JP2018135293A - Method for producing amide compound - Google Patents
Method for producing amide compound Download PDFInfo
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- JP2018135293A JP2018135293A JP2017030251A JP2017030251A JP2018135293A JP 2018135293 A JP2018135293 A JP 2018135293A JP 2017030251 A JP2017030251 A JP 2017030251A JP 2017030251 A JP2017030251 A JP 2017030251A JP 2018135293 A JP2018135293 A JP 2018135293A
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- Prior art keywords
- acid
- trifluoromethanesulfonate
- compound
- iii
- amide compound
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- -1 amide compound Chemical class 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000003377 acid catalyst Substances 0.000 claims abstract description 13
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006237 Beckmann rearrangement reaction Methods 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- HZXJVDYQRYYYOR-UHFFFAOYSA-K scandium(iii) trifluoromethanesulfonate Chemical compound [Sc+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F HZXJVDYQRYYYOR-UHFFFAOYSA-K 0.000 claims abstract description 7
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims abstract description 6
- NYENCOMLZDQKNH-UHFFFAOYSA-K bis(trifluoromethylsulfonyloxy)bismuthanyl trifluoromethanesulfonate Chemical compound [Bi+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F NYENCOMLZDQKNH-UHFFFAOYSA-K 0.000 claims abstract description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 6
- 229940098779 methanesulfonic acid Drugs 0.000 claims abstract description 6
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims abstract description 6
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims abstract description 5
- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical compound [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 claims abstract description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 150000002923 oximes Chemical class 0.000 abstract description 6
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 abstract description 4
- PGJLOGNVZGRMGX-UHFFFAOYSA-L iron(2+);trifluoromethanesulfonate Chemical compound [Fe+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F PGJLOGNVZGRMGX-UHFFFAOYSA-L 0.000 abstract description 2
- 150000004682 monohydrates Chemical class 0.000 abstract description 2
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000008707 rearrangement Effects 0.000 description 6
- XSAYZAUNJMRRIR-UHFFFAOYSA-N 2-acetylnaphthalene Chemical compound C1=CC=CC2=CC(C(=O)C)=CC=C21 XSAYZAUNJMRRIR-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 4
- 239000003905 agrochemical Substances 0.000 description 4
- 239000002537 cosmetic Substances 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 239000002360 explosive Substances 0.000 description 4
- 239000003205 fragrance Substances 0.000 description 4
- DIEOESIZLAHURK-UHFFFAOYSA-N n-naphthalen-2-ylacetamide Chemical compound C1=CC=CC2=CC(NC(=O)C)=CC=C21 DIEOESIZLAHURK-UHFFFAOYSA-N 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 229920002994 synthetic fiber Polymers 0.000 description 4
- 239000012209 synthetic fiber Substances 0.000 description 4
- FANCTJAFZSYTIS-IQUVVAJASA-N (1r,3s,5z)-5-[(2e)-2-[(1r,3as,7ar)-7a-methyl-1-[(2r)-4-(phenylsulfonimidoyl)butan-2-yl]-2,3,3a,5,6,7-hexahydro-1h-inden-4-ylidene]ethylidene]-4-methylidenecyclohexane-1,3-diol Chemical compound C([C@@H](C)[C@@H]1[C@]2(CCCC(/[C@@H]2CC1)=C\C=C\1C([C@@H](O)C[C@H](O)C/1)=C)C)CS(=N)(=O)C1=CC=CC=C1 FANCTJAFZSYTIS-IQUVVAJASA-N 0.000 description 3
- WYJOVVXUZNRJQY-UHFFFAOYSA-N 2-Acetylthiophene Chemical compound CC(=O)C1=CC=CS1 WYJOVVXUZNRJQY-UHFFFAOYSA-N 0.000 description 3
- LSKONYYRONEBKA-UHFFFAOYSA-N 2-Dodecanone Chemical compound CCCCCCCCCCC(C)=O LSKONYYRONEBKA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- YLEIFZAVNWDOBM-ZTNXSLBXSA-N ac1l9hc7 Chemical compound C([C@H]12)C[C@@H](C([C@@H](O)CC3)(C)C)[C@@]43C[C@@]14CC[C@@]1(C)[C@@]2(C)C[C@@H]2O[C@]3(O)[C@H](O)C(C)(C)O[C@@H]3[C@@H](C)[C@H]12 YLEIFZAVNWDOBM-ZTNXSLBXSA-N 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- YRNDGUSDBCARGC-UHFFFAOYSA-N 2-methoxyacetophenone Chemical compound COCC(=O)C1=CC=CC=C1 YRNDGUSDBCARGC-UHFFFAOYSA-N 0.000 description 2
- GNKZMNRKLCTJAY-UHFFFAOYSA-N 4'-Methylacetophenone Chemical compound CC(=O)C1=CC=C(C)C=C1 GNKZMNRKLCTJAY-UHFFFAOYSA-N 0.000 description 2
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- SXVPOSFURRDKBO-UHFFFAOYSA-N Cyclododecanone Chemical compound O=C1CCCCCCCCCCC1 SXVPOSFURRDKBO-UHFFFAOYSA-N 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229960001171 acetohydroxamic acid Drugs 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 150000002443 hydroxylamines Chemical class 0.000 description 2
- CCBCHURBDSNSTJ-UHFFFAOYSA-N n-hydroxybutanamide Chemical compound CCCC(=O)NO CCBCHURBDSNSTJ-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- AYTCGEDNSBGRFI-UHFFFAOYSA-N (butanoylamino) benzenesulfonate Chemical compound CCCC(=O)NOS(=O)(=O)C1=CC=CC=C1 AYTCGEDNSBGRFI-UHFFFAOYSA-N 0.000 description 1
- 0 *C(*)=NOS(c1ccc(*)cc1)(=O)=O Chemical compound *C(*)=NOS(c1ccc(*)cc1)(=O)=O 0.000 description 1
- BUZYGTVTZYSBCU-UHFFFAOYSA-N 1-(4-chlorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Cl)C=C1 BUZYGTVTZYSBCU-UHFFFAOYSA-N 0.000 description 1
- HHAISVSEJFEWBZ-UHFFFAOYSA-N 1-[4-(trifluoromethyl)phenyl]ethanone Chemical compound CC(=O)C1=CC=C(C(F)(F)F)C=C1 HHAISVSEJFEWBZ-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- YXWWHNCQZBVZPV-UHFFFAOYSA-N 2'-methylacetophenone Chemical compound CC(=O)C1=CC=CC=C1C YXWWHNCQZBVZPV-UHFFFAOYSA-N 0.000 description 1
- BSMGLVDZZMBWQB-UHFFFAOYSA-N 2-methyl-1-phenylpropan-1-one Chemical compound CC(C)C(=O)C1=CC=CC=C1 BSMGLVDZZMBWQB-UHFFFAOYSA-N 0.000 description 1
- LBWMQVOHFPLVBY-UHFFFAOYSA-N 3,3,3-trifluoro-1-phenylpropan-1-one Chemical compound FC(F)(F)CC(=O)C1=CC=CC=C1 LBWMQVOHFPLVBY-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 238000006085 Schmidt reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- FSPSELPMWGWDRY-UHFFFAOYSA-N m-Methylacetophenone Chemical compound CC(=O)C1=CC=CC(C)=C1 FSPSELPMWGWDRY-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- ZAJNGDIORYACQU-UHFFFAOYSA-N methyl n-octyl ketone Natural products CCCCCCCCC(C)=O ZAJNGDIORYACQU-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Landscapes
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Other In-Based Heterocyclic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明は、医薬品、農薬、化粧品、香料、合成繊維及びそれらの原材料として有用なアミド化合物の製造方法に関する。 The present invention relates to a method for producing amide compounds useful as pharmaceuticals, agricultural chemicals, cosmetics, fragrances, synthetic fibers, and raw materials thereof.
アミド化合物をケトン化合物から合成する方法としては、ケトオキシムを合成して単離し、高温かつ強酸性条件のもと、ベックマン転位させることによって合成する方法が知られている。しかしながら、ケトン化合物からアミド化合物を合成する際に、ケトオキシムを別途調整し、単離する必要があり、手間がかかるという問題がある。また、ケトオキシムからベックマン転位によってアミド化合物を合成する際に、高温かつ強酸性条件を必要とする。 As a method for synthesizing an amide compound from a ketone compound, a method is known in which ketoxime is synthesized and isolated, and synthesized by Beckmann rearrangement under high temperature and strong acidic conditions. However, when synthesizing an amide compound from a ketone compound, it is necessary to prepare and isolate the ketoxime separately, which is troublesome. Further, when an amide compound is synthesized from ketoxime by Beckmann rearrangement, high temperature and strong acid conditions are required.
アミド化合物をケトン化合物から直接的に変換する方法としては、爆発の危険性があるヒドロキシルアミンを高温条件で使用する方法や、同じく爆発性があり取扱に注意を要するヒドロキシルアミン誘導体を用いる方法（非特許文献１）、衝撃や加熱に対して爆発性を示すとともに、毒性が高いアジ化ナトリウムを用いるシュミット反応（非特許文献２）が知られている。しかしながら、高温下で危険なヒドロキシルアミンや、爆発性があり、保存や取扱いに注意を要するヒドロキシルアミン誘導体や、毒性が高いアジ化ナトリウムを用いる必要があった。 Methods for converting amide compounds directly from ketone compounds include the use of hydroxylamine, which is potentially explosive, at high temperatures, and the use of hydroxylamine derivatives that are also explosive and require careful handling. Patent Document 1), Schmidt reaction (Non-Patent Document 2) using sodium azide that exhibits explosive properties against impact and heating and has high toxicity is known. However, it has been necessary to use hydroxylamine which is dangerous at high temperature, hydroxylamine derivatives which are explosive and require careful storage and handling, and sodium azide which has high toxicity.
本発明では、ヒドロキシルアミン及びその誘導体を直接用いることなく、過酷な反応条件も必要としない、新たなアミド化合物の製造方法を提供することを目的とする。 An object of the present invention is to provide a novel method for producing an amide compound which does not require harsh reaction conditions without directly using hydroxylamine and its derivatives.
本発明者らは、温和な条件のもとケトンからの直接的なアミド化合物の合成を目指して検討を進めたところ、酸触媒と水によって反応剤オキシムから原料ケトンへオキシム転位を起こし、その後ベックマン転位と続き、生じた転位体が水と反応し、アミド化合物が合成されることを見出し、本発明を完成した。 The inventors of the present invention have studied for the direct synthesis of amide compounds from ketones under mild conditions. As a result, acid catalyst and water cause oxime rearrangement from the reactant oxime to the raw material ketone, and then Beckmann. Following the rearrangement, it was found that the resulting rearrangement reacted with water to synthesize an amide compound, thereby completing the present invention.
すなわち、本発明は、ケトン化合物およびオキシム化合物を、有機溶媒と酸触媒の存在下、トランスオキシム化させる工程、および、ベックマン転位させる工程を含むアミド化合物の製造方法に関する。 That is, the present invention relates to a method for producing an amide compound including a step of transoximing a ketone compound and an oxime compound in the presence of an organic solvent and an acid catalyst, and a step of Beckmann rearrangement.
酸触媒が、塩酸、硫酸、メタンスルホン酸、トシル酸一水和物、トリフルオロメタンスルホン酸、ビストリフルオロメタンスルホンイミド、三フッ化ホウ素ジエチルエーテル錯体、トリフルオロメタンスルホン酸スカンジウム（ＩＩＩ）、トリフルオロメタンスルホン酸鉄（ＩＩＩ）、トリフルオロメタンスルホン酸銅（ＩＩ）、トリフルオロメタンスルホン酸ビスマス（ＩＩＩ）、四塩化チタン、または、三塩化鉄であることが好ましい。 Acid catalyst is hydrochloric acid, sulfuric acid, methanesulfonic acid, tosylic acid monohydrate, trifluoromethanesulfonic acid, bistrifluoromethanesulfonimide, boron trifluoride diethyl ether complex, scandium (III) trifluoromethanesulfonate, trifluoromethanesulfone It is preferably iron (III) acid, copper (II) trifluoromethanesulfonate, bismuth (III) trifluoromethanesulfonate, titanium tetrachloride, or iron trichloride.
有機溶媒が、塩化メチレン、クロロホルム、ヘキサン、または、アセトニトリルであることが好ましい。 The organic solvent is preferably methylene chloride, chloroform, hexane, or acetonitrile.
オキシム化合物が、下記化学式
で表されるＯ−ベンゼンスルホニル−アセトヒドロキサム酸エステル誘導体であることが好ましい。
The oxime compound has the following chemical formula
It is preferable that it is O-benzenesulfonyl-acetohydroxamic acid ester derivative represented by these.
本発明によれば、酸触媒と水によって反応剤オキシム化合物から原料ケトンへオキシム転位を起こし、その後ベックマン転位と続き、生じた転位体が水と反応し、アミド化合物が合成されるため、温和な反応条件で、アミド化合物を合成することができる。得られたアミド化合物は、医薬品、農薬、化粧品、香料、合成繊維およびそれらの原材料として有用である。 According to the present invention, an oxime rearrangement from a reactant oxime compound to a raw material ketone is caused by an acid catalyst and water, followed by a Beckmann rearrangement, and the resulting rearrangement reacts with water to synthesize an amide compound. An amide compound can be synthesized under reaction conditions. The obtained amide compounds are useful as pharmaceuticals, agricultural chemicals, cosmetics, fragrances, synthetic fibers, and raw materials thereof.
本発明のアミド化合物の製造方法は、ケトン化合物およびオキシム化合物を、有機溶媒と酸触媒の存在下、トランスオキシム化させる工程、および、ベックマン転位させる工程を含むことを特徴とする。酸素置換された安定なオキシム化合物を酸素置換されたヒドロキシルアミン等価体とみなし、簡便でかつ温和な条件のもとケトン化合物からアミド化合物を製造する。ブレンステッド酸触媒と触媒量の水によって酸素置換されたアセトヒドロキサム酸エチルからケトン化合物へのトランスオキシム化反応が進行し、酸素置換されたケトオキシム化合物が合成され、得られたケトオキシム中間体が酸触媒によってベックマン転位を起こし、最後に水によって補足されることでアミド化合物へと変化する。 The method for producing an amide compound of the present invention is characterized in that it comprises a step of transoximing a ketone compound and an oxime compound in the presence of an organic solvent and an acid catalyst, and a step of Beckmann rearrangement. An oxygen-substituted stable oxime compound is regarded as an oxygen-substituted hydroxylamine equivalent, and an amide compound is produced from a ketone compound under simple and mild conditions. The transoximation reaction from ethyl acetohydroxamic acid oxygen-substituted with a Bronsted acid catalyst and a catalytic amount of water to the ketone compound proceeds to synthesize the oxygen-substituted ketoxime compound, and the resulting ketoxime intermediate is the acid catalyst. Causes a Beckmann rearrangement, and finally becomes a amide compound by being supplemented with water.
ケトン化合物は、カルボニル基を有する限り特に限定されないが、たとえば、アセトフェノン、２−アセトナフトンなどのアセトナフトン、２−メチルアセトフェノン、３−メチルアセトフェノン、４−メチルアセトフェノンなどのメチルアセトフェン、４−メトキシアセトフェノンなどのメトキシアセトフェノン、４−クロロアセトフェノンなどのクロロアセトフェン、４−トリフルオロメチルアセトフェノンなどのトリフルオロメチルアセトフェノン、シクロドデカノン、プロピオフェノン、イソブチロフェノン、２−アセチルチオフェンなどのアセチルチオフェン、２−ドデカノンなどのドデカノンなどが挙げられる。なかでも、電子供与性置換基を有する基質の点で、メトキシアセトフェノンが好ましい。 The ketone compound is not particularly limited as long as it has a carbonyl group. For example, acetonaphthone such as acetophenone and 2-acetonaphthone, 2-methylacetophenone, 3-methylacetophenone, methylacetophene such as 4-methylacetophenone, 4-methoxyacetophenone Methoxyacetophenone, chloroacetophene such as 4-chloroacetophenone, trifluoromethylacetophenone such as 4-trifluoromethylacetophenone, cyclododecanone, propiophenone, isobutyrophenone, acetylthiophene such as 2-acetylthiophene, 2-dodecanone And dodecanone. Of these, methoxyacetophenone is preferable in terms of a substrate having an electron-donating substituent.
オキシム化合物は、＞Ｃ＝Ｎ−ＯＨで表される構造を有する限り特に限定されないが、たとえば、下記化学式
で表されるＯ−ベンゼンスルホニル−アセトヒドロキサム酸エステル誘導体、Ｏ−４−トリフルオロメチルベンゼンスルホニル−アセトヒドロキサム酸エステル誘導体、Ｏ−ジフェニルホスフィニル−アセトヒドロキサム酸エステル誘導体などが挙げられる。なかでも、反応収率の点で、上記化学式で表されるＯ−ベンゼンスルホニル−アセトヒドロキサム酸エステル誘導体、Ｏ−４−トリフルオロメチルベンゼンスルホニル−アセトヒドロキサム酸エステル誘導体が好ましい。
The oxime compound is not particularly limited as long as it has a structure represented by> C═N—OH.
O-benzenesulfonyl-acetohydroxamic acid ester derivatives, O-4-trifluoromethylbenzenesulfonyl-acetohydroxamic acid ester derivatives, O-diphenylphosphinyl-acetohydroxamic acid ester derivatives and the like represented by Among these, in terms of reaction yield, O-benzenesulfonyl-acetohydroxamic acid ester derivatives and O-4-trifluoromethylbenzenesulfonyl-acetohydroxamic acid ester derivatives represented by the above chemical formula are preferable.
有機溶媒は特に限定されないが、たとえば塩化メチレン、クロロホルム、ヘキサン、トルエン、ジエチルエーテル、ヘキサン、トルエン、アセトニトリル、メタノール、テトラヒドロフラン、酢酸エチル、アセトン、ジメチルホルムアルデヒドなどが挙げられる。これらの有機溶媒は、２種以上を混合して使用することもできる。なかでも、反応収率の点で、塩化メチレン、クロロホルム、ヘキサン、アセトニトリルが好ましい。 The organic solvent is not particularly limited, and examples thereof include methylene chloride, chloroform, hexane, toluene, diethyl ether, hexane, toluene, acetonitrile, methanol, tetrahydrofuran, ethyl acetate, acetone, dimethylformaldehyde and the like. These organic solvents can be used in a mixture of two or more. Of these, methylene chloride, chloroform, hexane, and acetonitrile are preferable in terms of reaction yield.
酸触媒は特に限定されず、酸そのものだけでなく、その金属塩も含まれる。たとえば、塩酸、硫酸、メタンスルホン酸、トシル酸一水和物、トリフルオロメタンスルホン酸、ビストリフルオロメタンスルホンイミド、三フッ化ホウ素ジエチルエーテル錯体、トリフルオロメタンスルホン酸スカンジウム（ＩＩＩ）、トリフルオロメタンスルホン酸鉄（ＩＩＩ）、トリフルオロメタンスルホン酸銅（ＩＩ）、トリフルオロメタンスルホン酸ビスマス（ＩＩＩ）、四塩化チタン、三塩化鉄などが挙げられる。なかでも、反応時間の点で、硫酸、メタンスルホン酸、トシル酸一水和物、トリフルオロメタンスルホン酸、ビストリフルオロメタンスルホンイミド、トリフルオロメタンスルホン酸ビスマス（ＩＩＩ）、三塩化鉄が好ましい。 The acid catalyst is not particularly limited, and includes not only the acid itself but also a metal salt thereof. For example, hydrochloric acid, sulfuric acid, methanesulfonic acid, tosylic acid monohydrate, trifluoromethanesulfonic acid, bistrifluoromethanesulfonimide, boron trifluoride diethyl ether complex, scandium (III) trifluoromethanesulfonate, iron trifluoromethanesulfonate (III), copper (II) trifluoromethanesulfonate, bismuth (III) trifluoromethanesulfonate, titanium tetrachloride, iron trichloride and the like. Of these, sulfuric acid, methanesulfonic acid, tosylic acid monohydrate, trifluoromethanesulfonic acid, bistrifluoromethanesulfonimide, bismuth (III) trifluoromethanesulfonate, and iron trichloride are preferable in terms of reaction time.
ケトン化合物に対するオキシム化合物の添加量は、ケトン化合物１モルに対して１〜１０モルが好ましく、１〜２モルがより好ましい。１モル未満では、反応が完結しなくなる傾向がある。 1-10 mol is preferable with respect to 1 mol of ketone compounds, and, as for the addition amount of the oxime compound with respect to a ketone compound, 1-2 mol is more preferable. If it is less than 1 mol, the reaction tends to be incomplete.
酸触媒の添加量は、ケトン化合物１モルに対して０．００２５〜１モルが好ましく、０．０２５〜０．１０モルがより好ましい。０．００２５モル未満では、アミド化合物が生成しないため、反応が進まなくなる傾向がある。１モルを超えても、反応の促進効果は小さく、経済性を損なう傾向がある。 The addition amount of the acid catalyst is preferably 0.0025 to 1 mol, more preferably 0.025 to 0.10 mol, relative to 1 mol of the ketone compound. If the amount is less than 0.0025 mol, an amide compound is not generated, and thus the reaction tends not to proceed. Even if it exceeds 1 mol, the effect of promoting the reaction is small and tends to impair economic efficiency.
反応系中に水を加えることが好ましい。水の添加量は限定されないが、ケトン化合物１モルに対して１〜１０当量が好ましく、１〜２当量がより好ましい。１当量未満では、反応は完結しなくなり、１０当量を超えると反応の進行が遅くなる傾向がある。 It is preferable to add water to the reaction system. Although the addition amount of water is not limited, 1-10 equivalent is preferable with respect to 1 mol of ketone compounds, and 1-2 equivalent is more preferable. When the amount is less than 1 equivalent, the reaction is not completed, and when the amount exceeds 10 equivalents, the progress of the reaction tends to be slow.
反応温度は特に限定されないが、０〜４０℃が好ましく、２０〜３０℃がより好ましい。０℃を下回ると、アミド化合物の収率が低下し、反応が完結しない傾向がある。４０℃を超えても、収率の向上も小さく、エネルギーの消費を増大させる傾向がある。また、反応時間も特に限定されないが、１〜４８時間が好ましく、２４〜４８時間がより好ましい。１時間未満では、反応が完結しない傾向がある。４８時間を超えても、収率の向上も小さく、時間を消費するのみとなる傾向がある。 Although reaction temperature is not specifically limited, 0-40 degreeC is preferable and 20-30 degreeC is more preferable. When the temperature is lower than 0 ° C., the yield of the amide compound tends to decrease and the reaction tends not to be completed. Even if it exceeds 40 degreeC, the improvement of a yield is also small and there exists a tendency which increases consumption of energy. Moreover, although reaction time is not specifically limited, 1 to 48 hours are preferable and 24 to 48 hours are more preferable. If it is less than 1 hour, the reaction tends to be incomplete. Even if it exceeds 48 hours, the yield improvement is small, and there is a tendency that only time is consumed.
本発明の製造方法によって得られたアミド化合物は、医薬品、農薬、化粧品、香料、合成繊維およびそれらの原材料として有用である。 The amide compound obtained by the production method of the present invention is useful as pharmaceuticals, agricultural chemicals, cosmetics, fragrances, synthetic fibers and raw materials thereof.
以下、本発明の実施例について説明するが、本発明は、以下の実施例に限定されない。 Examples of the present invention will be described below, but the present invention is not limited to the following examples.
合成例１ Ｏ−ベンゼンスルホニル−アセトヒドロキサム酸エチル（化合物２ａ）の合成
室温で、アルゴン雰囲気下、２０ｍＬフラスコ（撹拌子入）に アセトヒドロキサム酸エチル（２００ｍｇ、１．９４ｍｍｏｌ、１．０ｅｑ．）、塩化ベンゼンスルホニル（０．３３ｍＬ、２．６２ｍｍｏｌ、１．３５ｅｑ．）、トリエチルアミン（０．３９ｍＬ、２．８１ｍｍｏｌ、１．４５ｅｑ．）、テトラヒドロフラン（６．４ｍｌ、０．３０Ｍ）を加え、室温で１時間、撹拌した。その後、飽和塩化アンモニウム水溶液で反応を停止し、テトラヒドロフランを減圧留去後に、ジエチルエーテル（２０ｍＬ×３回）を用いて抽出を行い、有機相を飽和食塩水で洗浄後、硫酸ナトリウムを用いて乾燥した。硫酸ナトリウムを綿栓濾過で濾別し、減圧下溶媒を留去してＮＭＲ（ＣＤＣｌ３）を測定した。シリカゲルカラムクロマトグラフィー（関東化学 ｓｉｌｉｃａ ｇｅｌ ６０（４０−５０μｍ）、ヘキサン／酢酸エチル＝９５／５）で精製し、白色のＯ−ベンゼンスルホニル−アセトヒドロキサム酸エチル（化合物２ａ）を３７６ｍｇ（収率８０％）得た。化合物２ａのＮＭＲデータは、以下の通りである。
Synthesis Example 1 Synthesis of ethyl O-benzenesulfonyl-acetohydroxamic acid (Compound 2a) In a 20 mL flask (with a stirring bar) at room temperature under an argon atmosphere, ethyl acetohydroxamic acid (200 mg, 1.94 mmol, 1.0 eq.), Benzenesulfonyl chloride (0.33 mL, 2.62 mmol, 1.35 eq.), Triethylamine (0.39 mL, 2.81 mmol, 1.45 eq.), Tetrahydrofuran (6.4 ml, 0.30 M) was added, and 1 at room temperature was added. Stir for hours. Thereafter, the reaction was stopped with a saturated aqueous ammonium chloride solution, and tetrahydrofuran was distilled off under reduced pressure, followed by extraction with diethyl ether (20 mL × 3 times). The organic phase was washed with saturated brine and then dried with sodium sulfate. did. Sodium sulfate was filtered off by cotton plug filtration, the solvent was distilled off under reduced pressure, and NMR (CDCl 3 ) was measured. Purification by silica gel column chromatography (Kanto Chemical Silica gel 60 (40-50 μm), hexane / ethyl acetate = 95/5) gave 376 mg (yield 80) of white O-benzenesulfonyl-acetohydroxamic acid ethyl (compound 2a). %)Obtained. The NMR data of compound 2a are as follows.
２ａ：１Ｈ−ＮＭＲ（４００Ｈｚ、ＣＤＣｌ３）δ１．２２（ｔ，Ｊ＝７．１Ｈｚ，３Ｈ），２．０２（ｓ，３Ｈ），３．９７（ｑ，Ｊ＝７．１Ｈｚ，２Ｈ），７．５４（ｄ，Ｊ＝７．５Ｈｚ，２Ｈ），７．６７（ｄ，Ｊ＝７．５Ｈｚ，１Ｈ），７．９７（ｄ，Ｊ＝７．５Ｈｚ，２Ｈ）；１３Ｃ−ＮＭＲ（ＣＤＣｌ３，１００ＭＨｚ）δ１４．８，１５．８，６４．７，１２９．６，１３４．６，１３６．３，１７０．８． 2a: 1 H-NMR (400 Hz, CDCl 3 ) δ 1.22 (t, J = 7.1 Hz, 3H), 2.02 (s, 3H), 3.97 (q, J = 7.1 Hz, 2H) , 7.54 (d, J = 7.5 Hz, 2H), 7.67 (d, J = 7.5 Hz, 1H), 7.97 (d, J = 7.5 Hz, 2H); 13 C-NMR (CDCl 3 , 100 MHz) δ 14.8, 15.8, 64.7, 129.6, 134.6, 136.3, 170.8.
実施例１ Ｎ−（２−ナフチル）アセトアミド（化合物３ａ）の合成
室温、アルゴン雰囲気下、試験管（撹拌子入）に２−アセトナフトン（８５．１ｍｇ，０．５０ｍｍｏｌ，１．０ｅｑ．）、トシル酸一水和物（２．４ｍｇ，０．０１２５ｍｍｏｌ，２．５ｍｏｌ％）、アセトニトリル（０．５０ｍＬ，１．０Ｍ）、Ｏ−ベンゼンスルホニル−アセトヒドロキサム酸エチル（１４６ｍｇ，０．６０ｍｍｏｌ，１．２ｅｑ．）を加え、室温で２４ｈ撹拌した。その後、飽和炭酸水素ナトリウム水溶液３ｍｌを加え、１０分撹拌し、酢酸エチル１０ｍＬで３回抽出を行った。集めた有機相を飽和食塩水で洗浄し、硫酸ナトリウムで乾燥した。その後、硫酸ナトリウムを除き、減圧下溶媒を留去してＮＭＲを測定した。シリカゲルカラムクロマトグラフィー（関東化学ｓｉｌｉｃａ ｇｅｌ ６０（４０−５０μｍ）、ヘキサン／酢酸エチル＝８／２から６／４）で精製し、白色のＮ−（２−ナフチル）アセトアミド（化合物３ａ）を８３．３ｍｇ（収率９０％）得た。化合物３ａのＮＭＲデータは、以下の通りである。
Example 1 Synthesis of N- (2-naphthyl) acetamide (Compound 3a) 2-acetonaphthone (85.1 mg, 0.50 mmol, 1.0 eq.), Tosyl in a test tube (with a stirring bar) at room temperature under an argon atmosphere Acid monohydrate (2.4 mg, 0.0125 mmol, 2.5 mol%), acetonitrile (0.50 mL, 1.0 M), ethyl O-benzenesulfonyl-acetohydroxamate (146 mg, 0.60 mmol, 1.2 eq) .) Was added and stirred at room temperature for 24 h. Thereafter, 3 ml of a saturated aqueous sodium hydrogen carbonate solution was added, stirred for 10 minutes, and extracted three times with 10 mL of ethyl acetate. The collected organic phase was washed with saturated brine and dried over sodium sulfate. Thereafter, sodium sulfate was removed, the solvent was distilled off under reduced pressure, and NMR was measured. Purification by silica gel column chromatography (Kanto Chemical silica gel 60 (40-50 μm), hexane / ethyl acetate = 8/2 to 6/4) gave white N- (2-naphthyl) acetamide (compound 3a) at 83. 3 mg (yield 90%) was obtained. The NMR data of compound 3a are as follows.
３ａ：１Ｈ−ＮＭＲ（ＣＤＣｌ３，４００ＭＨｚ，ｐｐｍ）δ８．１７（ｓ，１Ｈ），７．８１−７．７３（ｍ，４Ｈ），７．４６−７．３６（ｍ，３Ｈ），２．２０（ｓ，３Ｈ）；１３Ｃ ＮＭＲ（ＣＤＣｌ３，１００ＭＨｚ，ｐｐｍ）δ１６８．５，１３５．５，１３３．９，１３０．７，１２８．８，１２７．８，１２７．６，１２６．５，１２５．１，１２０．１，１１６．９，２４．７；ＬＣ−ＭＳ（ＥＳＩ，ｐｏｓｉｔｉｖｅ）ｍ／ｚ ｃａｌｃｄ ｆｏｒ Ｃ１２Ｈ１２ＮＯ＋［Ｍ＋Ｈ］：１８６．０９，ｆｏｕｎｄ １８６．１０． 3a: 1 H-NMR (CDCl 3 , 400 MHz, ppm) δ 8.17 (s, 1H), 7.81-7.73 (m, 4H), 7.46-7.36 (m, 3H), 2 .20 (s, 3H); 13 C NMR (CDCl 3 , 100 MHz, ppm) δ 168.5, 135.5, 133.9, 130.7, 128.8, 127.8, 127.6, 126.5 , 125.1,120.1,116.9,24.7; LC-MS (ESI , positive) m / z calcd for C 12 H 12 NO + [M + H]: 186.09, found 186.10.
実施例１の合成方法を利用して合成したアミド類を以下に示す（Ｓｃｈｅｍｅ １）。 Amides synthesized using the synthesis method of Example 1 are shown below (Scheme 1).
芳香族ケトンに対しては高収率で反応が進行した。置換基の位置や立体的に大きいナフタレン環についても良好な反応性を示した。電子的特性として電子供与性置換基の場合は、高い収率が得られるが、電子求引性置換基の時は転位が進みにくくなる傾向がある。脂肪族ケトンについては鎖状及び環状ともに反応が進行し、ナイロン−１２の原料となるＬａｕｒｏｌａｃｔａｍの合成にも適用可能である。 The reaction proceeded with high yield for aromatic ketones. Good reactivity was also observed for the position of the substituent and the sterically large naphthalene ring. In the case of an electron-donating substituent as an electronic property, a high yield can be obtained, but in the case of an electron-withdrawing substituent, rearrangement tends to be difficult to proceed. With regard to the aliphatic ketone, the reaction proceeds in both a chain form and a cyclic form, and can be applied to the synthesis of Laurolactam, which is a raw material for nylon-12.
実施例２
表１に保護基ＰＧを変更した反応剤の検討結果を示す。芳香族スルホニル基を有するオキシムにて良好な結果が得られることが分かり、なかでもベンゼンスルホニル基や４−トリフルオロメチルベンゼンスルホニル基が最も優れた結果を示すことが分かる（ｅｎｔｒｉｅｓ １、２）。
Example 2
Table 1 shows the results of investigation of the reactants with the protective group PG changed. It turns out that a favorable result is obtained with the oxime which has an aromatic sulfonyl group, and it turns out that a benzenesulfonyl group and 4-trifluoromethylbenzenesulfonyl group show the most excellent result (entries 1, 2).
実施例３
表２に、２−アセトナフトンからＮ−（２−ナフチル）アセトアミドを合成する反応における種々の触媒を検討した結果を示す。酸触媒としては塩酸、硫酸、メタンスルホン酸、トシル酸一水和物、トリフルオロメタンスルホン酸、ビストリフルオロメタンスルホンイミド、三フッ化ホウ素ジエチルエーテル錯体、トリフルオロメタンスルホン酸スカンジウム（ＩＩＩ）、トリフルオロメタンスルホン酸鉄（ＩＩＩ）、トリフルオロメタンスルホン酸銅（ＩＩ）、トリフルオロメタンスルホン酸ビスマス（ＩＩＩ）、四塩化チタン、三塩化鉄が優れた効果を示すことが分かる（Ｅｎｔｒｉｅｓ ２〜１４）。
Example 3
Table 2 shows the results of examining various catalysts in the reaction of synthesizing N- (2-naphthyl) acetamide from 2-acetonaphthone. Acid catalysts include hydrochloric acid, sulfuric acid, methanesulfonic acid, tosylic acid monohydrate, trifluoromethanesulfonic acid, bistrifluoromethanesulfonimide, boron trifluoride diethyl ether complex, scandium trifluoromethanesulfonate (III), trifluoromethanesulfone It can be seen that iron (III) acid, copper (II) trifluoromethanesulfonate, bismuth (III) trifluoromethanesulfonate, titanium tetrachloride, and iron trichloride show excellent effects (Entry 2-14).
実施例４
表３に、２−アセトナフトンからＮ−（２−ナフチル）アセトアミドを合成する反応における種々の溶媒を検討した結果を示す。塩化メチレン、クロロホルム、ヘキサン、アセトニトリルが効果があることがわかった（Ｅｎｔｒｉｅｓ １、２、４、６）。
Example 4
Table 3 shows the results of examining various solvents in the reaction for synthesizing N- (2-naphthyl) acetamide from 2-acetonaphthone. Methylene chloride, chloroform, hexane, and acetonitrile were found to be effective (Entry 1, 2, 4, 6).
本発明によれば、温和な反応条件で、アミド化合物を合成することができる。得られたアミド化合物は、医薬品、農薬、化粧品、香料、合成繊維およびそれらの原材料として有用である。
According to the present invention, an amide compound can be synthesized under mild reaction conditions. The obtained amide compounds are useful as pharmaceuticals, agricultural chemicals, cosmetics, fragrances, synthetic fibers, and raw materials thereof.
Claims (4)
で表されるＯ−ベンゼンスルホニル−アセトヒドロキサム酸エステル誘導体である請求項１〜３のいずれかに記載のアミド化合物の製造方法。
The oxime compound has the following chemical formula
The method for producing an amide compound according to claim 1, which is an O-benzenesulfonyl-acetohydroxamic acid ester derivative represented by the formula:
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| CN113321669A (en) * | 2020-02-28 | 2021-08-31 | 中国科学院上海有机化学研究所 | Sulfimide metal salt, preparation method and application thereof |
| CN115368258A (en) * | 2022-07-27 | 2022-11-22 | 浙江工业大学 | Preparation process of amide compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113321669A (en) * | 2020-02-28 | 2021-08-31 | 中国科学院上海有机化学研究所 | Sulfimide metal salt, preparation method and application thereof |
| CN113321669B (en) * | 2020-02-28 | 2023-03-24 | 中国科学院上海有机化学研究所 | Sulfimide metal salt, preparation method and application thereof |
| CN115368258A (en) * | 2022-07-27 | 2022-11-22 | 浙江工业大学 | Preparation process of amide compound |
| CN115368258B (en) * | 2022-07-27 | 2023-07-25 | 浙江工业大学 | Preparation process of amide compound |
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