dried and then recrystallized from isopropyl ether to obtain 18.3 g of yellow needle crystals. this
When analyzed by NMR, the target substance 2-(3′,
17.4 g (yield 85.5%) of 5'-diaminobenzoyloxy)ethyl methacrylate, the remainder being 2-(3',5'-diaminobenzoyloxy)
It was ethyl isobutyrate. Examples 2 to 7 Using the raw materials as in Examples 2 to 7 in Table 1, the same operations as in Example 1 were performed to obtain the results in Table 1. Examples 8 to 11 Using the raw materials as in Examples 8 to 11 in Table 2, the same procedure as in Example 1 was carried out to obtain the results in Table 2. Example 12 (a) Preparation of poisoned palladium catalyst In a 200 ml autoclave, 1.25 g of 3,5-dinitrobenzoic acid and poisoned palladium catalyst were added.
After charging 100 ml of 2.5 g methanol and purging with hydrogen three times, the hydrogen pressure was set to 50 to 60 Kg/cm 3 . Stirring was started when the internal temperature reached 70°C, and after stirring for 2 hours, the mixture was cooled to room temperature and the catalyst was separated.
After washing with methanol and drying, 2.4 g of modified catalyst was obtained. (b) Hydrogenation reaction: 2-(3′,5′-dini) in a 200ml autoclave.
【表】【table】
【表】
(1) 実施例１の(イ)と同様にして調整
[Table] (1) Adjustment in the same manner as (a) of Example 1
【表】【table】
【表】
(1) 実施例の(イ)と同様にして調整
トロベンゾイルオキシ）エチルメタクリレート
５ｇ、上記の修飾したパラジウム触媒を0.5ｇ
およびメタノール100mlを仕込んだ水素で３回
置換したあと水素圧を20Kg／cm2とした。容器を
徐々に加熱し、内温70℃になつた時点で、撹拌
を開始し、水素の吸収がなくなつた後（約２時
間）、室温まで冷却し、反応生成物を取り出し、
触媒を別後、メタノールを減圧留去した。残
留物を５％塩酸で溶解したのち不溶分を別
し、５％水酸化ナトリウム水溶液にてPH9.0と
し析出物を過した後乾燥した。収量3.8ｇで
あつた。得られた結晶をNMRにて確認したと
ころ、２−（3′，5′−ジアミノベンゾイルオキ
シ）エチルメタクリレート3.04ｇ（収率74.4
％）２−（3′，5′−ジアミノベンゾイルオキシ）
エチルイソブチリレート0.76ｇであつた。
実施例 13〜18
第３表の実施例13〜18のような原料を用い実施
例１と同様に操作し第３表の結果を得た。
比較例 １[Table] (1) 5 g of trobenzoyloxy)ethyl methacrylate prepared in the same manner as in Example (a), and 0.5 g of the above modified palladium catalyst.
After replacing 100 ml of methanol with hydrogen three times, the hydrogen pressure was set to 20 Kg/cm 2 . The container was gradually heated, and when the internal temperature reached 70°C, stirring was started, and after hydrogen was no longer absorbed (about 2 hours), it was cooled to room temperature, and the reaction product was taken out.
After removing the catalyst, methanol was distilled off under reduced pressure. After dissolving the residue with 5% hydrochloric acid, insoluble matter was separated, the pH was adjusted to 9.0 with a 5% aqueous sodium hydroxide solution, and the precipitate was filtered off, followed by drying. The yield was 3.8g. When the obtained crystals were confirmed by NMR, 3.04 g of 2-(3',5'-diaminobenzoyloxy)ethyl methacrylate (yield 74.4
%) 2-(3',5'-diaminobenzoyloxy)
The amount was 0.76 g of ethyl isobutyrate. Examples 13 to 18 Using the raw materials as in Examples 13 to 18 in Table 3, the same procedure as in Example 1 was carried out to obtain the results in Table 3. Comparative example 1
【表】【table】
【表】
｜ ｜
CH３ CH３
200mlオートクレーブ中に１ｇの２−（3′，5′−
ジニトロベンゾイルオキシ）エチルメタクリレー
ト、実施例１の(イ)で得た被毒パラジウム触媒0.1
ｇ、メタノール100mlを仕込み水素ガスで３回置
換した後、水素圧20Kg／cm2とし、内温を70℃とし
て撹拌を開始した。２時間撹拌後室温まで冷却し
たのち、反応生成物を取り出し、触媒を過後、
反応液を濃縮した。濃縮生成物についてNMRに
よる構造式の確認を行なつたところ、すべて２−
（3′，5′−ジアミノベンゾイルオキシ）エチルイ
ソブチリレートであつた。
比較例 ２
比較例１と同様に触媒としてパラジウム炭素を
用いて水素化反応を行なつたところ、生成物は２
−（3′，5′−ジアミノベンゾイルオキシ）エチル
イソブチレートであつた。
以上述べたように、本発明によれば各種の側鎖
に二重結合を有する芳香族ニトロ化合物のニトロ
基を選択的に還元して、側鎖に二重結合を有する
芳香族アミン化合物が得られる。[Table] ｜ ｜
CH 3 CH 3
1 g of 2-(3',5'-
Dinitrobenzoyloxy)ethyl methacrylate, poisoned palladium catalyst obtained in Example 1 (a) 0.1
After charging 100 ml of methanol and purging with hydrogen gas three times, the hydrogen pressure was set to 20 Kg/cm 2 , the internal temperature was set to 70°C, and stirring was started. After stirring for 2 hours and cooling to room temperature, the reaction product was taken out, and after filtering the catalyst,
The reaction solution was concentrated. When the structural formulas of the concentrated products were confirmed by NMR, all of them were 2-
It was (3',5'-diaminobenzoyloxy)ethylisobutyrate. Comparative Example 2 A hydrogenation reaction was carried out using palladium on carbon as a catalyst in the same manner as in Comparative Example 1, and the product was 2.
-(3',5'-diaminobenzoyloxy)ethyl isobutyrate. As described above, according to the present invention, aromatic amine compounds having a double bond in the side chain can be obtained by selectively reducing the nitro group of various aromatic nitro compounds having a double bond in the side chain. It will be done.
Claims (1)
る１種又は２種以上の芳香族ニトロ化合物を、鉛
化合物によつて被毒されたパラジウム−炭酸カル
シウム触媒と、有機カルボン酸存在下に有機溶剤
中で水素化反応させ、ニトロ基のみを選択的に還
元するか、あるいは、上記一般式で示される芳香
族ニトロ化合物をあらかじめ有機カルボン酸で処
理した鉛化合物で被毒されたパラジウム−炭酸カ
ルシウム触媒存在下に有機溶剤中で水素化反応を
行ない、ニトロ基のみを選択的に還元することを
特徴とする芳香族アミン化合物の製造方法。[Claims] 1. General formula (However, in the formula, R is [Formula] [Formula] X is -O-, [Formula], and m and n are 0 or 1.) Hydrogenation reaction of more than one aromatic nitro compound with a palladium-calcium carbonate catalyst poisoned by a lead compound in an organic solvent in the presence of an organic carboxylic acid to selectively reduce only the nitro group. Alternatively, the aromatic nitro compound represented by the above general formula is hydrogenated in an organic solvent in the presence of a palladium-calcium carbonate catalyst poisoned with a lead compound that has been previously treated with an organic carboxylic acid to remove only the nitro group. A method for producing an aromatic amine compound, characterized by selective reduction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP636881A JPS57120553A (en) | 1981-01-21 | 1981-01-21 | Preparation of aromatic amine compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP636881A JPS57120553A (en) | 1981-01-21 | 1981-01-21 | Preparation of aromatic amine compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57120553A JPS57120553A (en) | 1982-07-27 |
| JPS6326745B2 true JPS6326745B2 (en) | 1988-05-31 |
Family
ID=11636415
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP636881A Granted JPS57120553A (en) | 1981-01-21 | 1981-01-21 | Preparation of aromatic amine compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57120553A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009154208A1 (en) * | 2008-06-17 | 2009-12-23 | 日産化学工業株式会社 | Liquid-crystal alignment material, liquid-crystal display element employing same, and novel diamine |
-
1981
- 1981-01-21 JP JP636881A patent/JPS57120553A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57120553A (en) | 1982-07-27 |
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