JPS6115048B2 - - Google Patents
Info
- Publication number
- JPS6115048B2 JPS6115048B2 JP4049177A JP4049177A JPS6115048B2 JP S6115048 B2 JPS6115048 B2 JP S6115048B2 JP 4049177 A JP4049177 A JP 4049177A JP 4049177 A JP4049177 A JP 4049177A JP S6115048 B2 JPS6115048 B2 JP S6115048B2
- Authority
- JP
- Japan
- Prior art keywords
- nitro
- nitroso
- acid
- compounds
- formic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 36
- -1 hydroxylamino compound Chemical class 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 235000019253 formic acid Nutrition 0.000 claims description 18
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 18
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 13
- 150000002832 nitroso derivatives Chemical class 0.000 claims description 12
- 239000000852 hydrogen donor Substances 0.000 claims description 11
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 238000009901 transfer hydrogenation reaction Methods 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical group O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 7
- 125000000018 nitroso group Chemical group N(=O)* 0.000 claims description 6
- 150000005690 diesters Chemical class 0.000 claims description 5
- 239000000386 donor Substances 0.000 claims description 5
- 229910000510 noble metal Inorganic materials 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000003282 alkyl amino group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000010970 precious metal Substances 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 125000001475 halogen functional group Chemical group 0.000 claims 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
- 239000003610 charcoal Substances 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- RPNNPZHFJPXFQS-UHFFFAOYSA-N methane;rhodium Chemical compound C.[Rh] RPNNPZHFJPXFQS-UHFFFAOYSA-N 0.000 description 2
- 150000002828 nitro derivatives Chemical class 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- CMVQZRLQEOAYSW-UHFFFAOYSA-N 1,2-dichloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1Cl CMVQZRLQEOAYSW-UHFFFAOYSA-N 0.000 description 1
- AEBJDOTVYMITIA-UHFFFAOYSA-N 1,3,5-trichloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=C(Cl)C=C(Cl)C=C1Cl AEBJDOTVYMITIA-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- UPTOWXNJLZJTGD-UHFFFAOYSA-N 1,4-dimethoxy-2-nitrobenzene Chemical compound COC1=CC=C(OC)C([N+]([O-])=O)=C1 UPTOWXNJLZJTGD-UHFFFAOYSA-N 0.000 description 1
- NATVSFWWYVJTAZ-UHFFFAOYSA-N 2,4,6-trichloroaniline Chemical compound NC1=C(Cl)C=C(Cl)C=C1Cl NATVSFWWYVJTAZ-UHFFFAOYSA-N 0.000 description 1
- NUBDEJZUYICQKU-UHFFFAOYSA-N 2,5-dimethoxyaniline;hydron;chloride Chemical compound Cl.COC1=CC=C(OC)C(N)=C1 NUBDEJZUYICQKU-UHFFFAOYSA-N 0.000 description 1
- XTRDKALNCIHHNI-UHFFFAOYSA-N 2,6-dinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=CC=C1[N+]([O-])=O XTRDKALNCIHHNI-UHFFFAOYSA-N 0.000 description 1
- SDYWXFYBZPNOFX-UHFFFAOYSA-N 3,4-dichloroaniline Chemical compound NC1=CC=C(Cl)C(Cl)=C1 SDYWXFYBZPNOFX-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000007860 aryl ester derivatives Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000002051 biphasic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- VSPZSXLLFMWWLY-UHFFFAOYSA-N n-(3-nitrophenyl)hydroxylamine Chemical compound ONC1=CC=CC([N+]([O-])=O)=C1 VSPZSXLLFMWWLY-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/73—Unsubstituted amino or imino radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
- C07C273/1854—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas by reactions not involving the formation of the N-C(O)-N- moiety
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/88—Nitrogen atoms, e.g. allantoin
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
- C07D235/10—Radicals substituted by halogen atoms or nitro radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
- C07D285/14—Thiadiazoles; Hydrogenated thiadiazoles condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
- C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pyridine Compounds (AREA)
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
Description
本発明は、有機ニトロまたはニトロソ化合物の
水素添加によるヒドロキシルアミノおよび／また
はアミノ化合物の製法に関する。本発明は特に、
有機ニトロまたはニトロソ化合物の水素添加によ
るアミノ化合物の製法に関する。
ニトロまたはニトロソ基含有の有機化合物が、
遷移金属触媒例えばパラジウムの如き周期表第
族貴金属の存在下で分子水素により第一アミンに
還元され得ることは知られている。この方法の使
用に伴なう問題は、或種の化合物について水素添
加条件下で望ましくない副反応が起こり得ること
である。かように、環ハロ−置換基を有する芳香
族ニトロ化合物は、NO2基からNH2基への水素添
加を受け得るのみならずハロ−置換基除去をも受
け得る。また対応するヒドロキシルアミノ化合物
を選択的に得ることが非常に困難でもある。
有機化合物を水素添加するための代替的方法
は、接触移動添加（catalytic transfer
hydrogenation）による方法である〔この点の調
査についてはケミカル・レビユーズ（Chemical
Reviews）1974、第74巻、第567〜580頁参照〕。
この方法は、水素添加のための水素原子が、通常
水素供与体として言及される水素含有化合物から
誘導される点で、通常の接触水素添加と異なる。
今や、ハロゲン置換基が反応中に脱ハロゲン化
水素されないので、水素添加されるべき化合物中
にハロゲン置換基を存在させておく非常に穏やか
な条件下で、ニトロまたはニトロソ化合物を対応
するアミノまたはヒドロキシルアミノ化合物に変
換し得ることが判明した。
本発明は、水素供与体および周期表第族の貴
金属の存在下で芳香族のニトロまたはニトロソ基
含有有機化合物のニトロまたはニトロソ基を接触
移動水素添加して対応するアミノまたはヒドロキ
シルアミノ化合物を製造する方法において、水素
供与体が次亜燐酸、亜燐酸、それらの塩もしくは
モノ−またはジ−エステル、、ヒドラジンあるい
は蟻酸から選ばれ、但し蟻酸が用いられる場合は
多くて２％ｗの水の存在下で実施することを条件
とする、ことを特徴とする方法に関する。
ニトロまたはニトロソ化合物は斯くの如き環元
し得る基を３つまで含むことが適切である。これ
らの基は、任意に置換されてよいアルキル、アル
ケニル、シクロアルキルまたはアリール基に、ま
たは窒素、硫黄および／または酸素ヘテロ原子を
含む複素環式基に結合され得る。全般的に、ニト
ロまたはニトロソ化合物中には通常の置換基のい
ずれも存在し得る。斯くの如き置換基の例として
はハロ、ヒドロキシ、アルコキシ、アルキル、ア
ルケニル、フエニル、カルボキシ、アミノ、
（ジ）アルキルアミノ、シアノまたはアシル基が
挙げられる。
特定の反応条件に依存して、ヒドロキシルアミ
ノ化合物またはアミノ化合物が優先的に形成され
得ることが判明した。このことは、さらに行なわ
れる合成における中間体として好都合に使用され
得る異なる生成物を同一出発材料から製造し得る
という点で非常に有利である。全般に、接触移動
水素添加条件がゆるければゆるい程ヒドロキシル
アミノ化合物の収量が高いと言うことができる。
或反応条件下で非常に高収量のヒドロキシルア
ミノ化合物が得られ、一方実質的にアミノ化合物
が全く形成されなかつた。
（接触移動水素添加反応を用いて得られたか否
かに拘らず）ヒドロキシルアミノ化合物は、本発
明の接触移動水素添加法の使用によつて対応する
アミノ化合物に変換され得ることに注意すべきで
ある。しかしある場合においては、供与体として
蟻酸を用いた時に、ブロモ、ヨードまたはシアノ
基含有化合物が完全に水素添加されないことがあ
る。
適用されるべき貴金属触媒は、ルテニウム、ロ
ジウム、パラジウムまたは白金のうちの１種また
はそれ以上の金属であることが適切である。金属
は微細形態であることが適切であり、そして木炭
の如き適切な担体上に担持され得る。貴金属の使
用量は、蟻酸、次亜燐酸、亜燐酸、それらの塩も
しくはモノ−またはジ−エステルを用いたニトロ
またはニトロソ化合物の接触移動水素添加に適用
する場合には基体に基づいて計算して25％まで、
好ましくは10％までであることが適切であり、ヒ
ドラジンを用いたニトロまたはニトロソ化合物の
接触移動水素添加に適用する場合には基体に基づ
いて計算して10％まで、好ましくは５％までであ
ることが適切である。
蟻酸が水素供与体として使用され得る。蟻酸を
用いると非常に良好な結果が得られた。
水素供与体として次亜燐酸、亜燐酸、それらの
塩もしくはモノ−またはジ−エステルも用いられ
得る。塩は、次亜燐酸ナトリウムまたは亜燐酸ナ
トリウムの如きアルカリまたはアルカリ土類金属
塩または式NR4 +（式中各Ｒはアルキルまたはア
リール基を示す）で表わされるカチオンの塩であ
ることが適切である。エステルは例えばアルキル
またはアリールエステルであり得る。少量のパラ
ジウム／木炭の存在下に水性次亜燐酸ナトリウム
を用いると、しばしば85％よりも高い高収率にて
ヒドロキシルアミノ化合物が得られる。これらの
ゆるい水素添加条件下でｍ−ジニトロベンゼン中
の２つのニトロ基のうちの１つだけがヒドロキシ
ルアミノ基に変換される。
水素供与体としてヒドラジンを用いる時には、
特に比較的少量の触媒を用いた場合に、ヒドロキ
シルアミノ化合物が形成される。これらの条件下
ではまた極めてゆるやかな接触移動水素添加が起
こることが判明し、ｍ−ジニトロベンゼンから出
発するとニトロ基のうちの１つだけが55％の収率
でヒドロキシルアミノ化合物に変換された。
全般に、供与体の使用量は広範囲に変化し得
る。かように、蟻酸は水素供与体および反応用希
釈剤の両方として使用でき、その様な情況におい
ては蟻酸は通常大過剰量で存在する。他方ある場
合には理論量またはわずかに過剰量の供与体を用
いることが望ましいことがある。その様な場合に
は反応混合物はまた付加的な液体希釈剤を含み得
る。蟻酸を用いる場合には希釈剤は例えば水、メ
タノールまたはエタノールの如きアルコール、ま
たはテトラヒドロフランまたはジオキサンの如き
エーテルであり得る。アミノ化合物を得るために
水溶性燐化合物を用いる時の適切な希釈剤は、水
と、前記のもののうちの１種またはジメチルホル
ムアミドの如きジアルキルアミドの様な水混和性
有機溶剤との混合物である。また或水／テトラヒ
ドロフラン混合物の如き２相溶剤系も適切に適用
されることができ、これらの情況下にヒドロキシ
ルアミノ化合物が主に形成される。
水素添加反応は、金属触媒および任意に用いら
れてよい希釈剤の存在下にニトロまたはニトロソ
化合物と水素供与体とを一緒に混合することによ
つて実施されることが最も都合よい。反応混合物
から空気または酸素を排除するために特別な予防
措置をとる必要はない。多くの場合に反応は発熱
反応であるが、反応を完結させるために混合物を
例えば50゜〜100℃に温めることが必要であるこ
とがある。触媒は例えば過または遠心分離によ
つて反応混合物から分離され、生成物は慣用技法
によつて回収される。触媒は再生処理にかけずに
再使用され得る。
本発明の方法に従つて得られる化合物は、化学
合成例えば殺虫剤製造における中間体として適切
に使用され得る。
広範囲のニトロまたはニトロソ化合物を対応す
るヒドロキシルアミノまたはアミノ化合物に満足
に水素添加し得ることを特に示す次の例において
本発明の方法を説明する。化合物はその融点およ
び元素分析によつて特性表示された。
例 １
２・５−ジメトキシニトロベンゼン（0.3ｇ）
を蟻酸（98％、５ml）に溶解し、木炭（0.0795
ｇ）に担持された10％パラジウムをこの溶液に添
加した。泡だちが（15分で）止むまで、混合物を
撹拌し水浴上で温めた。次に濃塩酸（３ml）を添
加し触媒を別した。触媒を水洗しそして組合せ
られた液／洗液を蒸発させて、95％の収率で
２・５−ジメトキシアニリン塩酸塩を得た。
例 ２
蟻酸（20ml）に溶かした２・６−ジニトロトル
エン（2.0ｇ）の溶液を、木炭（0.2ｇ）に担持さ
れた10％パラジウムを蟻酸中に激しく撹拌して懸
濁させた液に添加した。泡だちが止んだ後に触媒
を別し蟻酸で洗浄した。次に蟻酸溶液を水（25
ml）で希釈しエーテル抽出した。抽出物を乾燥
し、エーテルを減圧下に除去した。残渣は２・６
−ジアミノトルエンからなつた（収率80％）。
例 ３〜22
例１および例２に記載の手順と同様にしてさら
にニトロおよびニトロソ化合物を水素添加した。
実験結果を表にまとめた（例９は本発明外にあ
るので参考例である。）。各々の場合の収率は75％
〜90％であつた。
The present invention relates to a process for the preparation of hydroxylamino and/or amino compounds by hydrogenation of organic nitro or nitroso compounds. In particular, the present invention
This invention relates to a method for producing amino compounds by hydrogenation of organic nitro or nitroso compounds. Organic compounds containing nitro or nitroso groups are
It is known that primary amines can be reduced by molecular hydrogen in the presence of transition metal catalysts, such as noble metals from Groups of the Periodic Table, such as palladium. A problem with the use of this method is that undesirable side reactions can occur for certain compounds under hydrogenation conditions. Thus, aromatic nitro compounds with ring halo-substituents can undergo not only hydrogenation from NO2 groups to NH2 groups, but also halo-substituent removal. It is also very difficult to selectively obtain the corresponding hydroxylamino compound. An alternative method for hydrogenating organic compounds is catalytic transfer addition.
hydrogenation) [For investigation of this point, see Chemical Reviews.
(Reviews) 1974, Vol. 74, pp. 567-580].
This method differs from conventional catalytic hydrogenation in that the hydrogen atoms for hydrogenation are derived from hydrogen-containing compounds, commonly referred to as hydrogen donors. Now, the nitro or nitroso compound can be converted to the corresponding amino or hydroxyl under very mild conditions, keeping the halogen substituent present in the compound to be hydrogenated, since the halogen substituent is not dehydrohalogenated during the reaction. It was found that it could be converted into an amino compound. The present invention involves the catalytic transfer hydrogenation of the nitro or nitroso group of an aromatic nitro or nitroso group-containing organic compound in the presence of a hydrogen donor and a noble metal from group 3 of the periodic table to produce the corresponding amino or hydroxylamino compound. In the process, the hydrogen donor is selected from hypophosphorous acid, phosphorous acid, salts or mono- or di-esters thereof, hydrazine or formic acid, provided that when formic acid is used, in the presence of at most 2% w of water. A method characterized in that it is carried out in. Suitably, the nitro or nitroso compound contains up to three such cyclic groups. These groups may be attached to optionally substituted alkyl, alkenyl, cycloalkyl or aryl groups or to heterocyclic groups containing nitrogen, sulfur and/or oxygen heteroatoms. In general, any of the conventional substituents may be present in a nitro or nitroso compound. Examples of such substituents include halo, hydroxy, alkoxy, alkyl, alkenyl, phenyl, carboxy, amino,
Mention may be made of (di)alkylamino, cyano or acyl groups. It has been found that depending on the specific reaction conditions, hydroxylamino or amino compounds may be preferentially formed. This is very advantageous in that different products can be prepared from the same starting material, which can advantageously be used as intermediates in further syntheses. In general, it can be said that the looser the catalytic transfer hydrogenation conditions, the higher the yield of the hydroxylamino compound. Under certain reaction conditions very high yields of hydroxylamino compounds were obtained, while virtually no amino compounds were formed. It should be noted that hydroxylamino compounds (whether obtained using a catalytic transfer hydrogenation reaction or not) can be converted to the corresponding amino compounds by use of the catalytic transfer hydrogenation method of the present invention. be. However, in some cases, bromo-, iodo- or cyano-containing compounds may not be completely hydrogenated when using formic acid as the donor. The noble metal catalyst to be applied is suitably one or more of the following metals: ruthenium, rhodium, palladium or platinum. The metal is suitably in finely divided form and may be supported on a suitable carrier such as charcoal. The amount of precious metal used is calculated on the basis of the substrate when applied to the catalytic transfer hydrogenation of nitro or nitroso compounds with formic acid, hypophosphorous acid, phosphorous acid, their salts or mono- or di-esters. up to 25%,
Preferably up to 10% is suitable, and when applied to catalytic transfer hydrogenation of nitro or nitroso compounds with hydrazine up to 10%, preferably up to 5%, calculated on the substrate. That is appropriate. Formic acid can be used as hydrogen donor. Very good results were obtained using formic acid. Hypophosphorous acid, phosphorous acid, salts or mono- or di-esters thereof can also be used as hydrogen donors. Suitably the salt is an alkali or alkaline earth metal salt such as sodium hypophosphite or sodium phosphite or a salt of a cation of the formula NR 4 + in which each R represents an alkyl or aryl group. be. Esters can be, for example, alkyl or aryl esters. Using aqueous sodium hypophosphite in the presence of small amounts of palladium/charcoal, hydroxylamino compounds are obtained in high yields, often higher than 85%. Under these mild hydrogenation conditions only one of the two nitro groups in m-dinitrobenzene is converted to a hydroxylamino group. When using hydrazine as a hydrogen donor,
Hydroxylamino compounds are formed, especially when relatively small amounts of catalyst are used. Under these conditions it was also found that a very slow catalytic transfer hydrogenation occurred, starting from m-dinitrobenzene, only one of the nitro groups was converted to the hydroxylamino compound with a yield of 55%. In general, the amount of donor used can vary over a wide range. Thus, formic acid can be used both as a hydrogen donor and as a diluent for the reaction, and in such situations, formic acid is usually present in large excess. On the other hand, in some cases it may be desirable to use a stoichiometric amount or a slight excess of donor. In such cases the reaction mixture may also contain additional liquid diluent. When using formic acid, the diluent can be, for example, water, an alcohol such as methanol or ethanol, or an ether such as tetrahydrofuran or dioxane. Suitable diluents when using water-soluble phosphorus compounds to obtain amino compounds are mixtures of water and water-miscible organic solvents such as one of those mentioned above or a dialkylamide such as dimethylformamide. . Also, biphasic solvent systems such as certain water/tetrahydrofuran mixtures can be suitably applied, and under these circumstances hydroxylamino compounds are predominantly formed. The hydrogenation reaction is most conveniently carried out by mixing together the nitro or nitroso compound and the hydrogen donor in the presence of a metal catalyst and an optional diluent. No special precautions need to be taken to exclude air or oxygen from the reaction mixture. Although in many cases the reaction is exothermic, it may be necessary to warm the mixture to, for example, 50° to 100°C to complete the reaction. The catalyst is separated from the reaction mixture, for example by filtration or centrifugation, and the product is recovered by conventional techniques. The catalyst can be reused without being subjected to regeneration treatment. The compounds obtained according to the method of the invention can suitably be used as intermediates in chemical synthesis, for example in the production of pesticides. The process of the invention is illustrated in the following examples which specifically demonstrate that a wide range of nitro or nitroso compounds can be satisfactorily hydrogenated to the corresponding hydroxylamino or amino compounds. The compound was characterized by its melting point and elemental analysis. Example 1 2,5-dimethoxynitrobenzene (0.3g)
was dissolved in formic acid (98%, 5 ml) and charcoal (0.0795
10% palladium supported on g) was added to this solution. The mixture was stirred and warmed on a water bath until the bubbling stopped (in 15 minutes). Concentrated hydrochloric acid (3 ml) was then added to separate the catalyst. The catalyst was washed with water and the combined liquor/washes were evaporated to give 2,5-dimethoxyaniline hydrochloride in 95% yield. Example 2 A solution of 2,6-dinitrotoluene (2.0 g) in formic acid (20 ml) is added to a vigorously stirred suspension of 10% palladium on charcoal (0.2 g) in formic acid. did. After the bubbling ceased, the catalyst was separated and washed with formic acid. Next, add the formic acid solution to water (25
ml) and extracted with ether. The extracts were dried and the ether removed under reduced pressure. The residue is 2.6
- diaminotoluene (yield 80%). Examples 3-22 Nitro and nitroso compounds were further hydrogenated analogously to the procedures described in Examples 1 and 2.
The experimental results are summarized in a table (Example 9 is a reference example because it is outside the scope of the present invention). Yield in each case is 75%
It was ~90%.
【表】【table】
【表】
水素供与体−蟻酸
例 23
温メタノール（15ml）中のニトロベンゼン（１
ml）を次亜燐酸（30％水溶液６ml）に添加した。
混合物を撹拌してこれに、木炭（0.1ｇ）に担持
された10％パラジウムを添加した。泡立ちが止ん
だ後に、混合物を還流下に約20分加熱し次に過
した。液を水酸化ナトリウム水溶液で中和しク
ロロホルムで抽出した。減圧下に乾燥抽出物から
溶剤を除去して収率70％にてアニリンを得た。
例 24
水性テトラヒドロフラン（20ml）中の３・４−
ジクロロニトロベンゼン（2.0ｇ）を、木炭（0.2
ｇ）に担持された10％パラジウムと共に撹拌し、
この懸濁液に、次亜燐酸ナトリウムの30％水溶液
を徐々に添加した。各少量添加の後に混合物を泡
立ちさせてからさらに添加した。ニトロ化合物の
存在が薄層クロマトグラフイによつてもはや検出
されなくなるまで添加を続けた。次に混合物を
過し、液を水（25ml）に注入した。水性混合物
をジクロロメタンで抽出した。次に減圧下に乾燥
抽出物から溶剤を除去して、90％収率にて３・４
−ジクロロアニリンを得た。
例 25
２・４・６−トリクロロニトロベンゼン（0.6
ｇ）を温エタノール（10ml）に溶かし、この溶液
に濃厚水性亜燐酸（16ｇ）および木炭（0.1ｇ）
担持10％パラジウムを添加した。溶液を70℃にて
10分間撹拌し次に過した。液を水（100ml）
で希釈し、水酸化ナトリウムの添加によつて強塩
基性にした。アルカリ性溶液をクロロホルム（３
×20ml）で抽出し、抽出物を乾燥（MgSO4）し蒸
発させた。残渣を水性エタノールから再結晶させ
て所要２・４・６−トリクロロアニリンを得た。
例 26
例24と同様の手順に従つて、触媒として木炭担
持５％ロジウムを用いてｍ−ジニトロベンゼンを
次亜燐酸で還元した。ｍ−ジアミノベンゼンの収
率は75％であつた。
例 27〜38
例23〜26と同様の手順を用いてなお一層のニト
ロ化合物を水素添加した。実験結果を表にまと
めた。各々の場合の収率は75〜90％であつた。
例 39
テトラヒドロフラン（20ml）にｍ−ジニトロベ
ンゼン（３ｇ）を溶かした溶液中に木炭担持５％
パラジウムを撹拌懸濁させた液に、次亜燐酸ナト
リウム（20ml中に３ｇ）の水溶液を添加した。温
度を約50℃に上昇させ撹拌を続けた。温度が室温
に下がつた時に触媒を別した。有機相を分離し
ジエチルエーテルをこの溶液に添加した。次にこ
の溶液を水洗し乾燥（MgSO4）した。蒸発によつ
てｍ−ニトロフエニルヒドロキシルアミン（2.3
ｇ、84％）を得た。
例 40〜56
例39に記された如き工程を用いてなお一層のヒ
ドロキシルアミノ化合物を得た。実験結果を表
にまとめた。[Table] Hydrogen donor - formic acid Example 23 Nitrobenzene (1
ml) was added to hypophosphorous acid (6 ml of 30% aqueous solution).
To the stirred mixture was added 10% palladium on charcoal (0.1 g). After the bubbling ceased, the mixture was heated under reflux for about 20 minutes and then filtered. The liquid was neutralized with an aqueous sodium hydroxide solution and extracted with chloroform. The solvent was removed from the dried extract under reduced pressure to obtain aniline in 70% yield. Example 24 3,4- in aqueous tetrahydrofuran (20 ml)
Dichloronitrobenzene (2.0g), charcoal (0.2g)
g) with 10% palladium supported on
A 30% aqueous solution of sodium hypophosphite was slowly added to this suspension. The mixture was allowed to foam after each small addition before further additions were made. Addition continued until the presence of nitro compounds could no longer be detected by thin layer chromatography. The mixture was then filtered and the liquid poured into water (25ml). The aqueous mixture was extracted with dichloromethane. The solvent was then removed from the dried extract under reduced pressure to yield 3.4
-Dichloroaniline was obtained. Example 25 2,4,6-trichloronitrobenzene (0.6
g) in warm ethanol (10 ml) and to this solution concentrated aqueous phosphorous acid (16 g) and charcoal (0.1 g).
10% palladium supported was added. Solution at 70℃
Stir for 10 minutes and then filter. Pour the liquid into water (100ml)
and made strongly basic by addition of sodium hydroxide. The alkaline solution was dissolved in chloroform (3
x 20 ml) and the extracts were dried (MgSO 4 ) and evaporated. The residue was recrystallized from aqueous ethanol to yield the required 2,4,6-trichloroaniline. Example 26 Following a similar procedure to Example 24, m-dinitrobenzene was reduced with hypophosphorous acid using 5% rhodium on charcoal as the catalyst. The yield of m-diaminobenzene was 75%. Examples 27-38 Further nitro compounds were hydrogenated using a procedure similar to Examples 23-26. The experimental results are summarized in a table. The yield in each case was 75-90%. Example 39 5% charcoal supported in a solution of m-dinitrobenzene (3 g) in tetrahydrofuran (20 ml)
An aqueous solution of sodium hypophosphite (3 g in 20 ml) was added to the stirred suspension of palladium. The temperature was raised to approximately 50°C and stirring continued. The catalyst was removed when the temperature fell to room temperature. The organic phase was separated and diethyl ether was added to the solution. This solution was then washed with water and dried (MgSO 4 ). By evaporation m-nitrophenylhydroxylamine (2.3
g, 84%). Examples 40-56 Using the process as described in Example 39, further hydroxylamino compounds were obtained. The experimental results are summarized in a table.
【表】【table】
【表】【table】
【表】【table】
【表】
れる合成に用いられた化合物
例 57〜61
例39に記載の如き技法を用いて表に示される
反応体を、木炭担持５％ロジウム触媒の存在下に
テトラヒドロフラン中の過剰量のヒドラジンと反
応させた。得られたヒドロキシルアミンを表に
示した。[Table] Compounds used in the synthesis of
Examples 57-61 Using techniques as described in Example 39, the reactants shown in the table were reacted with an excess of hydrazine in tetrahydrofuran in the presence of a 5% rhodium on charcoal catalyst. The obtained hydroxylamine is shown in the table.
Claims (1)
在下で芳香族のニトロまたはニトロソ基含有有機
化合物のニトロまたはニトロソ基を接触移動水素
添加して対応するアミノまたはヒドロキシルアミ
ノ化合物を製造する方法において、水素供与体が
次亜燐酸、亜燐酸、それらの塩もしくはモノ−ま
たはジ−エステル、ヒドラジンあるいは蟻酸から
選ばれ、但し蟻酸が用いられる場合は多くて２％
ｗの水の存在下で実施することを条件とする、こ
とを特徴とする方法。 ２ 還元されるべき芳香族のニトロまたはニトロ
ソ化合物がニトロまたはニトロソ基を３つまで含
む、特許請求の範囲第１項記載の方法。 ３ ニトロまたはニトロソ化合物がまた１つまた
はそれ以上のハロ、ヒドロキシ、アルコキシ、ア
ルキル、アルケニル、フエニル、カルボキシ、ア
ミノ、（ジ）アルキルアミノ、シアノまたはアシ
ル基を含む、特許請求の範囲第２項記載の方法。 ４ 適切な担体に、担持されたルテニウム、ロジ
ウム、パラジウムまたは白金を触媒として使用す
る、特許請求の範囲第１〜３項のいずれか一項に
記載の方法。 ５ 供与体として蟻酸、次亜燐酸、亜燐酸、それ
らの塩もしくはモノ−またはジ−エステルを用い
る場合、基体に基づいて25％まで好ましくは10％
までの貴金属を還元に用いる、特許請求の範囲第
４項記載の方法。 ６ 供与体としてヒトラジンを用いる場合に、基
体に基づいて10％まで好ましくは５％までの貴金
属を還元に用いる、特許請求の範囲第４項記載の
方法。[Scope of Claims] 1. Catalytic transfer hydrogenation of the nitro or nitroso group of an aromatic nitro or nitroso group-containing organic compound in the presence of a hydrogen donor and a noble metal of Group Group of the Periodic Table to produce a corresponding amino or hydroxylamino compound. In the process for producing phosphorous acid, the hydrogen donor is selected from hypophosphorous acid, phosphorous acid, salts or mono- or di-esters thereof, hydrazine or formic acid, provided that if formic acid is used, at most 2%
A method characterized in that it is carried out in the presence of water. 2. The method of claim 1, wherein the aromatic nitro or nitroso compound to be reduced contains up to three nitro or nitroso groups. 3. The nitro or nitroso compound also contains one or more halo, hydroxy, alkoxy, alkyl, alkenyl, phenyl, carboxy, amino, (di)alkylamino, cyano or acyl groups. the method of. 4. Process according to any one of claims 1 to 3, using ruthenium, rhodium, palladium or platinum supported on a suitable support as a catalyst. 5. If formic acid, hypophosphorous acid, phosphorous acid, salts or mono- or di-esters thereof are used as donor, up to 25%, preferably 10%, based on the substrate.
5. The method according to claim 4, wherein up to 100 precious metals are used for reduction. 6. Process according to claim 4, in which up to 10%, preferably up to 5%, of noble metals, based on the substrate, are used for the reduction when using hytrazine as donor.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1482576A GB1575808A (en) | 1976-04-12 | 1976-04-12 | Hydrogenation process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS52125101A JPS52125101A (en) | 1977-10-20 |
| JPS6115048B2 true JPS6115048B2 (en) | 1986-04-22 |
Family
ID=10048147
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4049177A Granted JPS52125101A (en) | 1976-04-12 | 1977-04-11 | Process for preparing hydroxylamino and or amino compound |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS52125101A (en) |
| CH (1) | CH635817A5 (en) |
| DE (1) | DE2715785A1 (en) |
| FR (1) | FR2348187A1 (en) |
| GB (1) | GB1575808A (en) |
| NL (1) | NL7703841A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3717881A1 (en) * | 1987-05-27 | 1988-12-08 | Basf Ag | CATALYTIC TRANSFER HYDRATION WITH AROMATIC NITRO COMPOUNDS AS A HYDROGEN ACCEPTOR |
| US5336808A (en) * | 1990-12-10 | 1994-08-09 | Occidental Chemical Corporation | Process for the preparation of 3,5-diaminobenzotrifluoride |
| FR2686877B1 (en) * | 1992-01-31 | 1995-03-24 | Hoechst France | PROCESS FOR THE PREPARATION OF ORTHOHYDROXYPHENYLACETIC ACID. |
| FR2686876B1 (en) * | 1992-02-04 | 1994-05-13 | Hoechst Ste Francaise | PROCESS FOR THE PREPARATION OF ARYLACETIC ACIDS AND THEIR SALTS OF ALKALINE METALS. |
| US5478548A (en) * | 1994-02-04 | 1995-12-26 | Rogers; Charles J. | Methods for the synthesis of chemical compounds |
| CN110841636B (en) * | 2019-12-02 | 2023-10-17 | 西安凯立新材料股份有限公司 | Catalyst for preparing 5-amino isophthalic acid and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2768209A (en) * | 1951-01-30 | 1956-10-23 | Ringwood Chemical Corp | Reduction of 2-nitro 1-phenyl propene-1 |
| US3239563A (en) * | 1962-12-13 | 1966-03-08 | Parke Davis & Co | Reduction of 1-phenyl-nitropropane-1, 3-diol |
-
1976
- 1976-04-12 GB GB1482576A patent/GB1575808A/en not_active Expired
-
1977
- 1977-04-07 CH CH445077A patent/CH635817A5/en not_active IP Right Cessation
- 1977-04-07 NL NL7703841A patent/NL7703841A/en not_active Application Discontinuation
- 1977-04-07 DE DE19772715785 patent/DE2715785A1/en active Granted
- 1977-04-11 JP JP4049177A patent/JPS52125101A/en active Granted
- 1977-04-12 FR FR7710896A patent/FR2348187A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DE2715785C2 (en) | 1987-03-05 |
| GB1575808A (en) | 1980-10-01 |
| JPS52125101A (en) | 1977-10-20 |
| DE2715785A1 (en) | 1977-10-20 |
| FR2348187A1 (en) | 1977-11-10 |
| CH635817A5 (en) | 1983-04-29 |
| FR2348187B1 (en) | 1980-12-05 |
| NL7703841A (en) | 1977-10-14 |
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