JPS6345272A - Production of substituted-4-chromanone compound - Google Patents
Production of substituted-4-chromanone compoundInfo
- Publication number
- JPS6345272A JPS6345272A JP15802886A JP15802886A JPS6345272A JP S6345272 A JPS6345272 A JP S6345272A JP 15802886 A JP15802886 A JP 15802886A JP 15802886 A JP15802886 A JP 15802886A JP S6345272 A JPS6345272 A JP S6345272A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- formula
- chromanone
- compound
- chromanones
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 substituted-4-chromanone compound Chemical class 0.000 title description 7
- 238000004519 manufacturing process Methods 0.000 title description 5
- BUSOTUQRURCMCM-UHFFFAOYSA-N 3-Phenoxypropionic acid Chemical class OC(=O)CCOC1=CC=CC=C1 BUSOTUQRURCMCM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract 2
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 238000006798 ring closing metathesis reaction Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- 239000002253 acid Substances 0.000 abstract description 17
- 239000002994 raw material Substances 0.000 abstract description 10
- 239000002699 waste material Substances 0.000 abstract description 7
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 abstract description 6
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 4
- 239000003504 photosensitizing agent Substances 0.000 abstract description 4
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000007363 ring formation reaction Methods 0.000 abstract 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000002904 solvent Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 7
- SWBBIJZMIGAZHW-UHFFFAOYSA-N 6-fluoro-2,3-dihydrochromen-4-one Chemical compound O1CCC(=O)C2=CC(F)=CC=C21 SWBBIJZMIGAZHW-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- MSTDXOZUKAQDRL-UHFFFAOYSA-N 4-Chromanone Chemical class C1=CC=C2C(=O)CCOC2=C1 MSTDXOZUKAQDRL-UHFFFAOYSA-N 0.000 description 5
- 239000005457 ice water Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- PVWQUIQBDIXHSA-UHFFFAOYSA-N 2,2-dimethoxy-3H-chromen-4-one Chemical compound COC1(OC2=CC=CC=C2C(C1)=O)OC PVWQUIQBDIXHSA-UHFFFAOYSA-N 0.000 description 1
- SXERGJJQSKIUIC-UHFFFAOYSA-N 2-Phenoxypropionic acid Chemical class OC(=O)C(C)OC1=CC=CC=C1 SXERGJJQSKIUIC-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- GQRWYCNYSHFLAI-UHFFFAOYSA-N 2-nitro-2,3-dihydrochromen-4-one Chemical class [N+](=O)([O-])C1OC2=C(C(C1)=O)C=CC=C2 GQRWYCNYSHFLAI-UHFFFAOYSA-N 0.000 description 1
- FOIVIMILEOKLCH-UHFFFAOYSA-N 3-(2,4-dimethylphenoxy)propanoic acid Chemical compound CC1=CC=C(OCCC(O)=O)C(C)=C1 FOIVIMILEOKLCH-UHFFFAOYSA-N 0.000 description 1
- OWHJDUCBLVMRBJ-UHFFFAOYSA-N 3-(4-chlorophenoxy)propanoic acid Chemical compound OC(=O)CCOC1=CC=C(Cl)C=C1 OWHJDUCBLVMRBJ-UHFFFAOYSA-N 0.000 description 1
- RRQDYEMTBDVXQY-UHFFFAOYSA-N 3-(4-nitrophenoxy)propanoic acid Chemical compound OC(=O)CCOC1=CC=C([N+]([O-])=O)C=C1 RRQDYEMTBDVXQY-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- IYQNYCVNEQXHGU-UHFFFAOYSA-N 6,8-difluoro-2,3-dihydrochromen-4-one Chemical compound O1CCC(=O)C2=CC(F)=CC(F)=C21 IYQNYCVNEQXHGU-UHFFFAOYSA-N 0.000 description 1
- NBHOWUREPUUWOL-UHFFFAOYSA-N 6,8-dimethyl-2,3-dihydrochromen-4-one Chemical compound O1CCC(=O)C2=CC(C)=CC(C)=C21 NBHOWUREPUUWOL-UHFFFAOYSA-N 0.000 description 1
- PFLPVOXSUCCZDH-UHFFFAOYSA-N 6-bromo-2,3-dihydrochromen-4-one Chemical compound O1CCC(=O)C2=CC(Br)=CC=C21 PFLPVOXSUCCZDH-UHFFFAOYSA-N 0.000 description 1
- LLTDYHFVIVSQPJ-UHFFFAOYSA-N 6-chloro-2,3-dihydrochromen-4-one Chemical compound O1CCC(=O)C2=CC(Cl)=CC=C21 LLTDYHFVIVSQPJ-UHFFFAOYSA-N 0.000 description 1
- LQIYOSKKKUPTRP-UHFFFAOYSA-N 6-methoxy-2,3-dihydrochromen-4-one Chemical compound O1CCC(=O)C2=CC(OC)=CC=C21 LQIYOSKKKUPTRP-UHFFFAOYSA-N 0.000 description 1
- RJHXEPLSJAVTFW-UHFFFAOYSA-N 6-methyl-2,3-dihydrochromen-4-one Chemical compound O1CCC(=O)C2=CC(C)=CC=C21 RJHXEPLSJAVTFW-UHFFFAOYSA-N 0.000 description 1
- KUAWMWVXZMQZLD-UHFFFAOYSA-N 6-nitro-2,3-dihydrochromen-4-one Chemical compound O1CCC(=O)C2=CC([N+](=O)[O-])=CC=C21 KUAWMWVXZMQZLD-UHFFFAOYSA-N 0.000 description 1
- VWENHHJICDZGQB-UHFFFAOYSA-N 8-chloro-2,3-dihydrochromen-4-one Chemical compound O=C1CCOC2=C1C=CC=C2Cl VWENHHJICDZGQB-UHFFFAOYSA-N 0.000 description 1
- 229940118148 Aldose reductase inhibitor Drugs 0.000 description 1
- QWOJMRHUQHTCJG-UHFFFAOYSA-N CC([CH2-])=O Chemical compound CC([CH2-])=O QWOJMRHUQHTCJG-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000003288 aldose reductase inhibitor Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- MNQZXJOMYWMBOU-UHFFFAOYSA-N glyceraldehyde Chemical compound OCC(O)C=O MNQZXJOMYWMBOU-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Pyrane Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は中間体の製造方法に関する。更に詳しくは医薬
、農薬、光増感剤の原料として有用なりロマノン誘導体
の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for producing intermediates. More specifically, the present invention relates to a method for producing romanone derivatives, which are useful as raw materials for medicines, agricultural chemicals, and photosensitizers.
従来の技術
本発明で目的とする置換−４−クロマノンは医薬、農薬
、光増感剤等の原料として有用な化合物である。特に、
６−フルオロ−４−クロマノンは、アルドースレダクタ
ーゼ阻害剤として糖尿病の治療に用いられる「ツルビニ
ル」トシて知られろ医薬品の中間体として重要である。BACKGROUND OF THE INVENTION Substituted-4-chromanone, which is the object of the present invention, is a compound useful as a raw material for medicines, agricultural chemicals, photosensitizers, and the like. especially,
6-Fluoro-4-chromanone is important as an intermediate in the pharmaceutical product known as "Turvinyl", which is used in the treatment of diabetes as an aldose reductase inhibitor.
４−クロマノン類の製造方法についての従来の技術とし
て例えば、特開昭５３−５３６５３゜特開昭６０−１３
７７４等に記載されている様シζ３− （，１−フルオ
ロフェノキシ）フロピオン酸にポリリン酸を作用させる
事により、粗６−フルオロー４−クロマノンとなしこれ
を再結晶（精製）して目的物をえる方法が知られている
。Conventional techniques for producing 4-chromanones include, for example, JP-A-53-53653 and JP-A-60-13.
774 etc. By reacting polyphosphoric acid with ζ3-(,1-fluorophenoxy)furopionic acid, crude 6-fluoro-4-chromanone is obtained, which is recrystallized (purified) to obtain the target product. There are known ways to
また、Ｊ、Ａｍ、Ｃｈｅｍ−８ｏｃ、 ７６、５０６５
（］ ９５４）においては、３−（４−クロロフェノ
キシ）プロピオン酸又は、３−（４−ニトロフェノキシ
）プロピオン酸を、ａ硫酸で脱水閉環し、６６％の収率
で６−クロロ−４−クロマノンを、又１７％の収率で６
−二トロー４−クロマノンを得ている。Also, J, Am, Chem-8oc, 76, 5065
(] 954), 3-(4-chlorophenoxy)propionic acid or 3-(4-nitrophenoxy)propionic acid was dehydrated and ring-closed with a sulfuric acid to form 6-chloro-4- with a yield of 66%. Chromanone was also converted into 6 with a yield of 17%.
- ditro-4-chromanone is obtained.
また、３−フェノキシプロピオン酸類な、五塩化リン、
や塩化チオニル等で、相当する醸クロライドとし、塩化
アルミニウムや塩化第二鉄等のルイス酸触媒で、フリー
デルクラフッ型の反応を行いクロマノン類を製造する方
法等も容易に考えられる方法である。ベンゼン系の溶媒
中五酸化リンで脱水閉環する事もよく知られている。（
例えば、Ｊ、 Ｉｎｄｉａｎ−Ｃｈｅｍ−Ｓｏｃ・］
６．６３９（］９３９））
発明が解決しようとする問題点
従来の技術においては、いづれも試薬が高価であるとか
、反応の収率が悪いとか、得られろ目的物の純度が悪い
とか、反応中や、反応後の操作がやっかいであるとか、
又廃棄物処理の問題があったりして工業的有利さで置換
−４−クロマノン類を製造する方法が確立されていると
はいいがたい。例えば、ボＩＪ ＩＪン酸を用いる方法
では、収率は約９０％とかなり高いが、ポリリン酸は、
高価であり、廃棄物の処理に大きな問題がある。Also, 3-phenoxypropionic acids, phosphorus pentachloride,
Another method that can easily be considered is to produce chromanones by using a corresponding chloride such as chloride or thionyl chloride, and performing a Friedel-Crach-type reaction with a Lewis acid catalyst such as aluminum chloride or ferric chloride. . Dehydration and ring closure with phosphorus pentoxide in a benzene-based solvent is also well known. (
For example, J. Indian-Chem-Soc.]
6.639 (]939)) Problems to be solved by the invention In conventional techniques, the reagents are expensive, the reaction yield is poor, and the purity of the target product is poor. Operations during or after the reaction are difficult.
Furthermore, it cannot be said that a method for producing substituted-4-chromanones with industrial advantage has been established due to the problem of waste disposal. For example, the method using phosphoric acid has a fairly high yield of about 90%, but polyphosphoric acid
It is expensive and there are major problems in waste disposal.
また、この方法で得られる目的物の純度が悪いので、再
結晶又は昇華等による精製が必要であると特開昭５３−
５３６５３及び特開昭６０−１３７７４に記載されてい
る。In addition, since the purity of the target product obtained by this method is poor, purification by recrystallization or sublimation is necessary.
53653 and JP-A-60-13774.
濃硫酸を用いろ閉環法では収率が低く、ぼた、多量の廃
硫酸の処理に問題もある。The ring-closing method using concentrated sulfuric acid has a low yield, and there are also problems in processing waste sulfuric acid and large amounts of waste sulfuric acid.
酸クロライドを経由し、フリーデルクラフッ型の反応を
おこさせる場合は、高価な試薬を必要とし、また繰作が
繁雑であり、酸クロライドの様な活性の高い状態を経由
するために、分子間の反応や溶媒との反応か起きるとい
った欠点が考えられる。ベンゼン系の溶媒中で五酸化リ
ンを使用する方法も、やはり試薬が高価であるとか、廃
棄物の問題、溶媒との反応が起きるといった様な問題が
ある。When a Friedel-Crach-type reaction occurs via an acid chloride, expensive reagents are required, and the steps are complicated. Possible drawbacks include reactions between the molecules and the solvent. The method of using phosphorus pentoxide in a benzene-based solvent also has problems such as expensive reagents, waste, and reactions with the solvent.
問題点を解決するための手段
本発明は、上記の問題を解決すべく鋭意研究を重ねた結
果、ハロゲノスルホン酸又ハ、ＳＯ３を使用して３−フ
ェノキシプロピオン酸誘導体を脱水閉環せしめ目的物を
えろという方法により前記したような問題点を解決でき
ろことを見出し、本発明を完成させた。Means for Solving the Problems As a result of intensive research to solve the above-mentioned problems, the present invention has been developed by dehydrating and ring-closing a 3-phenoxypropionic acid derivative using halogenosulfonic acid or SO3 to obtain the desired product. The inventors discovered that the above-mentioned problems could be solved by a method called Ero, and completed the present invention.
、ｉ’ｏら本発明は式（２）
（式（２）にな（・てＸ、Ｙ及びＺはそれぞれ独豆にＨ
、Ｆ 、 ｃｌ、 Ｂｒ、 ＮＯ２，Ｃ１−４の７．レ
キ、又レエＣ＋−４のアルコキシを表す。但しＸ、Ｙ、
Ｚが共にＨを表すことはない）
で示すれる３−フェノキシプロピオン酸誘導体をＷＳＯ
，Ｈ（ＷはＦ又はＣＩを表す）又はＳＯ，の存在下に脱
水閉環することを特徴とする式（１）（式（１）におい
てＸ、Ｙ及びＺは前記と同じ意味を表す）
で示される置換−４−クロマノン類の製造方法を提供す
る。, i'o et al.
, F, cl, Br, NO2, 7 of C1-4. Reki, also represents alkoxy of Reki C+-4. However, X, Y,
(Z does not both represent H) 3-phenoxypropionic acid derivative represented by
, H (W represents F or CI) or SO, (in formula (1), X, Y and Z have the same meanings as above) A method for producing the substituted-4-chromanones shown is provided.
本発明の方法は安価な試薬を使用し、簡単な操作により
高収率で目的物をえろことができるので工業的メリット
が極めて大きい。なお廃棄物処理の問題も脱水閉環剤（
ＷＳＯ３Ｈ）としてクロルスルホン酸（ＣＩＳＯ３Ｈ）
又はＳＯ３ヲ用いた場合には工業的と大きな支障になる
ことはない。The method of the present invention uses inexpensive reagents and can obtain the target product in high yield through simple operations, so it has extremely large industrial merits. Furthermore, the issue of waste treatment is also caused by dehydrating ring-closing agents (
Chlorsulfonic acid (CISO3H) as WSO3H)
Alternatively, if SO3 is used, there will be no major problem industrially.
本発明の方法を実施するに当り、脱水閉環剤として用い
ろハロゲノスルホン酸（Ｗ ＳＯ３Ｈ）はクロロスルホ
ン酸又はフルオロスルホン酸であり、クロロスルホン酸
が特に優れている。これらの使用量は、原料である前記
式（２）で示されろ３−フェノキシプロピオン酸誘導体
の０．８倍モル力ら１０倍モル、好ましくは】〜５倍モ
ルである。−・ロゲノスルホン酸はできるだけ純粋なも
のがよいが、ハロゲン化水素、硫酸等を若干含むもので
あっても差しつかえないが、これらの不純物が多量に存
在すると収率低下を招くおそれがある。又ＳＯ３として
は無水硫酸、又は発煙硫酸の形で用いる事ができるが、
発煙硫酸の場合は、できるだけ高濃度のものが望ましい
。In carrying out the method of the present invention, the halogenosulfonic acid (WSO3H) used as the dehydration ring-closing agent is chlorosulfonic acid or fluorosulfonic acid, with chlorosulfonic acid being particularly preferred. The amount of these to be used is 0.8 to 10 times the molar amount of the 3-phenoxypropionic acid derivative represented by the above formula (2), which is the raw material, and preferably 1 to 5 times the molar amount. -.logenosulfonic acid is preferably as pure as possible, but it may contain some hydrogen halide, sulfuric acid, etc., but the presence of large amounts of these impurities may lead to a decrease in yield. Also, SO3 can be used in the form of sulfuric anhydride or fuming sulfuric acid,
In the case of fuming sulfuric acid, it is desirable to have as high a concentration as possible.
３０％程度以上の発煙硫酸を用いた時、良い結果が得ら
れる。その使用量はＳ０３として３−フェノキシ−プロ
ピオン酸誘導体の１〜６倍モル特に１．５〜４倍モルが
最適である。Good results are obtained when using oleum of about 30% or more. The optimal amount to be used is 1 to 6 times the mole of the 3-phenoxy-propionic acid derivative as S03, especially 1.5 to 4 times the mole.
式（１）で示される本発明の目的とする化合物のり１１
としては例えば６−フルオロ−４−りＱ−ｚ／ン、６−
クロロ−４−クロマノン、６−７’ロモ−４−クロマノ
ン、８−フルオロ−４−１０マノン、８−クロロ−４−
クロマノン、８−クロモ−４−クロマノン等のハロゲノ
−４−クロマノン類、６−メチル−４−クロマノン、６
−イソプロビル−４−クロマノン等のアルキル−４−ク
ロマノン類、６−メドキシー４−クロマノア 等ノフル
コキシクロマノン急、６−二トロー４−クロマノン等の
ニトロ−４−クロマノン類、６、８−ジフルオロ−４−
クロマノン、８−１０ロー６−フルオロ−４−クロマノ
ン、５，８−ジクロロ−４−１０マノン、６．７−シフ
ルオロー４−１’ロマノン、５．８−ジフルオロ−４−
１０マノン等のジハロゲノ−４−クロマノン類、６゜８
−ジメチル−４−クロマノン、６，７−シメチルー４−
クロマノン、６−インプロビル−８−メチル−４−クロ
マノン等のジアルキル−４−クロマノン類、６．７−シ
メトキシー４−クロマノン等のジメトキシ−４−クロマ
ノン類、８−フルオロ−６−メドキシー４−クロマノン
等のアルコキシ−ハロゲノ−４−りｏマ／ン類、５．３
−シ’／ロロー６−メトキシー４−クロマノン、５．８
−ジフルオロ−６−メドキシー４−クロマノン等のアル
コキシ−ジハロゲノ−４−クロマノン類、８−クロロ−
６−メチル−４−１０マノン＋ ６−フルオロ−８−メ
チル−４−１０マノン等のアルキル−ハロゲン−４−ク
ロマノン類等をあげることができる。Compound 11 of the object of the present invention represented by formula (1)
For example, 6-fluoro-4-riQ-z/n, 6-
Chloro-4-chromanone, 6-7'lomo-4-chromanone, 8-fluoro-4-10manone, 8-chloro-4-
Chromanone, halogeno-4-chromanones such as 8-chromo-4-chromanone, 6-methyl-4-chromanone, 6
- Alkyl-4-chromanones such as isoprobyl-4-chromanone, 6-medoxy-4-chromanoa, etc. Noflukoxychromanone, nitro-4-chromanones such as 6-nitro-4-chromanone, 6,8- difluoro-4-
Chromanone, 8-10ro-6-fluoro-4-chromanone, 5,8-dichloro-4-10manone, 6.7-cyfluoro-4-1'romanone, 5.8-difluoro-4-
Dihalogeno-4-chromanones such as 10 manone, 6°8
-dimethyl-4-chromanone, 6,7-dimethyl-4-
Dialkyl-4-chromanones such as chromanone, 6-improvir-8-methyl-4-chromanone, dimethoxy-4-chromanone such as 6,7-simethoxy-4-chromanone, 8-fluoro-6-medoxy-4-chromanone Alkoxy-halogeno-4-riomanes such as 5.3
-Si'/Roro 6-methoxy 4-chromanone, 5.8
-Alkoxy-dihalogeno-4-chromanones such as difluoro-6-medoxy-4-chromanone, 8-chloro-
Examples include alkyl-halogen-4-chromanones such as 6-methyl-4-10 manone + 6-fluoro-8-methyl-4-10 manone.
又式（２）で示される本発明で原料として用いる３一フ
エノキシプロビオン駿誘導体の具体例としては矢のよう
なものが挙げられる。Specific examples of the 3-phenoxyprobion Shun derivative represented by formula (2) used as a raw material in the present invention include arrow-like derivatives.
反応は、式（２）の３−フェノキシプロピオン酸誘導体
を溶媒の存在下、又は非存在下で・・ロゲノスルホン酸
又は８０３と一３０〜＋１００°Ｃ好讐しくは、−１０
℃〜＋７０℃の温度で接１独させることにより実施され
る。この際の溶媒としては、水反応条件下でハロゲノス
ルホン酸又は８０３ど反応しないものを使用するのがよ
くその例をあげると、塩ｆヒメチレン、クロロホルム、
四塩化炭素、塩化エチレン、パークレン等の脂肪族・・
ロゲン化炭化水素類、ヘキサン、ヘプタン、オクタン等
の脂肪族炭化水素類、ニトロベンゼン、クロロベンゼン
、ジクロロベンゼン等のニトロ又はハロゲン化芳香族炭
化水素類、アセトニドＩＪ ル、プロピオニトリル等の
脂肪族ニトリル類、ニトロメタン、ニトロエタン等の脂
肪族ニトロ化合物類、ギ酸、酢酸、プロピオン酸等の低
級脂肪酸類等をあげることができるが、特に、これらに
限定されるものではない。The reaction is carried out by combining the 3-phenoxypropionic acid derivative of formula (2) with logenosulfonic acid or 803 in the presence or absence of a solvent at 30 to +100°C, preferably at -10°C.
It is carried out by contacting at a temperature of 0.degree. C. to +70.degree. As a solvent in this case, it is best to use a solvent that does not react under water reaction conditions, such as halogenosulfonic acid or 803, for example, salt f himethylene, chloroform,
Aliphatics such as carbon tetrachloride, ethylene chloride, perchloride, etc.
halogenated hydrocarbons, aliphatic hydrocarbons such as hexane, heptane, octane, nitro or halogenated aromatic hydrocarbons such as nitrobenzene, chlorobenzene, dichlorobenzene, aliphatic nitrites such as acetonide, propionitrile, etc. , aliphatic nitro compounds such as nitromethane and nitroethane, and lower fatty acids such as formic acid, acetic acid and propionic acid, but are not particularly limited to these.
溶媒の使用量は、原料である３−フェノキシプロビン酸
誘導体に対し１〜１０重量倍程度使用するのが適当であ
る。The appropriate amount of the solvent to be used is about 1 to 10 times the weight of the 3-phenoxyprobic acid derivative as the raw material.
場合によっては、溶媒を用いず、・・ロゲノスルホン酸
又は発煙硫酸の中に３−フェノキシプロピオン酸類を徐
々に添加して反応させることも出来る。In some cases, the reaction may be carried out by gradually adding 3-phenoxypropionic acids to logenosulfonic acid or fuming sulfuric acid without using a solvent.
溶某を用いる場合には、溶媒中に式（２）で示される３
−フェノキシプロピオン酸誘導体を溶着又は：′ひ濁さ
せておき、ハロゲノスルホン酸又は発煙１−酸を滴下す
る方告か好ましい。When using a certain solution, 3 shown by formula (2) in the solvent
- It is preferable to weld the phenoxypropionic acid derivative or to leave it cloudy and then dropwise dropwise added halogenosulfonic acid or fuming acid.
反応時間は原料の種類、反応温度、・・ロゲノスルホン
酸又はＳ０３の使用清洗より変わるが通常の条件下では
０５時間から８時間程度で完結させるのが好ましい。The reaction time varies depending on the type of raw materials, the reaction temperature, and the use and washing of logenosulfonic acid or S03, but under normal conditions, it is preferable to complete the reaction in about 0.5 to 8 hours.
反応終了後は、反応液を氷水中に注ぎ、溶媒抽出により
目的物を採取するか、目的物が結晶として析出する場合
には濾過により取り出す。After the reaction is completed, the reaction solution is poured into ice water and the target product is collected by solvent extraction, or if the target product precipitates as crystals, it is removed by filtration.
本発明の方法によってえられる置換−４−クロマノン類
は十分な細度を有するのでこのま１医薬、農薬、光増感
剤の原料として用いられるが必要に応じて再結晶などに
よって精製してもよい。Since the substituted-4-chromanones obtained by the method of the present invention have sufficient fineness, they can be used as raw materials for pharmaceuticals, agricultural chemicals, and photosensitizers, but if necessary, they can be purified by recrystallization etc. good.
本発明の方法は、高価な原料を用いることもなく高純度
、高収率で置換−４−クロマノン順をえることができる
ので工業的価値が極めてたかい。The method of the present invention has extremely high industrial value because it can produce substituted 4-chromanone with high purity and high yield without using expensive raw materials.
実施例 本発明を実施例により具体的に説明する。Example The present invention will be specifically explained with reference to Examples.
実施例１゜
ｓｏｍｉのフラスコ中にクロロスルホン酸４１０ｇ仕込
み、水浴で３〜５℃に冷却しつつ、３−（４−フルオロ
フェノキシ）フロピオン酸５ｇを１時間を要して徐々に
添加した。仕込終了後、０．５時間借拝し、２０ｇの氷
と２０ｇの水を攪拌している中に徐々に反応混合物を注
ぎ沈殿を生成させた。この沈殿を戸別し水洗した。Example 1 410 g of chlorosulfonic acid was placed in a flask of 2.0 mm, and 5 g of 3-(4-fluorophenoxy)furopionic acid was gradually added over 1 hour while cooling the flask to 3-5° C. in a water bath. After the preparation was completed, the reaction mixture was gradually poured into a stirred mixture of 20 g of ice and 20 g of water for 0.5 hour to form a precipitate. This precipitate was taken from house to house and washed with water.
デシケータで乾Ｄｉ、白色の６−フルオロ−４−クロマ
ノンが３．７１ｇ得られた。融点は、１１５〜１１７．
５°Ｃ１収率は８２．３％、ＧＣ純度は９９９％（ＧＣ
測定条件後記）であった。3.71 g of white 6-fluoro-4-chromanone was obtained by drying Di in a desiccator. The melting point is 115-117.
5°C1 yield is 82.3%, GC purity is 999% (GC
Measurement conditions (see below) were met.
実施例２゜
５０ｍ１のフラスコに塩化メチレン２０ｇ及び３−（４
−フルオロフェノキシクープロピオン酸５ｇを仕込み撹
拌しつつ３〜５℃に冷却した。Example 2 20 g of methylene chloride and 3-(4
- 5 g of fluorophenoxycupropionic acid was charged and cooled to 3 to 5° C. with stirring.
ここ疋、６．３ｇのクロロスルホン酸を０．５時間を要
して滴下し、滴下終了後５℃てて３時間攪拌した。これ
を氷水中にあけ、塩化メチレンを５０ｇ追加して抽出し
た。Then, 6.3 g of chlorosulfonic acid was added dropwise over 0.5 hours, and after the dropwise addition was completed, the mixture was heated to 5° C. and stirred for 3 hours. This was poured into ice water and extracted with an additional 50 g of methylene chloride.
塩化メチレン層を薄い力性ソーダ水＠？Ｊｔ ］ Ｏｍ
ｌで洗浄した。ロータリーエバポレータで塩化メチレン
を留去すると白色の６−フルオロ−４−クロマノンが得
られた。６０°Ｃで乾燥した後、収量は、４．０７ｇで
あり、収率は９０２％であった。融点は１１６〜１１８
°Ｃを示した。ガスクロマトグラフによる細度は９９．
９％であった。Add diluted methylene chloride layer to diluted soda water @? Jt ] Om
Washed with l. Methylene chloride was distilled off using a rotary evaporator to obtain white 6-fluoro-4-chromanone. After drying at 60°C, the yield was 4.07g, with a yield of 902%. Melting point is 116-118
It showed °C. Fineness measured by gas chromatography is 99.
It was 9%.
実施例３゜
溶媒として、２０ｇの塩化エチレンを用いた他は、実施
例２と同様に反応させた。反応終了後氷水アケして塩化
メチレンで同様に処理して４．１ｇの６−フルオロ−４
−クロマノン類得り。Example 3 The reaction was carried out in the same manner as in Example 2, except that 20 g of ethylene chloride was used as the solvent. After the reaction was completed, it was washed with ice water and treated in the same manner with methylene chloride to give 4.1 g of 6-fluoro-4.
- Obtaining chromanones.
収率は９】％であり、融点は１１６〜】１８℃を示した
。ＧＣＩ度は９９．９％であった。The yield was 9%, and the melting point was 116-18°C. The GCI degree was 99.9%.
実、層側４〜］ １゜
実７施例２に進じて５種々の４−クロマノン類を得たう
結果を表にして示す。生成物はいづれもＭａｓｓスペク
トルで最大ピークが分子量と一致した。In fact, layer side 4~] 1° Example 7 Proceeding to Example 2, five different 4-chromanones were obtained. The results are shown in a table. The maximum peak of each product in the mass spectrum matched the molecular weight.
実施例］ ２゜
５０ ｍｌのフラスコに塩化メチレン２５ｇ及び３−
（１１−フルオロフェノキシ）−フロピオン酸５ｇを仕
込み攪拌した。これを０℃に冷却しここに６０％発煙硫
酸７．２５ ｇを４０分で滴下した。温度は５°Ｃ以下
に保持した。滴下終了後２°Ｃで３０分遣拌し反応を、
終了した。これを４．３ｇの力性ソーダを俗解している
水１２ｇ中に１５゛Ｃ以下で／坏下した。温度が上昇し
ない様に氷４０ｇを途中で添加した。この後ｐＨを８と
し、加熱して塩化メチレンを留去した。析出している結
晶を冷却後、戸別し、水洗、乾燥して３．９６ｇの６−
フルオロ−４−クロマノン類得た。収率は８８％であっ
た。Example] 25 g of methylene chloride and 3-
5 g of (11-fluorophenoxy)-furopionic acid was charged and stirred. This was cooled to 0°C, and 7.25 g of 60% oleum was added dropwise thereto over 40 minutes. The temperature was kept below 5°C. After the dropwise addition was completed, the reaction was stirred at 2°C for 30 minutes.
finished. 4.3 g of sodium hydroxide was added to 12 g of water at a temperature below 15°C. 40 g of ice was added halfway to prevent the temperature from rising. Thereafter, the pH was adjusted to 8, and methylene chloride was distilled off by heating. After cooling the precipitated crystals, they were separated, washed with water, and dried to give 3.96 g of 6-
Fluoro-4-chromanones were obtained. The yield was 88%.
融点は】１５〜】】７℃であり、ガスクロマトグラフで
の純度は９９９％であった。The melting point was 15 to 7°C, and the purity as measured by gas chromatography was 999%.
実施例］３゜
実施夕！１１２において６０％発煙硫酸７．２５ ｇの
かわりに３０％発煙硫酸】４５ｇを用い、１だ反応終了
後のクエンチは力性ソーダ１２．６ｇを含む２８％の水
溶液を用い、氷は７５ｇ使用する他は、実施例】２と同
様友して処理して６−フルオロ−４−クロマノンをエタ
。収量は３．７０ｇであり、収率は８２％であった。Example] 3゜ implementation evening! In 112, 45 g of 30% oleum was used instead of 7.25 g of 60% oleum, and for quenching after the completion of the reaction, a 28% aqueous solution containing 12.6 g of sodium hydroxide was used, and 75 g of ice was used. The rest was treated in the same manner as in Example 2 to evaporate 6-fluoro-4-chromanone. The yield was 3.70 g, and the yield was 82%.
融点は】】５〜１１７℃でありガスクロマトグラフでの
純度は９９８％であった。The melting point was 5-117°C, and the purity as determined by gas chromatography was 998%.
実施例１４゜
５０ｍ１フラスコに３−（４−ブロモフェノキシ）プロ
ピオンｆｆ１５ｇ、塩化メチレン３５ｇを仕込み、２℃
において６０％発煙ｔＡ酸５．７ｇを３０分で滴下し、
３°Ｃにて３０分間攪拌した。Example 14 15 g of 3-(4-bromophenoxy)propion ff and 35 g of methylene chloride were placed in a 50 ml flask and heated at 2°C.
5.7 g of 60% fuming tA acid was added dropwise over 30 minutes.
Stirred at 3°C for 30 minutes.
その後、多量の氷水中に注ぎ、塩化メチレン５０ｇを追
加して抽出した。塩化メチレン層を薄いカ性ソーダ水溶
腹で洗浄し、エバポレータで塩化メチレンを留去した。Thereafter, the mixture was poured into a large amount of ice water, and extracted with 50 g of methylene chloride. The methylene chloride layer was washed with a dilute aqueous solution of caustic soda, and the methylene chloride was distilled off using an evaporator.
乾燥後６−ブロモ−４−クロマノン３．５６ｇが得られ
、収率は７７％であった。融点は７８〜７９℃であり、
ガスクロマトグラフてよる純度は９７．１％であった。After drying, 3.56 g of 6-bromo-4-chromanone was obtained, with a yield of 77%. The melting point is 78-79°C,
Purity as determined by gas chromatography was 97.1%.
実施例】５゜
実ｂ１例１４と同様に５ｇの３−（２，４−ジメチルフ
ェノキシ）プロピオン酸を３．４ｇの６０％発煙硫酸を
用いて閉環した。３．２ｇの６，８−ジメチル−４−ク
ロマノンが得らね、収率は７１％であった。冷却しても
オイル状であり、ガスクロマトグラフ江よる純度）ま９
７％であった。（ガスクロマトグラフ条件は前記した条
件による）
発明の効果
ｅ換−４−クロマノン類が５安価な／−Ｏケンスルホン
酸又はＳＯ３を用いる墨により工業的に有利：（製造で
きる様になった。EXAMPLE 5゜Example b1 In the same manner as in Example 14, 5 g of 3-(2,4-dimethylphenoxy)propionic acid was ring-closed using 3.4 g of 60% oleum. 3.2 g of 6,8-dimethyl-4-chromanone was obtained, with a yield of 71%. It remains oily even after cooling, and its purity is determined by gas chromatography.
It was 7%. (Gas chromatography conditions are as described above.) Effects of the Invention E-substituted-4-chromanones can now be produced industrially by using inexpensive /-O kenesulfonic acid or SO3.
特許出頭入 日本化薬株式会社Patent filing Nippon Kayaku Co., Ltd.
Claims (1)
Ｆ、Ｃｌ、Ｂｒ、ＮＯ＿２、Ｃ＿１＿〜＿４のアルキル
又はＣ＿１＿〜＿４のアルコキシを表す。但しＸ、Ｙ、
Ｚが共にＨを表すことはない） で示される３−フェノキシプロピオン酸誘導体をＷＳＯ
＿３Ｈ（ＷはＦ又はＣｌを表す）又はＳＯ＿３の存在下
に脱水閉環することを特徴とする式（１） ▲数式、化学式、表等があります▼（１） （式（１）においてＸ、Ｙ及びＺは前記と同じ意味を表
す） で示される置換−４−クロマノン類の製造方法(1) Formula (2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2) (In formula (2), X, Y, and Z are each independently H,
Represents F, Cl, Br, NO_2, alkyl of C_1_ to_4, or alkoxy of C_1_ to_4. However, X, Y,
(Z does not both represent H) 3-phenoxypropionic acid derivative represented by
Formula (1) characterized by dehydration ring closure in the presence of _3H (W represents F or Cl) or SO_3 ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) (In formula (1), X, Y and Z have the same meanings as above)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7560486 | 1986-04-03 | ||
| JP61-75604 | 1986-04-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6345272A true JPS6345272A (en) | 1988-02-26 |
| JPH0613498B2 JPH0613498B2 (en) | 1994-02-23 |
Family
ID=13580977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15802886A Expired - Lifetime JPH0613498B2 (en) | 1986-04-03 | 1986-07-07 | Method for producing substituted-4-chromanones |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0613498B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008246832A (en) * | 2007-03-30 | 2008-10-16 | Fujifilm Corp | Ink set for inkjet recording, and inkjet recording method |
| EP2042563A1 (en) * | 2007-09-25 | 2009-04-01 | FUJIFILM Corporation | Photocurable coating composition, and overprint and process for producing same |
| JP2010024295A (en) * | 2008-07-16 | 2010-02-04 | Fujifilm Corp | Photocurable composition, ink composition and inkjet recording method using the ink composition |
-
1986
- 1986-07-07 JP JP15802886A patent/JPH0613498B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008246832A (en) * | 2007-03-30 | 2008-10-16 | Fujifilm Corp | Ink set for inkjet recording, and inkjet recording method |
| JP4601009B2 (en) * | 2007-03-30 | 2010-12-22 | 富士フイルム株式会社 | Ink set for inkjet recording and inkjet recording method |
| US8147921B2 (en) | 2007-03-30 | 2012-04-03 | Fujifilm Corporation | Ink set for inkjet recording and inkjet recording method |
| EP2042563A1 (en) * | 2007-09-25 | 2009-04-01 | FUJIFILM Corporation | Photocurable coating composition, and overprint and process for producing same |
| JP2010024295A (en) * | 2008-07-16 | 2010-02-04 | Fujifilm Corp | Photocurable composition, ink composition and inkjet recording method using the ink composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0613498B2 (en) | 1994-02-23 |
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