JP6920917B2 - 6-Hydroxy-2-naphthoic acid alkenyl ester and its production method - Google Patents
6-Hydroxy-2-naphthoic acid alkenyl ester and its production method Download PDFInfo
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- -1 6-Hydroxy-2-naphthoic acid alkenyl ester Chemical class 0.000 title claims description 40
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 150000002148 esters Chemical class 0.000 claims description 11
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000006196 deacetylation Effects 0.000 description 7
- 238000003381 deacetylation reaction Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 5
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- NFTLBCXRDNIJMI-UHFFFAOYSA-N 6-acetyloxynaphthalene-2-carboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(OC(=O)C)=CC=C21 NFTLBCXRDNIJMI-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 229920000800 acrylic rubber Polymers 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000645 desinfectant Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 150000007514 bases Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- GQAXSRIBRIMFIT-UHFFFAOYSA-N (6-carbonochloridoylnaphthalen-2-yl) acetate Chemical compound C1=C(C(Cl)=O)C=CC2=CC(OC(=O)C)=CC=C21 GQAXSRIBRIMFIT-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JKLUVCHKXQJGIG-UHFFFAOYSA-N 2-Methylenebutan-1-ol Chemical compound CCC(=C)CO JKLUVCHKXQJGIG-UHFFFAOYSA-N 0.000 description 1
- BXJQZHHEWYUFAC-UHFFFAOYSA-N 2-methylidenepentan-1-ol Chemical compound CCCC(=C)CO BXJQZHHEWYUFAC-UHFFFAOYSA-N 0.000 description 1
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 description 1
- BWROKMCJAGKDDI-UHFFFAOYSA-N 3-methylidenehexan-1-ol Chemical compound CCCC(=C)CCO BWROKMCJAGKDDI-UHFFFAOYSA-N 0.000 description 1
- IFPAPBFCYGUMJZ-UHFFFAOYSA-N 3-methylidenepentan-1-ol Chemical compound CCC(=C)CCO IFPAPBFCYGUMJZ-UHFFFAOYSA-N 0.000 description 1
- ZPDCMMAJDPNCST-UHFFFAOYSA-N 4-methylidenehexan-1-ol Chemical compound CCC(=C)CCCO ZPDCMMAJDPNCST-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 0 C*(CN(C)C(C)=C)OC(c1ccc(cc(cc2)O)c2c1)=O Chemical compound C*(CN(C)C(C)=C)OC(c1ccc(cc(cc2)O)c2c1)=O 0.000 description 1
- NGQIGNYFXCCVCX-UHFFFAOYSA-N CCCC(=C)CCCO Chemical compound CCCC(=C)CCCO NGQIGNYFXCCVCX-UHFFFAOYSA-N 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N acetaldehyde dimethyl acetal Natural products COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 229940069428 antacid Drugs 0.000 description 1
- 239000003159 antacid agent Substances 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- LQAVWYMTUMSFBE-UHFFFAOYSA-N pent-4-en-1-ol Chemical compound OCCCC=C LQAVWYMTUMSFBE-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、新規な6−ヒドロキシ−2−ナフトエ酸アルケニルエステルおよびその製造方法に関する。 The present invention relates to a novel 6-hydroxy-2-naphthoic acid alkenyl ester and a method for producing the same.
分子内にヒドロキシル基とアルケニル基を有する芳香族化合物は、アクリルゴムや抗菌性樹脂のモノマー、および工業用殺菌剤等としての使用が提案されている(特許文献1〜4)。 Aromatic compounds having a hydroxyl group and an alkenyl group in the molecule have been proposed to be used as monomers of acrylic rubber and antibacterial resins, industrial disinfectants and the like (Patent Documents 1 to 4).
このような芳香族化合物としては、ベンゼン骨格を有する化合物が知られているが、ナフタレン骨格を有する化合物は知られていなかった。 As such an aromatic compound, a compound having a benzene skeleton is known, but a compound having a naphthalene skeleton is not known.
本発明の目的は、アクリルゴムや抗菌性樹脂のモノマー、および工業用殺菌剤等として有用な、新規なナフタレン環を有する化合物を提供することにある。また、本発明の他の目的は新規な6−ヒドロキシ−2−ナフトエ酸アルケニルエステルの製造方法を提供することにある。 An object of the present invention is to provide a compound having a novel naphthalene ring, which is useful as a monomer of acrylic rubber or an antibacterial resin, and an industrial disinfectant or the like. Another object of the present invention is to provide a novel method for producing a 6-hydroxy-2-naphthoic acid alkenyl ester.
本発明は、式(1)で表される6−ヒドロキシ−2−ナフトエ酸アルケニルエステルに関する。
また、本発明は式(2)で表される6−アセトキシ−2−ナフトエ酸ハライドと式(3)で表されるアルケニルアルコールを反応させる工程を含む式(1)で表される6−ヒドロキシ−2−ナフトエ酸アルケニルエステルの製造方法に関する。
本発明の6−ヒドロキシ−2−ナフトエ酸アルケニルエステルは、アクリルゴムや抗菌性樹脂のモノマー、および工業用殺菌剤等として使用できる。 The 6-hydroxy-2-naphthoic acid alkenyl ester of the present invention can be used as a monomer of acrylic rubber or an antibacterial resin, an industrial disinfectant, or the like.
本発明は、式(1)で表される6−ヒドロキシ−2−ナフトエ酸アルケニルエステルである。
nとmの合計は好ましくは1〜5、より好ましくは2〜4、さらに好ましくは2である。
The present invention is a 6-hydroxy-2-naphthoic acid alkenyl ester represented by the formula (1).
The total of n and m is preferably 1 to 5, more preferably 2 to 4, and even more preferably 2.
本発明の好ましい態様において、式(1)で表される6−ヒドロキシ−2−ナフトエ酸アルケニルエステルとしては、nが1であり、かつ、mが1である、すなわち、式(4)で表される6−ヒドロキシ−2−ナフトエ酸メタリルエステルである。
本発明の式(1)で表される6−ヒドロキシ−2−ナフトエ酸アルケニルエステルの製造方法は、例えば式(2)で表される6−アセトキシ−2−ナフトエ酸ハライドと式(3)で表されるアルケニルアルコールを反応させる工程を含む製造方法である。
式(2)で表されるアセトキシナフタレンカルボン酸ハライドおよび式(3)で表されるアルケニルアルコールとしては、市販のものや、当業者に知られた方法で製造したものを用いることができる。 As the acetoxynaphthalene carboxylic acid halide represented by the formula (2) and the alkenyl alcohol represented by the formula (3), commercially available ones or those produced by a method known to those skilled in the art can be used.
式(2)で表される6−アセトキシ−2−ナフトエ酸ハライドの製造方法は、例えば6−アセトキシ−2−ナフトエ酸と塩化チオニルを反応させる工程を含む製造方法である。 The method for producing a 6-acetoxy-2-naphthoic acid halide represented by the formula (2) is, for example, a production method including a step of reacting 6-acetoxy-2-naphthoic acid with thionyl chloride.
式(3)で表されるアルケニルアルコールとしては、ビニルアルコール(エテノール)、アリルアルコール(2−プロペン−1−オール)、3−ブテン−1−オール、4−ペンテン−1−オール、1−メチル−2−エテン−1−オール、2−メチル−2−プロペン−1−オール(β−メタリルアルコール)、3−メチル−3−ブテン−1−オール、4−メチル−4−ペンテン−1−オール、1−エチル−2−エテン−1−オール、2−エチル−2−プロペン−1−オール、3−エチル−3−ブテン−1−オール、4−エチル−4−ペンテン−1−オール、1−プロピル−2−エテン−1−オール、2−プロピル−2−プロペン−1−オール、3−プロピル−3−ブテン−1−オールおよび4−プロピル−4−ペンテン−1−オールからなる群から選択される一種以上が挙げられる。これらの中で、入手容易性および安全性に優れる点で2−メチル−2−プロペン−1−オール(β−メタリルアルコール)が好ましい。 Examples of the alkenyl alcohol represented by the formula (3) include vinyl alcohol (ethenol), allyl alcohol (2-propen-1-ol), 3-butene-1-ol, 4-penten-1-ol, and 1-methyl. -2-Eten-1-ol, 2-Methyl-2-propen-1-ol (β-Metalyl alcohol), 3-Methyl-3-buten-1-ol, 4-Methyl-4-penten-1- All, 1-ethyl-2-ethane-1-ol, 2-ethyl-2-propen-1-ol, 3-ethyl-3-buten-1-ol, 4-ethyl-4-penten-1-ol, Group consisting of 1-propyl-2-ethen-1-ol, 2-propyl-2-propen-1-ol, 3-propyl-3-buten-1-ol and 4-propyl-4-penten-1-ol One or more selected from. Of these, 2-methyl-2-propen-1-ol (β-metharyl alcohol) is preferable because of its excellent availability and safety.
式(2)で表される6−アセトキシ−2−ナフトエ酸ハライドと式(3)で表されるアルケニルアルコールを反応させる工程は、脱酸剤および/または溶媒の存在下で実施してもよい。 The step of reacting the 6-acetoxy-2-naphthoic acid halide represented by the formula (2) with the alkenyl alcohol represented by the formula (3) may be carried out in the presence of an antacid and / or a solvent. ..
脱酸剤としては、炭酸水素ナトリウム、炭酸ナトリウム、炭酸カリウム、ピリジンおよびトリエチルアミンからなる群から選択される一種以上が挙げられ、反応性に優れる点でピリジンが好ましい。 Examples of the deoxidizing agent include one or more selected from the group consisting of sodium hydrogen carbonate, sodium carbonate, potassium carbonate, pyridine and triethylamine, and pyridine is preferable in terms of excellent reactivity.
脱酸剤の使用量としては、特に限定されないが、通常、原料である式(2)で表される6−アセトキシ−2−ナフトエ酸ハライド化合物1モル当量に対して0.1〜10モル当量が好ましく、0.6〜1.5モル当量がより好ましい。 The amount of the deoxidizing agent used is not particularly limited, but is usually 0.1 to 10 molar equivalents with respect to 1 molar equivalent of the 6-acetoxy-2-naphthoic acid halide compound represented by the formula (2), which is a raw material. Is preferable, and 0.6 to 1.5 molar equivalents are more preferable.
溶媒としては、テトラヒドロフラン、DMF、DMA、メタノール、エタノール、イソプロパノール、アセトン、ジエチルエーテル、クロロベンゼン、ヘキサン、ヘプタン、デカン、ニトロベンゼン、二硫化炭素、ニトロメタン、ジクロロメタン、ジクロロエタン、テトラヒドロフラン、ジオキサン、ベンゼン、トルエン、キシレン、四塩化炭素、ニトロメタン、アセトニトリルおよび軽油からなる群から選択される一種以上が挙げられ、反応性に優れる点でテトラヒドロフランが好ましい。 Solvents include tetrahydrofuran, DMF, DMA, methanol, ethanol, isopropanol, acetone, diethyl ether, chlorobenzene, hexane, heptane, decane, nitrobenzene, carbon disulfide, nitromethane, dichloromethane, dichloroethane, tetrahydrofuran, dioxane, benzene, toluene, xylene. , One or more selected from the group consisting of carbon tetrachloride, nitromethane, acetonitrile and light oil, and tetrahydrofuran is preferable in terms of excellent reactivity.
溶媒の使用量としては、特に限定されないが、通常、原料である式(2)で表される6−アセトキシ−2−ナフトエ酸ハライド100重量部に対して100〜500重量部であるのが好ましく、1.5〜3.0重量部であるのがより好ましい。 The amount of the solvent used is not particularly limited, but is usually preferably 100 to 500 parts by weight with respect to 100 parts by weight of the 6-acetoxy-2-naphthoic acid halide represented by the formula (2), which is a raw material. , 1.5 to 3.0 parts by weight, more preferably.
式(2)で表される6−アセトキシ−2−ナフトエ酸ハライドは、式(3)で表されるアルケニルアルコール1モル当量に対して0.5〜2.0モル当量存在させて反応することが好ましく、0.7〜1.5モル当量存在させて反応することがより好ましい。式(2)で表される6−アセトキシ−2−ナフトエ酸ハライドが式(3)で表されるアルケニルアルコール1モル当量に対して0.5モル当量未満である場合、また、式(2)で表される6−アセトキシ−2−ナフトエ酸ハライドが式(3)で表されるアルケニルアルコール1モル当量に対して2モル当量を超過する場合、反応が十分に進行せず、副生物が生成する傾向がある。 The 6-acetoxy-2-naphthoic acid halide represented by the formula (2) reacts in the presence of 0.5 to 2.0 molar equivalents with respect to 1 molar equivalent of the alkenyl alcohol represented by the formula (3). Is preferable, and it is more preferable to react in the presence of 0.7 to 1.5 molar equivalents. When the 6-acetoxy-2-naphthoic acid halide represented by the formula (2) is less than 0.5 molar equivalent to 1 molar equivalent of the alkenyl alcohol represented by the formula (3), and also when the formula (2) When the 6-acetoxy-2-naphthoic acid halide represented by (3) exceeds 2 molar equivalents with respect to 1 molar equivalent of the alkenyl alcohol represented by the formula (3), the reaction does not proceed sufficiently and by-products are produced. Tend to.
反応温度は原料や溶媒などによって異なるため、特に限定されないが、通常50〜150℃で行われ、好ましくは用いる溶媒の沸点近傍温度で還流しながら反応を実施するのがよい。 Since the reaction temperature varies depending on the raw material, solvent and the like, it is not particularly limited, but it is usually carried out at 50 to 150 ° C., and it is preferable to carry out the reaction while refluxing at a temperature near the boiling point of the solvent to be used.
反応時間は原料や溶媒などによって異なるため、特に限定されないが、通常1〜4時間行われる。 Since the reaction time varies depending on the raw material, solvent and the like, it is not particularly limited, but is usually carried out for 1 to 4 hours.
このようにして得られた6−アセトキシ−2−ナフトエ酸アルケニルエステルは、次いで脱アセチル化工程に供される。 The 6-acetoxy-2-naphthoic acid alkenyl ester thus obtained is then subjected to a deacetylation step.
脱アセチル化工程は、通常、塩基性化合物および溶媒の存在下で実施される。 The deacetylation step is usually carried out in the presence of basic compounds and solvents.
脱アセチル化工程における塩基性化合物としては、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、水酸化マグネシウム、炭酸ナトリウム、炭酸カリウム、炭酸カルシウムおよび炭酸マグネシウムからなる群から選択される1種以上が挙げられ、アルケニルエステルを分解し難い点で炭酸水素ナトリウムが特に好ましい。 Examples of the basic compound in the deacetylation step include one or more selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate and magnesium carbonate. Sodium hydrogen carbonate is particularly preferable because it does not easily decompose the alkenyl ester.
脱アセチル化工程における塩基性化合物の使用量としては、特に限定されないが、通常、6−アセトキシ−2−ナフトエ酸アルケニルエステル1モル当量に対して1.0〜3.0モル当量が好ましい。 The amount of the basic compound used in the deacetylation step is not particularly limited, but is usually preferably 1.0 to 3.0 molar equivalents with respect to 1 molar equivalent of 6-acetoxy-2-naphthoic acid alkenyl ester.
脱アセチル化工程における溶媒としては、水、メタノール、エタノールおよびプロパノールからなる群から選択される一種以上が挙げられ、反応性の観点から水を含むものが好ましい。 Examples of the solvent in the deacetylation step include one or more selected from the group consisting of water, methanol, ethanol and propanol, and those containing water are preferable from the viewpoint of reactivity.
溶媒の使用量としては、特に限定されないが、通常、原料である式(2)で表される6−アセトキシ−2−ナフトエ酸ハライド100重量部に対して100〜500重量部であるのが好ましい。 The amount of the solvent used is not particularly limited, but is usually preferably 100 to 500 parts by weight with respect to 100 parts by weight of the 6-acetoxy-2-naphthoic acid halide represented by the formula (2), which is a raw material. ..
脱アセチル化工程における反応温度は原料や溶媒などによって異なるため、特に限定されないが、通常40〜100℃で行われる。 The reaction temperature in the deacetylation step varies depending on the raw material, solvent, etc., and is not particularly limited, but is usually 40 to 100 ° C.
脱アセチル化工程における反応時間は原料や溶媒などによって異なるため、特に限定されないが、通常1〜10時間行われる。 The reaction time in the deacetylation step varies depending on the raw material, solvent, etc., and is not particularly limited, but is usually carried out for 1 to 10 hours.
反応後、得られた芳香族化合物は、精製によって純度を向上させることができる。精製は、濾過、洗浄、濃縮、抽出、蒸留、カラムクロマト分離等の一般的な精製操作を経て、適宜目的とする純度まで精製することができる。 After the reaction, the obtained aromatic compound can be purified to improve its purity. Purification can be carried out to a desired purity as appropriate through general purification operations such as filtration, washing, concentration, extraction, distillation, and column chromatographic separation.
このようにして得られた6−ヒドロキシ−2−ナフトエ酸アルケニルエステルは、アクリルゴムや抗菌性樹脂のモノマー、および工業用殺菌剤等として有用である。 The 6-hydroxy-2-naphthoic acid alkenyl ester thus obtained is useful as a monomer of acrylic rubber or an antibacterial resin, an industrial disinfectant, or the like.
以下、実施例により本発明を詳細に説明するが、本発明はこれに限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.
各化合物は以下の分析方法によって分析した。
<1H−NMRスペクトル>
サンプル10mgを重クロロホルム2mLで溶解し、Bruker Biospin AV400M(Bruker社製)を用いて、溶液状態での1H−NMRスペクトルを測定した。
Each compound was analyzed by the following analytical method.
< 1 1 H-NMR spectrum>
10 mg of the sample was dissolved in 2 mL of deuterated chloroform, and 1 1 H-NMR spectrum in a solution state was measured using Bruker Biospin AV400M (manufactured by Bruker).
<FT−IRスペクトル>
Spectrum One(PerkinElmer社製)を用いてFT−IRスペクトルを測定した。
<FT-IR spectrum>
The FT-IR spectrum was measured using Spectrum One (manufactured by PerkinElmer).
<MSスペクトル>
Waters 2690/2996 Alliance−TQ Detectorを用いてMSスペクトルを測定した。
<MS spectrum>
MS spectra were measured using Waters 2690/2996 Alliance-TQ Detector.
<高速液体クロマトグラフィー(HPLC)>
装置: Waters アライアンス 2690/2996
カラム型番: L−Column
液量: 1.0mL/分
溶媒比: H2O(pH2.3)/CH3OH=50/50(4分)→25/75(20分)→10/90(14分)、グラジエント分析
波長: 229nm
カラム温度: 40℃
尚、6−ヒドロキシ−2−ナフトエ酸メタリルエステルの純度は、HPLCチャートの面積%から算出した。
<High Performance Liquid Chromatography (HPLC)>
Equipment: Waters Alliance 2690/2996
Column model number: L-Column
Liquid volume: 1.0 mL / min Solvent ratio: H 2 O (pH 2.3) / CH 3 OH = 50/50 (4 minutes) → 25/75 (20 minutes) → 10/90 (14 minutes), gradient analysis Wavelength: 229 nm
Column temperature: 40 ° C
The purity of 6-hydroxy-2-naphthoic acid metallyl ester was calculated from the area% of the HPLC chart.
実施例1
撹拌機、温度センサーおよび還流管を備えた2Lの4口フラスコに、6−アセトキシ−2−ナフトエ酸230.2g(1.0mol)、塩化チオニル130.9g(1.1mol)およびテトラヒドロフラン690.6gを加え、窒素気流下、撹拌しながら還流するまで昇温し、同温度で2.5時間撹拌した。次いで、18℃まで冷却した後、減圧によって溶媒を留去し、6−アセトキシ−2−ナフタレンカルボン酸クロリドの固体を得た。
Example 1
230.2 g (1.0 mol) of 6-acetoxy-2-naphthoic acid, 130.9 g (1.1 mol) of thionyl chloride and 690.6 g of tetrahydrofuran in a 2 L 4-neck flask equipped with a stirrer, a temperature sensor and a reflux tube. Was added, the temperature was raised to reflux while stirring under a nitrogen stream, and the mixture was stirred at the same temperature for 2.5 hours. Then, after cooling to 18 ° C., the solvent was distilled off by reduced pressure to obtain a solid of 6-acetoxy-2-naphthalenecarboxylic acid chloride.
続いて、そこへテトラヒドロフラン575gを加え、窒素気流下、撹拌しながらさらにβ−メタリルアルコール75.7g(1.05mol)およびピリジン83.1g(1.05mol)を加えた後、還流するまで昇温し、同温度で2時間撹拌した。その後、反応液を60℃まで冷却し、同温度で析出固体を濾別し、反応液を得た。 Subsequently, 575 g of tetrahydrofuran is added thereto, and 75.7 g (1.05 mol) of β-metharyl alcohol and 83.1 g (1.05 mol) of pyridine are further added with stirring under a nitrogen stream, and then the temperature rises until reflux is performed. It was warmed and stirred at the same temperature for 2 hours. Then, the reaction solution was cooled to 60 ° C., and the precipitated solid was filtered off at the same temperature to obtain a reaction solution.
得られた反応液の溶媒を減圧により留去し、6−ヒドロキシ−2−ナフトエ酸メタリルエステルを含む粗組成物を得た。そこへ、酢酸エチル460gおよび水230gを加え、撹拌後、静置し、有機層を抽出した。抽出した有機層の溶媒を減圧により留去し、6−アセトキシ−2−ナフトエ酸メタリルエステル310.9gを得た。 The solvent of the obtained reaction solution was distilled off under reduced pressure to obtain a crude composition containing 6-hydroxy-2-naphthoic acid metallyl ester. 460 g of ethyl acetate and 230 g of water were added thereto, and the mixture was stirred and allowed to stand to extract an organic layer. The solvent of the extracted organic layer was distilled off under reduced pressure to obtain 310.9 g of 6-acetoxy-2-naphthoic acid metalyl ester.
撹拌機、温度センサーおよび還流管を備えた2Lの4口フラスコに、得られた6−アセトキシ−2−ナフトエ酸メタリルエステル310.9gを加え、さらにメタノール310.9g、水310.9gおよび炭酸水素ナトリウム126.0gを加え、窒素気流下、撹拌しながら60℃まで昇温し、同温度で7時間撹拌した。次いで、反応液を18℃まで冷却した後、析出固体を濾別し、固形物356.6gを得た。 310.9 g of the obtained 6-acetoxy-2-naphthoic acid metalyl ester was added to a 2 L 4-neck flask equipped with a stirrer, a temperature sensor and a reflux tube, and 310.9 g of methanol, 310.9 g of water and hydrogen carbonate were further added. 126.0 g of sodium was added, the temperature was raised to 60 ° C. with stirring under a nitrogen stream, and the mixture was stirred at the same temperature for 7 hours. Then, the reaction solution was cooled to 18 ° C., and then the precipitated solid was filtered off to obtain 356.6 g of a solid.
撹拌機、温度センサーおよび還流管を備えた2Lの4口フラスコに、得られた固形物356.6gおよびメタノール360gを加えた後、窒素気流下、撹拌しながら60℃まで昇温し、同温度で析出固体を濾別し、反応液を得た。得られた反応液を別の4口フラスコに加え、60℃に保持したまま、さらに水212gを加えた。その後、反応液を18℃まで冷却した後、析出固体を濾別し、固形物を得た。得られた固形物を50%メタノール水240gで洗浄し、減圧乾燥することで6−ヒドロキシ−2−ナフトエ酸メタリルエステルの結晶213.4g(純度96.6%、収率88.1%)を得た。 After adding 356.6 g of the obtained solid and 360 g of methanol to a 2 L 4-neck flask equipped with a stirrer, a temperature sensor and a reflux tube, the temperature was raised to 60 ° C. with stirring under a nitrogen stream to the same temperature. The precipitated solid was separated by filtration to obtain a reaction solution. The obtained reaction solution was added to another 4-neck flask, and 212 g of water was further added while maintaining the temperature at 60 ° C. Then, the reaction solution was cooled to 18 ° C., and then the precipitated solid was filtered off to obtain a solid. The obtained solid was washed with 240 g of 50% methanol water and dried under reduced pressure to obtain 213.4 g of crystals of 6-hydroxy-2-naphthoic acid metalyl ester (purity 96.6%, yield 88.1%). Obtained.
得られた6−ヒドロキシ−2−ナフトエ酸メタリルエステルの結晶について1H−NMRスペクトル、FT−IRスペクトルおよびMSスペクトルを測定した。1H−NMRスペクトルを図1に、FT−IRスペクトルを図2に、MSスペクトルを図3に示す。
本発明の好ましい態様は以下を包含する。
〔1〕式(1)で表される6−ヒドロキシ−2−ナフトエ酸アルケニルエステル。
[化1]
(式中、nは0〜3の整数を示し、mは0〜3の整数を示す。)
〔2〕式(1)において、nが1であり、かつ、mが1である、〔1〕に記載の6−ヒドロキシ−2−ナフトエ酸アルケニルエステル。
〔3〕式(2)で表される6−アセトキシ−2−ナフトエ酸ハライドと式(3)で表されるアルケニルアルコールを反応させる工程を含む、〔1〕または〔2〕に記載の6−ヒドロキシ−2−ナフトエ酸アルケニルエステルの製造方法。
[化2]
(式中、Acはアセチル基を示し、Xは塩素原子または臭素原子またはヨウ素原子を示す。)
[化3]
(式中、nは0〜3の整数を示し、mは0〜3の整数を示す。)
1 H-NMR spectrum, FT-IR spectrum and MS spectrum were measured for the obtained crystals of 6-hydroxy-2-naphthoic acid metalyl ester. 1 The 1 H-NMR spectrum is shown in FIG. 1, the FT-IR spectrum is shown in FIG. 2, and the MS spectrum is shown in FIG.
Preferred embodiments of the present invention include:
[1] A 6-hydroxy-2-naphthoic acid alkenyl ester represented by the formula (1).
[Chemical 1]
(In the formula, n indicates an integer of 0 to 3, and m indicates an integer of 0 to 3.)
[2] The 6-hydroxy-2-naphthoic acid alkenyl ester according to [1], wherein n is 1 and m is 1 in the formula (1).
[3] The 6-described in [1] or [2], which comprises a step of reacting the 6-acetoxy-2-naphthoic acid halide represented by the formula (2) with the alkenyl alcohol represented by the formula (3). A method for producing a hydroxy-2-naphthoic acid alkenyl ester.
[Chemical 2]
(In the formula, Ac represents an acetyl group and X represents a chlorine atom, a bromine atom or an iodine atom.)
[Chemical 3]
(In the formula, n indicates an integer of 0 to 3, and m indicates an integer of 0 to 3.)
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