JPH0327345A - Production of phenetylamines - Google Patents
Production of phenetylaminesInfo
- Publication number
- JPH0327345A JPH0327345A JP16095089A JP16095089A JPH0327345A JP H0327345 A JPH0327345 A JP H0327345A JP 16095089 A JP16095089 A JP 16095089A JP 16095089 A JP16095089 A JP 16095089A JP H0327345 A JPH0327345 A JP H0327345A
- Authority
- JP
- Japan
- Prior art keywords
- nitrostyrene
- formula
- hydrogen
- reaction
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- PIAOLBVUVDXHHL-VOTSOKGWSA-N β-nitrostyrene Chemical compound [O-][N+](=O)\C=C\C1=CC=CC=C1 PIAOLBVUVDXHHL-VOTSOKGWSA-N 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000005530 alkylenedioxy group Chemical group 0.000 claims abstract description 5
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical class NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 claims description 11
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- PIAOLBVUVDXHHL-SREVYHEPSA-N [(z)-2-nitroethenyl]benzene Chemical compound [O-][N+](=O)\C=C/C1=CC=CC=C1 PIAOLBVUVDXHHL-SREVYHEPSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 20
- 239000002904 solvent Substances 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 12
- 150000001875 compounds Chemical class 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 7
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 abstract description 6
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 abstract description 5
- 229960003638 dopamine Drugs 0.000 abstract description 2
- 230000001766 physiological effect Effects 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- UWYZHKAOTLEWKK-UHFFFAOYSA-N 1,2,3,4-tetrahydroisoquinoline Chemical compound C1=CC=C2CNCCC2=C1 UWYZHKAOTLEWKK-UHFFFAOYSA-N 0.000 abstract 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 2
- IMPPGHMHELILKG-UHFFFAOYSA-N 4-ethoxyaniline Chemical compound CCOC1=CC=C(N)C=C1 IMPPGHMHELILKG-UHFFFAOYSA-N 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 34
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 33
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 18
- PIAOLBVUVDXHHL-UHFFFAOYSA-N 2-nitroethenylbenzene Chemical class [O-][N+](=O)C=CC1=CC=CC=C1 PIAOLBVUVDXHHL-UHFFFAOYSA-N 0.000 description 10
- -1 lithium aluminum hydride Chemical compound 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- DZGWFCGJZKJUFP-UHFFFAOYSA-N tyramine Chemical compound NCCC1=CC=C(O)C=C1 DZGWFCGJZKJUFP-UHFFFAOYSA-N 0.000 description 3
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- UIAAKXDJMXMFMG-UHFFFAOYSA-N 1,2,3-trimethoxy-4-(2-nitroethenyl)benzene Chemical compound COC1=CC=C(C=C[N+]([O-])=O)C(OC)=C1OC UIAAKXDJMXMFMG-UHFFFAOYSA-N 0.000 description 1
- JKQUXSHVQGBODD-VOTSOKGWSA-N 1-(4-Methoxyphenyl)-2-nitroethylene Chemical compound COC1=CC=C(\C=C\[N+]([O-])=O)C=C1 JKQUXSHVQGBODD-VOTSOKGWSA-N 0.000 description 1
- IJBGIPFDIABTKB-AATRIKPKSA-N 1-methoxy-3-[(e)-2-nitroethenyl]benzene Chemical compound COC1=CC=CC(\C=C\[N+]([O-])=O)=C1 IJBGIPFDIABTKB-AATRIKPKSA-N 0.000 description 1
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 1
- XVXCSPJSXIUNQJ-UHFFFAOYSA-N 2-methoxy-4-(2-nitroethenyl)phenol Chemical compound COC1=CC(C=C[N+]([O-])=O)=CC=C1O XVXCSPJSXIUNQJ-UHFFFAOYSA-N 0.000 description 1
- QGCVJPGJBCRIEV-UHFFFAOYSA-N 2-methoxy-5-(2-nitroethenyl)phenol Chemical compound COC1=CC=C(C=C[N+]([O-])=O)C=C1O QGCVJPGJBCRIEV-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- ANOUKFYBOAKOIR-UHFFFAOYSA-N 3,4-dimethoxyphenylethylamine Chemical compound COC1=CC=C(CCN)C=C1OC ANOUKFYBOAKOIR-UHFFFAOYSA-N 0.000 description 1
- DIVQKHQLANKJQO-UHFFFAOYSA-N 3-methoxytyramine Chemical compound COC1=CC(CCN)=CC=C1O DIVQKHQLANKJQO-UHFFFAOYSA-N 0.000 description 1
- CHTJRVASYXOBSO-UHFFFAOYSA-N 4-(2-nitroethenyl)-1,2-bis(phenylmethoxy)benzene Chemical compound C=1C=CC=CC=1COC1=CC(C=C[N+](=O)[O-])=CC=C1OCC1=CC=CC=C1 CHTJRVASYXOBSO-UHFFFAOYSA-N 0.000 description 1
- 238000006407 Bischler-Napieralski reaction Methods 0.000 description 1
- PZAGQUOSOTUKEC-UHFFFAOYSA-N acetic acid;sulfuric acid Chemical compound CC(O)=O.OS(O)(=O)=O PZAGQUOSOTUKEC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000003935 benzaldehydes Chemical class 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- MXXMJJSIJDMYJZ-UHFFFAOYSA-N n-(2-phenylethyl)hydroxylamine Chemical class ONCCC1=CC=CC=C1 MXXMJJSIJDMYJZ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229960003732 tyramine Drugs 0.000 description 1
Landscapes
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、それ自体生理活性を有する化合物であるか、
または、ｌ．２．３．４−テトラヒドロイソキノリン等
の生理活性を有する化合物の前駆体として用いることの
できるフェネチルアミン類又はその塩の製造法に関する
ものである．（従来技術及び発明が解決しようとする課
題）従来、一般式（Ｈ）で示されるフェネチルアミン類
の製造方法としては、一般式（Ｉ）で示されるβ−ニト
ロスチレン類の水素化リチウムアルミニウムを用いた還
元（Ｊ． Ａｍ． Ｃｈｅｒａ． Ｓｏｃ．， ７２．
２７８１ （１９５０１及びＴｅｔｒａｈｅｄｒｏｎ
１４４６（１９６１１）が−穀的に知られている．しか
しこの方法では、高価な水素化リチウムアルミニウムを
使用しなければならない．
また、接触還元の例としては、β−ニトロスチレンのパ
ラジウムを用いた還元が知られているが、これらはいず
れら水素圧３５気圧、塩酸水溶液中８５℃という条件（
Ｈｅｌｖ． Ｃｈｉｓ． Ａｃｔａ．５１ １９７２
Ｔ１９６８１ １や、水素圧は常圧ながら酢酸一硫酸中
５０℃での水素化（Ｂｅｒ．． ６８Ｂ． １５７９（
１９３５））という厳しい反応条件下で行われている．
これらの方法では、反応に特殊な装置を必要としたり、
反応後に生成物を取り出すために多大の労力を必要とす
るため工業的な方法としては採用しがたい．
このような事情に鑑み、濃和な条件下でかかる反応を進
行させる触媒の開発を鋭意検討した結果，本発明を完成
させるに至った．
（課題を解決するための手段及び作用）本発明者らは上
記問題点を検討した結果、パラジウム−炭素触媒を用い
、溶媒として無機鉱酸を含むアルコールを用いると、驚
くべきことに、β−ニトロスチレンの水素による触媒還
元が、常圧下、室温以下で６容易に進行し，対応するフ
エネチルアミン類を高収率で与えることを見出し本発明
を完成させるに至った．
すなわち本発明は、対応するベンズアルデヒドとニトロ
メタンとから容易に得られる次式（工）：〔式中、Ｒ，
〜Ｒ，は、水素又はＯＲで示される基であるか（ここで
、Ｒは水素、低級アルキル基、アラルキル基を示し．Ｒ
，−Ｒ．の少なくとちーはＯＲである）、あるいはＲ１
〜Ｒ，の隣接する二つの基が一緒になってアルキレンジ
才キシ基を形成していてもよい〕
で示される（Ｚ）及び／又は（Ｅｌ一〇一ニトロスチレ
ン誘導体を，パラジウム−炭素触媒の存在下、無機鉱酸
を含むアルコール溶媒中で水素と接触還元することによ
り、目的とする次式（ ＩＩ ｌ ：（式中、Ｒ ＋
＝ Ｒ ｓは上記記載の意味を有する）で示されるフエ
ネチルアミン類又はその塩を高収率で得る方法に関する
．本発明方法によれば、反応を常温以下、常圧において
も行なうことができ、特殊な装置は必要ではなく、また
触媒を除去した後に溶媒を除去するのみで純度の高い目
的物が得られ、従来の方法の欠点を殆ど回避することが
できる．
上記式において、品は、シス及び／又はトランス異性体
を意味するものである．
上式（Ｉ）及び（ＴＩ）において、Ｒが低級アルキルで
ある場合には、１〜６個、好ましくは１〜３個の炭素原
子を有する直鎖又は分岐鎖のアルキル基であってよく、
その例としては、メチル、エチル、ｎ−プロビル、ｎ−
ブチル等が挙げられる．特にメチルが好ましい．また、
Ｒがアラルキルである場合には，ベンジル，２−フエニ
ルエチル、ｌ−フェニルエチル等であってよく、ベンジ
ルが好ましい．また、Ｒ，〜Ｒ，の隣接する２つの基が
アルキレンジオキシ基を形成している場合には、かかる
アルキレン基は１〜３個、好ましくは１〜２個の炭素原
子を有する直鎖又は分岐鎖のアルキレンであってよく、
かかるアルキレンジオキシの例としては、メチレンジ才
キシ，エチレンジオキシ等が挙げられる．
出発物質として用いられるβ−ニトロスチレン類は、公
知の方法によって、対応するベンズアルデヒド類とニト
ロメタンとから容易に得られる．このようなβ−ニトロ
スチレン類としては３−メトキシーβ−ニトロスチレン
、４−メトキシーβ−ニトロスチレン、３−エトキシー
β−ニトロスチレン、４−エトキシーβ−ニトロスチレ
ン、３．４−メチレンジ才キシ一〇一二トロスチレン，
３．４−ジメトキシーβ−ニトロスチレン、３．４−ジ
エトキシーβ−ニトロスチレン，３−メトキシ−４−ヒ
ドロキシーβ−ニトロスチレン、３−ヒドロキシ−４−
メトキシーβ−ニトロスチレン、３．４−ジベンジルオ
キシーβ一ニトロスチレン、３−ペンジルオキシーβ−
ニトロスチレン、４−ペンジルオキシーβ−ニトロスチ
レン、２，３．４−トリメトキシーβ−ニトロスチレン
等が挙げられる．
反応溶媒としては、アルコール類が適している．アルコ
ール類の例としては、メタノール、エタノール，プロバ
ノール、インブロパノール，ブタノール等が挙げられる
．
これらの溶媒の使用量は、β−ニトロスチレン類の１．
０〜１００容量倍の範囲である．通常、生産性、反応性
を考慮して、２．０〜５０容量倍を使用する．
触媒はパラジウム−炭素を使用し、そのパラジウム含有
量はＯ．１％〜５０％の範囲のものが使用可能であり、
好ましくは１〜２０％パラジウム−炭素が用いられる．
β−ニトロスチレン類に対する、パラジウムの使用量は
、β−ニトロスチレン類１モルあたり０．０００１〜０
．５ｇ原子の範囲であり、経済性、反応効率を考慮する
と、○．○ｌ〜０．２ｇ原子が好ましい．
本発明の特徴の一つである、溶媒において用いる酸の例
としては、塩酸が最も好適であるが、他の無機鉱酸、例
えば臭化水素、ヨウ化水素、過塩素酸等も同様に用いる
ことができることが当業者に容易に理解されるであろう
．
塩酸を使用する場合には、生成するフエネチルアミン類
が塩酸を塩酸塩として消費するので、通常、使用される
β−ニトロスチレン類と当量以上の量を使用する．好適
には、用いられるβ−ニトロスチレン類１モルあたり１
．０〜１０モルの塩酸を使用し，さらに好適には０．１
０〜５．０モル使用する．塩酸の供給方法としては、濃
塩酸を加えてもよく、また、塩酸ガスを反応溶媒に溶解
する方法を採用してもよい。Detailed Description of the Invention (Industrial Application Field) The present invention relates to a compound that itself has physiological activity,
Or l. 2.3. It relates to a method for producing phenethylamines or salts thereof that can be used as precursors of physiologically active compounds such as 4-tetrahydroisoquinoline. (Prior Art and Problems to be Solved by the Invention) Conventionally, as a method for producing phenethylamines represented by the general formula (H), lithium aluminum hydride of β-nitrostyrenes represented by the general formula (I) has been used. (J. Am. Chera. Soc., 72.
2781 (19501 and Tetrahedron
1446 (19611) is known as a grain. However, this method requires the use of expensive lithium aluminum hydride. In addition, as an example of catalytic reduction, reduction of β-nitrostyrene using palladium is known, but these were carried out under the conditions of hydrogen pressure of 35 atm and 85°C in an aqueous hydrochloric acid solution (
Helv. Chis. Acta. 51 1972
T19681 1, hydrogenation at 50°C in acetic acid monosulfuric acid at normal hydrogen pressure (Ber.. 68B. 1579 (
The reaction was carried out under severe reaction conditions (1935)).
These methods require special equipment for the reaction or
This method is difficult to adopt as an industrial method because it requires a great deal of effort to extract the product after the reaction. In view of these circumstances, the present invention was completed as a result of intensive research into the development of a catalyst that allows such reactions to proceed under concentrated conditions. (Means and effects for solving the problem) As a result of studying the above-mentioned problems, the present inventors found that, surprisingly, when using a palladium-carbon catalyst and using an alcohol containing an inorganic mineral acid as a solvent, β- The present inventors have completed the present invention by discovering that catalytic reduction of nitrostyrene with hydrogen proceeds easily under normal pressure and below room temperature to give the corresponding phenethylamines in high yields. That is, the present invention provides the following formula easily obtained from the corresponding benzaldehyde and nitromethane: [wherein R,
~R, is hydrogen or a group represented by OR (where R represents hydrogen, a lower alkyl group, or an aralkyl group.
,-R. at least and chi are OR), or R1
Two adjacent groups of ~R, may be taken together to form an alkylene dioxy group] By catalytic reduction with hydrogen in an alcoholic solvent containing an inorganic mineral acid in the presence of
The present invention relates to a method for obtaining phenethylamines or salts thereof represented by the formula (Rs has the meaning as described above) in high yield. According to the method of the present invention, the reaction can be carried out at room temperature or below and at normal pressure, no special equipment is required, and the target product with high purity can be obtained by simply removing the solvent after removing the catalyst. Most of the drawbacks of conventional methods can be avoided. In the above formula, the product refers to cis and/or trans isomers. In the above formulas (I) and (TI), when R is lower alkyl, it may be a straight or branched alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms,
Examples include methyl, ethyl, n-probyl, n-
Examples include butyl. Methyl is particularly preferred. Also,
When R is aralkyl, it may be benzyl, 2-phenylethyl, l-phenylethyl, etc., with benzyl being preferred. In addition, when two adjacent groups R, ~R, form an alkylene dioxy group, such alkylene group is a straight chain having 1 to 3, preferably 1 to 2 carbon atoms or It may be a branched alkylene,
Examples of such alkylene dioxy include methylene dioxy, ethylene dioxy, and the like. The β-nitrostyrenes used as starting materials can be easily obtained from the corresponding benzaldehydes and nitromethane by known methods. Such β-nitrostyrenes include 3-methoxy β-nitrostyrene, 4-methoxy β-nitrostyrene, 3-ethoxy β-nitrostyrene, 4-ethoxy β-nitrostyrene, and 3,4-methylene dioxy-nitrostyrene. 〇12 Trostyrene,
3.4-dimethoxy β-nitrostyrene, 3.4-diethoxy β-nitrostyrene, 3-methoxy-4-hydroxy-β-nitrostyrene, 3-hydroxy-4-
Methoxy-β-nitrostyrene, 3,4-dibenzyloxy-β-nitrostyrene, 3-penzyloxy-β-
Examples include nitrostyrene, 4-penzyloxy-β-nitrostyrene, 2,3,4-trimethoxyβ-nitrostyrene, and the like. Alcohols are suitable as reaction solvents. Examples of alcohols include methanol, ethanol, probanol, imbropanol, butanol, and the like. The amount of these solvents to be used is 1.
The range is 0 to 100 times the capacity. Usually, 2.0 to 50 times the volume is used in consideration of productivity and reactivity. The catalyst used is palladium-carbon, the palladium content of which is O. A range of 1% to 50% can be used,
Preferably 1-20% palladium-carbon is used. The amount of palladium used for β-nitrostyrenes is 0.0001 to 0 per mole of β-nitrostyrenes.
．． It is within the range of 5g atoms, and considering economic efficiency and reaction efficiency, ○. ○l~0.2g atoms are preferred. As an example of the acid used in the solvent, which is one of the features of the present invention, hydrochloric acid is the most suitable example, but other inorganic mineral acids such as hydrogen bromide, hydrogen iodide, perchloric acid, etc. can be used as well. Those skilled in the art will readily understand that this can be done. When using hydrochloric acid, the generated phenethylamines consume the hydrochloric acid as a hydrochloride salt, so the amount used is usually at least equivalent to the β-nitrostyrene used. Preferably 1 mole of β-nitrostyrene used
．． Use 0 to 10 mol of hydrochloric acid, more preferably 0.1
Use 0 to 5.0 mol. As a method for supplying hydrochloric acid, concentrated hydrochloric acid may be added, or a method of dissolving hydrochloric acid gas in the reaction solvent may be adopted.
反応温度は、−３０〜１００℃の範囲で実施可能である
．しかしながら、室温以上の温度では副生物が増加する
傾向が見られるので、通常−２０〜３０℃の範囲が好適
である．
反応の水素圧力は、１気圧で十分であるが、それ以上の
高圧にしても反応は進行する．また窒素等の不活性ガス
で希釈して使用して６良い．反応時間は、温度、圧力、
触媒量等により変動するが通常０．５〜５０時間の範囲
で終了する．
反応は通常、出発物質であるβ−ニトロスチレン誘導体
類、溶媒アルコール、無機鉱酸、触媒であるパラジウム
−炭素の混合物を、所定温度に保ち、水素雰囲気下に撹
拌することによって行なわれる．各成分の添加順序に制
限は無い．このようにして得られた反応混合物から目的
反応生成物を取得する方法は、溶媒、触媒を蒸留、ｔ戸
過等の通常の方法で除いた後、反応混合物をアンモニア
、水酸化アルカリ等で塩基性にし、適当な溶媒で抽出す
ることにより得られる．ここで用いる抽出溶媒としては
、ケトン、アルデヒド等のアミン類と反応する溶媒以外
であれば使用可能であり，例としては、塩化メチレン、
エチルエーテル、ペンゼン、トルエン等が挙げられる．
次いで抽出溶媒を蒸留等の通常の除去方法で除くと目的
物が得られる．また、無機鉱酸として塩酸を用いて目的
化合物の塩酸塩を得るときは、反応混合物を塩基性にす
ることなく、溶媒で抽出すると塩酸塩が得られる．この
際の溶媒としては上記と同様の溶媒が使用できるが、塩
化メチレン、クロロホルム、ジクロロエタン等の溶媒が
優れている．
反応の成績が良い場合には、触媒、溶媒を除去するのみ
で目的物の塩酸塩が高純度に得られる．
通常、出発原料に対応するフェネチルアミン類が得られ
るが、ペンジルオキシ置換基、または置換ベンジルオキ
シ置換基を持つβ−ニトロスチレン類（一般式（Ｉ）で
Ｒ１〜Ｒ，がベンジルオキシ基もしくは置換ペンジルオ
キシ基である場合）を使用すると，反応条件下でこれら
のベンジル基ち水素化分解され、対応するヒドロキシフ
エネチルアミン類を生成する。The reaction temperature can be carried out in the range of -30 to 100°C. However, since by-products tend to increase at temperatures above room temperature, a temperature range of -20 to 30°C is usually preferred. A hydrogen pressure of 1 atm is sufficient for the reaction, but the reaction will proceed even if the pressure is higher than that. It may also be used after diluting it with an inert gas such as nitrogen. Reaction time depends on temperature, pressure,
Although it varies depending on the amount of catalyst etc., it usually ends in the range of 0.5 to 50 hours. The reaction is usually carried out by stirring a mixture of β-nitrostyrene derivatives as a starting material, an alcohol solvent, an inorganic mineral acid, and a palladium-carbon catalyst under a hydrogen atmosphere while maintaining the mixture at a predetermined temperature. There are no restrictions on the order in which each component is added. The method of obtaining the desired reaction product from the reaction mixture obtained in this way is to remove the solvent and catalyst by a conventional method such as distillation or filtration, and then convert the reaction mixture into a base using ammonia, alkali hydroxide, etc. It can be obtained by drying and extracting with an appropriate solvent. As the extraction solvent used here, any solvent other than those that react with amines such as ketones and aldehydes can be used. Examples include methylene chloride,
Examples include ethyl ether, penzene, and toluene.
The target product is then obtained by removing the extraction solvent using a conventional removal method such as distillation. Furthermore, when using hydrochloric acid as an inorganic mineral acid to obtain the hydrochloride of the target compound, the hydrochloride can be obtained by extraction with a solvent without making the reaction mixture basic. As the solvent in this case, the same solvents as above can be used, but solvents such as methylene chloride, chloroform, and dichloroethane are excellent. If the reaction results are good, the desired hydrochloride salt can be obtained with high purity simply by removing the catalyst and solvent. Usually, phenethylamines corresponding to the starting materials are obtained, but β-nitrostyrenes having a penzyloxy substituent or a substituted benzyloxy substituent (in general formula (I), R1 to R, are benzyloxy groups or substituted penzyloxy groups) ), these benzyl groups are hydrogenolyzed under the reaction conditions to produce the corresponding hydroxyphenethylamines.
本反応で得られる，フエネチルアミン類とじては（塩酸
塩を含む１、３．４−メチレンジオキシーβ−フエネチ
ルアミン、３．４−ジメトキシーβ−フエネチルアミン
，３−メトキシ−４−ヒドロキシーβ−フェネチルアミ
ン、３−ヒドロキシ−４−メトキシ−β−フエネチルア
ミン、３．４−ジヒドロキシーβ−フェネチルアミン、
４−ヒドロキシーβ−フエネチルアミン、２．３．４−
トリメトキシーβ−フエネチルアミン等が挙げられる．
このようにして得られたフェネチルアミン類は、Ｂｉｓ
ｃｈｌｅｒ−Ｎａｐｉｅｒａｌｓｋｉ反応あるいはＰｉ
ｃｔｅｓｔ−Ｓｐｅｎｇｌｅｒ反応により、対応するｌ
，２．３．４−テトラヒドロイソキノリンに誘導するこ
とができ、本反応の有用性が認められる．また、式（Ｉ
Ｉ）においてＲ，及びＲｓがＯＨであり、Ｒ．Ｒ４及び
Ｒｉが水素原子である化合物はドーパミンとして知られ
ている生理学的に活性な有用な化合物である．
（発明の効果）
以上説明したように、本発明方法によれば、有用な化合
物であるフエネチルアミン類を、特殊な装置や、反応後
に生成物を取り出すための多大の労力を必要としないで
、温和な条件下で製造することができる．
（実施例）
次に実施例をあげて更に具体的に本発明について説明す
る．
３．４−メチレンジ才キシーβ−ニトロスチレン（１１
（０．５００ｇ，２．５９ｍｍｏｉ’ｌ，５％Ｐｄ−Ｃ
Ｋタイプ（日本エンゲルハルト製）（０．５５３ｇ
，Ｐｄ ： ０．２６ｍｍｏｆ）を濃塩酸（０． ５ｍ
ｔ’）及びエタノール（１０ｄ）中、水素雰囲気下，氷
水冷却下で３時間撹拌した．Ｐｄ−Ｃを炉別後、濃縮し
，水（４０ｙ７）を加え，塩化メチレン（２０ＭＩＸ３
）で水層を洗浄した．水層に、アンモニア水をアルカリ
性になるまで加え、塩化メチレン（２０ｙ＋ｆＸ４）で
抽出し、Ｎａ＊ｓＯ４で乾燥した後、濃縮して茶色の油
状物である化合物（２１（０．３０３ｇ、１ ． ８
３ｎ＋ｍｏ７）を得た．（収率７ｌ％）
３．４−ジメトキシーβ−ニトロスチレン（３）（０．
５００ｇ． ２． ３９１１１０１０ノ）、５
％Ｐｄ−ＣＫタイプ（日本エンゲルハルト製ＮＯ．５０
９ｇ，Ｐ ｄ ： ０． ２ ４ｍｍｏｆ）を濃塩酸（
０．５ｄ）及びエタノール（１０ｍｌ）中、水素雰囲気
下，室温で２４時間撹拌した，Ｐｄ−Ｃを炉別後．１１
縮し、水（２０ｍｌ’）を加え、塩化メチレン（２ ０
ｄＸ３）で水層を洗浄した．水層に、アンモニア水をア
ルカリ性になるまで加え、塩化メチレン（２０ｄＸ３）
で抽出し、Ｎａ富ＳＯ．で乾燥した後、濃縮して茶色の
油秋物である化合物（４）（０．３１６ｇ、１ ． ７
４ｍｍｏｆ）を得た．（収率７３％）
丈思盟旦
３− ト シ−４−ヒ゛ロ シ一 一フェニルエ３−メ
トキシー４−ヒドロキシーβ−ニトロスチレン（５）（
０．５００ｇ，２．５６ｍｍｏ１１．５％Ｐｄ−Ｇ
Ｋタイプ（日本エンゲルハルト製）（０．５４５ｇ．Ｐ
ｄ ： ０．２６ｍｍｏｉ’）を濃塩酸（０． ５１Ｒ
１）及びエタノール（１０ｍｊ）中、水素雰囲気下，氷
水冷却下で３時間撹拌した．Ｐｄ−Ｃを枦別後、濃縮し
、水（４０ｄ）を加え、塩化メチレン（３０ｄＸ３）で
水層を洗浄し、濃縮して淡灰色結晶の化合物（６）（０
．４４２ｇ、２． １８ｍｍｏｆ）を得た．（収率８
１％）３−ヒドロキシ−４−メトキシーβ−ニトロスチ
レン（７ＮＯ．５００ｇ、２．５６ｍｍｏノ）、５％Ｐ
ｄ−Ｇ Ｋタイプ（日本エンゲルハルト製）（０．５
４５ｇ．Ｐｄ ： ０．２６ｍｍｏｆ）を濃塩酸（０．
５−）及びエタノール（１０ｄ）中、水素雰囲気下、氷
水冷却下で３時間撹拌した．Ｐｄ−Ｃを炉別後、濃縮し
、水（４０ｄ）を加え、塩化メチレン（３ ０−Ｘ ３
）で水層を洗浄し、濃縮して淡黄色結晶の化合物（８０
０．４７３ｇ、２ ． ３ ３ ｍｎ＋ｏｆ）を得た．
（収率９ｌ％）３．４−ジベンジルオキシーβ−ニトロ
スチレン（９ＮＯ．５００ｇ．１．３８ｍｍｏｆ１．５
％Ｐｄ−Ｃ Ｋタイプ（日本エンゲルハルト製）（０
．５４５ｇ．Ｐｄ ： ０．１４ｍｍｏｆ’）を濃塩酸
（０． ３１ｎＩ）及びエタノール（ｌｏＷｌｌ）中、
水素雰囲気下、室温で２４時間撹拌した．Ｐｄ−Ｃをｔ
戸別後、濃縮し、白色結晶の化合物（Ｉ Ｏ）（０．２
６０ｇ．１．３７ｍｍｏ７）を得た．（収率９９％）
量 １２ チラミン
４−ペンジルオキシ一〇一二トロスチレン（１ １１
（０． ５００ｇ、 １ ． ９ ６ ｍｍｏ７）
． ５％Ｐｄ−Ｃ Ｋタイプ（日本エンゲルハルト製
）（０． ４ １ ７ｇ． Ｐｄ ： ０． ２０ｍｍ
ｏｆ）を濃塩酸（０． ４ｔｌ’）及びエタノール（ｌ
ｏｕｔ’）中、水素雰囲気下、氷水冷却下で３時間撹拌
した．Ｐｄ−Ｃを炉別後、濃縮し、水（４ ０１ＩＪ！
）を加え、塩化メチレン（３０Ｗｄ！Ｘ３）で水層を洗
浄し、濃縮して淡灰色結晶の化合物（１ ２）（０．
３ １ ９ ｇ、１ ． ８ ４ｍｍｏｆ）を得た．（
収率９４％）２．３．４−トリメトキシ一〇一ニトロス
チレン（１３）（０．４００ｇ、１ ． ６ ７ ｍｍ
ｏｆ１． ５％Ｐｄ−Ｃ Ｋタイプ（日本エンゲノレ
ハノレト製）（０．３５６ｇ，Ｐｄ ： ０．１ ７ｍ
ｍｏｆ）を濃塩酸（０．４ｄ）及びエタノール（８−）
中、水素雰囲気下、氷水冷却下で３時間撹拌した．Ｐｄ
−Ｃを炉別後、２ＩＩｗＡ・し、水（４ ０ｍｌ）を加
え、塩化メチレン（２０ｄＸ３）で水層を洗浄した．水
層に、アンモニア水をアルカリ性になるまで加え、塩化
メチレン（２０１ｄＸ４）で抽出し、ＮａｘＳＯ＜で乾
燥した後、濃縮して黄色の油状物である化合物（１４１
（０．２２８ｇ、１ ． ０ ８ ＋ｏｎ＋ｏ７）を得
た．（収率６５％）
上記の反応の出発物質、生成物、及び収率を下表に示す
．
（ｌ３）
（ｌ４）The phenethylamines obtained in this reaction (1,3,4-methylenedioxy-β-phenethylamine including hydrochloride, 3,4-dimethoxy-β-phenethylamine, 3-methoxy-4-hydroxy-β-phenethylamine, -Hydroxy-4-methoxy-β-phenethylamine, 3,4-dihydroxy-β-phenethylamine,
4-Hydroxy-β-phenethylamine, 2.3.4-
Examples include trimethoxy β-phenethylamine. The phenethylamines thus obtained are Bis
Chler-Napieralski reaction or Pi
By ctest-Spengler reaction, the corresponding l
, 2.3.4-tetrahydroisoquinoline, and the usefulness of this reaction is recognized. Also, the formula (I
In I), R and Rs are OH, and R. The compound in which R4 and Ri are hydrogen atoms is a useful physiologically active compound known as dopamine. (Effects of the Invention) As explained above, according to the method of the present invention, phenethylamines, which are useful compounds, can be produced in a gentle manner without requiring special equipment or a great deal of effort to take out the product after the reaction. It can be manufactured under suitable conditions. (Example) Next, the present invention will be explained in more detail with reference to Examples. 3.4-methylenedioxy-β-nitrostyrene (11
(0.500g, 2.59mmoi'l, 5%Pd-C
K type (manufactured by Engelhard Japan) (0.553g
, Pd: 0.26 mmof) in concentrated hydrochloric acid (0.5 m
t') and ethanol (10d) under a hydrogen atmosphere and cooling with ice water for 3 hours. After the Pd-C was separated from the furnace, it was concentrated, water (40y7) was added, and methylene chloride (20MIX3
) to wash the aqueous layer. Ammonia water was added to the aqueous layer until it became alkaline, extracted with methylene chloride (20y + f
3n+mo7) was obtained. (Yield 7l%) 3.4-Dimethoxy β-nitrostyrene (3) (0.
500g. 2. 39111010ノ), 5
%Pd-CK type (No.50 made by Engelhard Japan)
9g, Pd: 0. 24 mmof) in concentrated hydrochloric acid (
0.5d) and ethanol (10 ml) under a hydrogen atmosphere at room temperature for 24 hours. 11
water (20 ml') was added, and methylene chloride (20 ml') was added.
The aqueous layer was washed with dX3). Add ammonia water to the aqueous layer until it becomes alkaline, add methylene chloride (20dX3)
Extracted with Na-rich SO. Compound (4) (0.316 g, 1.7
4 mmof) was obtained. (yield 73%)
0.500g, 2.56mmo11.5%Pd-G
K type (manufactured by Engelhard Japan) (0.545g.P
d: 0.26mmoi') in concentrated hydrochloric acid (0.51R
1) and ethanol (10 mj) under a hydrogen atmosphere and under cooling with ice water for 3 hours. After separating the Pd-C, it was concentrated, water (40d) was added, the aqueous layer was washed with methylene chloride (30dX3), and concentrated to give light gray crystal compound (6) (0
．． 442g, 2. 18 mmof) was obtained. (yield 8
1%) 3-hydroxy-4-methoxy β-nitrostyrene (7NO.500g, 2.56mmon), 5%P
d-G K type (manufactured by Engelhard Japan) (0.5
45g. Pd: 0.26 mmof) was dissolved in concentrated hydrochloric acid (0.26 mmof).
5-) and ethanol (10d) under a hydrogen atmosphere under cooling with ice water for 3 hours. After the Pd-C was separated from the furnace, it was concentrated, water (40d) was added, and methylene chloride (30-X3
) and concentrated to give pale yellow crystal compound (80
0.473g, 2. 3 3 mn+of) was obtained.
(Yield 9l%) 3.4-dibenzyloxy-β-nitrostyrene (9NO.500g.1.38mmof1.5
%Pd-C K type (manufactured by Engelhard Japan) (0
．． 545g. Pd: 0.14 mmof') in concentrated hydrochloric acid (0.31 nI) and ethanol (loWll).
The mixture was stirred at room temperature for 24 hours under a hydrogen atmosphere. Pd-C
After going door to door, it was concentrated and white crystal compound (IO) (0.2
60g. 1.37 mmo7) was obtained. (Yield 99%) Amount 12 Tyramine 4-penzyloxy 101 ditrostyrene (1 11
(0.500g, 1.96 mmo7)
．． 5% Pd-C K type (manufactured by Engelhard Japan) (0.417g. Pd: 0.20mm
of) in concentrated hydrochloric acid (0.4 tl') and ethanol (l
The mixture was stirred for 3 hours under ice water cooling in a hydrogen atmosphere. After the Pd-C is separated from the furnace, it is concentrated and water (401IJ!
) was added, the aqueous layer was washed with methylene chloride (30 Wd!
3 19 g, 1. 84mmof) was obtained. (
Yield 94%) 2.3.4-trimethoxy-101 nitrostyrene (13) (0.400 g, 1.67 mm
of1. 5% Pd-C K type (manufactured by Nihon Engenorehanoreto) (0.356g, Pd: 0.1 7m
mof) in concentrated hydrochloric acid (0.4d) and ethanol (8-)
The mixture was stirred for 3 hours under ice water cooling under a hydrogen atmosphere. Pd
After the -C was separated from the furnace, it was heated to 2IIwA, water (40ml) was added, and the aqueous layer was washed with methylene chloride (20dX3). Aqueous ammonia was added to the aqueous layer until it became alkaline, extracted with methylene chloride (201dX4), dried over NaxSO, and concentrated to yield a yellow oily compound (141
(0.228g, 1.08+on+o7) was obtained. (Yield: 65%) The starting materials, products, and yields of the above reaction are shown in the table below. (l3) (l4)
Claims (1)
炭素を触媒として、一般式（ I ）：▲数式、化学式、
表等があります▼（ I ） ［式中、Ｒ＿１〜Ｒ＿５は、水素又はＯＲで示される基
であるか（ここで、Ｒは水素、低級アルキル基、アラル
キル基を示し、Ｒ＿１〜Ｒ＿５の少なくとも一はＯＲで
ある）、あるいはＲ＿１〜Ｒ＿５の隣接する二つの基が
一緒になってアルキレンジオキシ基を形成していてもよ
い］ で示される（Ｚ）及び／又は（Ｅ）−β−ニトロスチレ
ン誘導体を、水素で接触還元することを特徴とする、一
般式（II）： ▲数式、化学式、表等があります▼（II） （式中、Ｒ＿１〜Ｒ＿５は上記記載の意味を有する）で
示されるフェネチルアミン類又はその塩を製造する方法
。(1) Palladium-
Using carbon as a catalyst, general formula (I): ▲mathematical formula, chemical formula,
There are tables, etc. ▼ (I) [In the formula, R_1 to R_5 are hydrogen or a group represented by OR (here, R represents hydrogen, a lower alkyl group, or an aralkyl group, and at least one of R_1 to R_5 is is OR), or two adjacent groups of R_1 to R_5 may form an alkylene dioxy group together] (Z) and/or (E)-β-nitrostyrene represented by General formula (II) characterized by catalytic reduction of a derivative with hydrogen: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (In the formula, R_1 to R_5 have the meanings described above) A method for producing phenethylamines or salts thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16095089A JPH082844B2 (en) | 1989-06-26 | 1989-06-26 | Method for producing phenethylamines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16095089A JPH082844B2 (en) | 1989-06-26 | 1989-06-26 | Method for producing phenethylamines |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0327345A true JPH0327345A (en) | 1991-02-05 |
| JPH082844B2 JPH082844B2 (en) | 1996-01-17 |
Family
ID=15725708
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16095089A Expired - Fee Related JPH082844B2 (en) | 1989-06-26 | 1989-06-26 | Method for producing phenethylamines |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH082844B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106053657A (en) * | 2016-07-01 | 2016-10-26 | 东北制药集团股份有限公司 | Method for detecting content of chiral phenylethylamine by adopting high-performance liquid chromatography |
| CN111892507A (en) * | 2020-08-24 | 2020-11-06 | 山东达冠医药科技有限公司 | Synthesis method of high-purity dopamine hydrochloride |
| CN114716331A (en) * | 2022-03-03 | 2022-07-08 | 福安药业集团宁波天衡制药有限公司 | Preparation method of dopamine hydrochloride |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755576A (en) * | 2014-01-23 | 2014-04-30 | 上海旭新化工科技有限公司 | Synthesis method of N-methyl tyramine hydrochloride |
-
1989
- 1989-06-26 JP JP16095089A patent/JPH082844B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106053657A (en) * | 2016-07-01 | 2016-10-26 | 东北制药集团股份有限公司 | Method for detecting content of chiral phenylethylamine by adopting high-performance liquid chromatography |
| CN111892507A (en) * | 2020-08-24 | 2020-11-06 | 山东达冠医药科技有限公司 | Synthesis method of high-purity dopamine hydrochloride |
| CN114716331A (en) * | 2022-03-03 | 2022-07-08 | 福安药业集团宁波天衡制药有限公司 | Preparation method of dopamine hydrochloride |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH082844B2 (en) | 1996-01-17 |
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