JP3545466B2 - Dihydrochromancarboxylic acids and method for producing the same - Google Patents
Dihydrochromancarboxylic acids and method for producing the same Download PDFInfo
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- JP3545466B2 JP3545466B2 JP24837894A JP24837894A JP3545466B2 JP 3545466 B2 JP3545466 B2 JP 3545466B2 JP 24837894 A JP24837894 A JP 24837894A JP 24837894 A JP24837894 A JP 24837894A JP 3545466 B2 JP3545466 B2 JP 3545466B2
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- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000002253 acid Substances 0.000 title description 3
- 150000007513 acids Chemical class 0.000 title 1
- 238000000034 method Methods 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- -1 5-methyl-7,8-dihydro-6-chromanic acid ester Chemical class 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 5
- 239000003880 polar aprotic solvent Substances 0.000 claims description 5
- 239000003799 water insoluble solvent Substances 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000003444 phase transfer catalyst Substances 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 229940117389 dichlorobenzene Drugs 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- MQSVLEXCVMBNIC-UHFFFAOYSA-N 5-methyl-3,4,7,8-tetrahydro-2H-chromene-6-carboxylic acid Chemical compound CC=1C=2CCCOC=2CCC=1C(=O)O MQSVLEXCVMBNIC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 150000002366 halogen compounds Chemical class 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 150000004714 phosphonium salts Chemical class 0.000 claims 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- YRNPLIQELBCWNK-UHFFFAOYSA-N ethyl 5-methyl-3,4,7,8-tetrahydro-2H-chromene-6-carboxylate Chemical compound CCOC(=O)C1=C(C)C2=C(CC1)OCCC2 YRNPLIQELBCWNK-UHFFFAOYSA-N 0.000 description 6
- MFESCIUQSIBMSM-UHFFFAOYSA-N I-BCP Chemical group ClCCCBr MFESCIUQSIBMSM-UHFFFAOYSA-N 0.000 description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 5
- 235000019341 magnesium sulphate Nutrition 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- VLTANIMRIRCCOQ-UHFFFAOYSA-N hagemann's ester Chemical compound CCOC(=O)C1CCC(=O)C=C1C VLTANIMRIRCCOQ-UHFFFAOYSA-N 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- OFLCFRRPJGEXIK-UHFFFAOYSA-N propan-2-yl 2-methyl-4-oxocyclohex-2-ene-1-carboxylate Chemical compound CC(C)OC(=O)C1CCC(=O)C=C1C OFLCFRRPJGEXIK-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 230000000749 insecticidal effect Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- QPIRAJBDZMEJQT-UHFFFAOYSA-N propan-2-yl 5-methyl-3,4,7,8-tetrahydro-2h-chromene-6-carboxylate Chemical compound O1CCCC2=C1CCC(C(=O)OC(C)C)=C2C QPIRAJBDZMEJQT-UHFFFAOYSA-N 0.000 description 3
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- SBYIWHPHFZBCCN-UHFFFAOYSA-N 5-methyl-3,4-dihydro-2h-chromene-6-carboxylic acid Chemical compound C1CCOC2=CC=C(C(O)=O)C(C)=C21 SBYIWHPHFZBCCN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003413 spiro compounds Chemical class 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- GRRIYLZJLGTQJX-UHFFFAOYSA-N 1,2-dibenzoylhydrazine Chemical compound C=1C=CC=CC=1C(=O)NNC(=O)C1=CC=CC=C1 GRRIYLZJLGTQJX-UHFFFAOYSA-N 0.000 description 1
- HYOAGWAIGJXNQH-UHFFFAOYSA-N 1-bromo-1-chloropropane Chemical compound CCC(Cl)Br HYOAGWAIGJXNQH-UHFFFAOYSA-N 0.000 description 1
- SFOYQZYQTQDRIY-UHFFFAOYSA-N 1-chloro-3-iodopropane Chemical compound ClCCCI SFOYQZYQTQDRIY-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 description 1
- MLMQPDHYNJCQAO-UHFFFAOYSA-N 3,3-dimethylbutyric acid Chemical compound CC(C)(C)CC(O)=O MLMQPDHYNJCQAO-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 0 CC1=C(*)CCC2=C1CCCO2 Chemical compound CC1=C(*)CCC2=C1CCCO2 0.000 description 1
- RMLBTDFFLRZUDJ-UHFFFAOYSA-N CC=1C=2CCCOC2CCC1C(=O)OC Chemical compound CC=1C=2CCCOC2CCC1C(=O)OC RMLBTDFFLRZUDJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000255777 Lepidoptera Species 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 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
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000950 dibromo group Chemical group Br* 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- AGOJIHXCXNTMPM-UHFFFAOYSA-N methyl 2-methyl-4-oxocyclohex-2-ene-1-carboxylate Chemical compound COC(=O)C1CCC(=O)C=C1C AGOJIHXCXNTMPM-UHFFFAOYSA-N 0.000 description 1
- LSEFCHWGJNHZNT-UHFFFAOYSA-M methyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 LSEFCHWGJNHZNT-UHFFFAOYSA-M 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- GVIIRWAJDFKJMJ-UHFFFAOYSA-N propan-2-yl 3-oxobutanoate Chemical compound CC(C)OC(=O)CC(C)=O GVIIRWAJDFKJMJ-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pyrane Compounds (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、殺虫活性を有することが知られている１ーアルキルー１、２ージベンゾイルヒドラジン類（特開平５ー１６３２６６号）を製造する工程に於ける有用な中間体であるクロマン酸の前駆体であるジヒドロクロマン酸類及びその製造方法に関する。該ヒドラジン類は農業用殺虫剤として有用である。
【０００２】
【従来の技術】
シクロヘキセノンエステルと１，３−ジブロモプロパンをｔ−ブタノール中ｔ−ブトキシドカリウムを用いて反応させジヒドロクロマンカルボン酸エステルを得る方法が知られている。（Ｊ．Ｉｎｄｉａｎ Ｃｈｅｍ．Ｓｏｃ．，４５，２００（１９６８））
また４ーオキソー２ーメチルー２ーシクロヘキセンカルボン酸エチルエステルは、
Ｈａｇｅｍａｎｎｓ エステルとして知られている。（Ｊ．Ａｍｅｒ．Ｃｈｅｍ．Ｓｏｃ．，６５，６３１（１９４３）、Ｊ．Ｃ．Ｓ．Ｐｒｅｋｉｎ１，６０２，１９７２）
【０００３】
【発明が解決しようとする課題】
従来の技術は工業的見地から見ると、危険性の面から扱い難く且つ高価であるｔ−ブトキサイド及び水溶性で回収の困難な溶媒（ｔ−ブタノール）を使用し、また精製の困難なスピロ化合物を副生するなど工業的製造法ではない。このため回収容易な溶媒を用い、安価で収率の良い工業的に有利な製法が望まれていた。
【０００４】
【課題を解決するための手段】
本発明は、下式（２）
【０００５】
【化６】
（式中、ＲはＣ１ 〜Ｃ６ の低級アルキル基を表わす。）
で表わされる４ーオキソー２ーメチルー２ーシクロヘキセンカルボン酸エステルと下式（３）
【０００７】
【化７】
（式中、Ｘ及びＹはハロゲン原子を表わす。）
で表わされるハロゲン化合物を反応させることによる下式（１）
【０００９】
【化８】
（式中、ＲはＣ１ 〜Ｃ６ の低級アルキル基を表す。）
で表わされる５ーメチル−７、８−ジヒドロ−６クロマン酸エステルの工業的に有利な製造方法に関するものである。
【００１１】
具体的には、（Ａ）塩基の存在下、水と非水溶性溶媒の２相系に於いて反応を行う方法と、（Ｂ）塩基の存在下、極性非プロトン性溶媒中で反応を行う方法を提供するものである。
すなわち本製法により、水酸化ナトリウムや炭酸カリウム等の安価な塩基を用い且つ収率良くジヒドロクロマン酸エステルを得る事ができる。
【００１２】
用いる非水溶性溶媒は、例えばジクロロメタン、クロロホルム、１，１，１−トリクロロエタン、テトラクロロエチレン、クロロベンゼン、ジクロロベンゼン等のハロゲン化炭化水素、メチルブチルケトン、酢酸ｔ−ブチルエステル、キシレン、トルエン、等の炭化水素をあげる事が出来る。好ましくは、ジクロロメタン、クロロベンゼン、ジクロロベンゼン、トルエン、キシレンである。
用いる極性非プロトン性溶媒としては、Ｎ−メチルピロリジノン（ＮＭＰ）、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡＣ）、Ｎ，Ｎ−ジメチルイミダゾリノン（ＤＭＩ）、ジメチルスルホキサイド（ＤＭＳＯ）等を挙げることが出来る。好ましくは、ＮＭＰ、ＤＭＡＣである。溶媒の使用量は、式（２）の化合物に対して２００ー１５００ｍｌ／ｍｏｌであり、好ましくは４００ー１０００ｍｌ／ｍｏｌである。
【００１３】
使用する塩基は、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム等のアルカリ金属及びアルカリ土類金属の水酸化物、炭酸ナトリウム、炭酸カリウム、炭酸カルシウム等のアルカリ及びアルカリ土類金属の炭酸塩をあげる事ができる。
水と非水溶性溶媒を用いる方法（Ａ法）の場合、好ましくは、水酸化ナトリウム及び水酸化カリウムが挙げられる。
極性非プロトン性溶媒を用いる方法（Ｂ法）の場合、好ましくは、炭酸カリウム、炭酸ナトリウムが挙げられる。
塩基の使用量は、式（２）の化合物に対して２ー８ｅｑ／ ｍｏｌであり、好ましくは２ー５ｅｑ／ ｍｏｌである。
塩基の濃度は、任意でもよいが生産性や反応速度を考慮するとできるだけ濃い方が好ましい。例えば（Ａ）法に於いて、水酸化ナトリウムを用いた場合には塩基の濃度が高いほど反応速度が速く、また反応機当たりの生産性も良い。水酸化ナトリウムの場合には水を用いずに固体（粒状から微粒状）のまま添加してもよい。
【００１４】
（Ａ）法に於いては、相間移動触媒を添加すると、反応速度を早める事が出来る。
使用する相間移動触媒はテトラブチルアンモニウムブロミド、テトラメチルアンモニウムクロリド、ベンジルトリメチルアンモニウムクロリド、ベンジルトリエチルアンモニウムクロリド、ベンジルトリブチルアンモニウムクロリド、メチルトリオクチルアンモニウムクロライド、メチルトリフェニルフォスフォニウムブロマイド、アミルトリフェニルフォスフォニウムブロマイドであり、好ましくはテトラブチルアンモニウムブロミド、メチルトリオクチルアンモニウムクロライドである。
相間移動触媒の添加量は式（２）で表わされる化合物に対して０．０１〜２０％当量であることが好ましい。
【００１５】
（Ｂ）法に於いては、ヨウ化カリウムを添加することにより収率が向上することを見いだした。添加するヨウ化カリウムの量は、式（２）の化合物に対して０．０５〜１．０当量であり、好ましくは０．１〜０．３当量である。
【００１６】
アルキル化及び環化に用いる式（３）で表される１、３ージハロゲノプロパンは、１、３ージクロロ、１、３ージブロモ、１、３ージヨード、１ークロロー３ーブロモ、１ークロロー３ーヨード、１ーブロモー３ーヨードプロパンを示す。
好ましくは、１ークロロー３ーブロモ、及び１ークロロー３ーヨードプロパンであり、さらに好ましくは１ークロロー３ーブロモプロパンである。
１、３ージハロゲノプロパンの使用量は、１ー５ｅｑ／ ｍｏｌであり、好ましくは（Ａ）法に於いては１〜１．５ｅｑ／ ｍｏｌ、（Ｂ）法に於いては１〜３ｅｑ／ｍｏｌである。
【００１７】
反応温度は、（Ａ）法に於いては０〜１００℃でよいが好ましくは０から６０℃である。（Ｂ）法に於いては５０〜溶媒の沸点が好ましく更に好ましくは９０〜１７０℃である。
【００１８】
式（１）及び式（２）で表される化合物の置換基の具体例としては、Ｒはメチル、エチル、プロピル等の直鎖アルキル及びイソプロピル、ｔ−ブチル、ｓｅｃーブチル等の分支アルキル基が挙げられる。ここで、Ｒとしてメチル基、エチル基及びｔ−ブチル基を除いた式（２）で示される４ーオキソー２ーメチルー２ーシクロヘキセンカルボン酸エステル、及びＲとしてエチル基を除いた式（１）で示される５ーメチルー７、８ージヒドロー６ークロマン酸エステルは文献未記載の化合物である。
【００１９】
式（１）の化合物は、酸化することにより５ーメチルー６ークロマン酸エステルとし、次いでエステル基を加水分解することにより５ーメチルー６ークロマン酸に導くことが出来る。該化合物は特開平５ー１６３２６６に記載されている鱗し目、半し目その他の害虫に対し優れた殺虫活性を有するジベンゾイルヒドラジン系化合物の原料として用いることができる。
【００２０】
【実施例】
以下に実施例をあげて本発明をさらに具体的に説明するが、本発明はこれのみに限定されるものではない。
【００２１】
実施例１ ５−メチル−７、８−ジヒドロ−６−クロマンカルボン酸エチルの製造
４−オキソ−２−メチル−２−シクロヘキセンカルボン酸エチル８０ｇ（純度９５％，０．４１８ｍｏｌ）、１−ブロモ−３−クロロプロパン６９ｇ（０．４４ｍｏｌ）及びテトラブチルアンモニウムブロマイド６．７ｇ（０．０２ｍｏｌ）をジクロロメタン３００ｍｌに溶解し、撹拌下２０−３０℃にて４８％苛性ソ−ダ水１３４ｇを滴下した。滴下終了後４０℃にて１時間撹拌後氷冷下１０℃以下にて水８０ｍｌを加えた。水層を分液後、有機層を水洗、乾燥（硫酸マグネシウム）、濃縮することによって淡褐色オイル１１１．３ｇを得た。このものの純度は５５．１％（ガスクロマトグラフィー、内部標準法）であり純収率は６６％であった。
この淡褐色オイルを減圧下蒸留することにより目的とする５−メチル−７、８−ジヒドロ−６−クロマンカルボン酸エチル５５．１ｇを得た。Ｂ．ｐ．１３０−１３５℃／ ２ｍｍＨｇ、融点：６８−９℃。
Ｈ−ＮＭＲ δ（ｐｐｍ） ４． １７（２Ｈ，ｑ，Ｊ＝７Ｈｚ），４．０１（２Ｈ，ｔ，Ｊ＝４．６Ｈｚ）、２．４５（２Ｈ，ｍ），２．１７（３Ｈ，ｓ），２．３−１．８（６Ｈ，Ｍ）
【００２２】
実施例２ ５ーメチルー７、８ージヒドロー６ークロマンカルボン酸イソプロピルの製造
４ーオキソー２ーメチルー２ーシクロヘキセンカルボン酸イソプロピル４０ｇ（純度９４．８％、０．１９３ｍｏｌ）、１−ブロモ−３−クロロプロパン３１．９ｇ（０．２０３ｍｏｌ）及びテトラブチルアンモニウムブロマイド１．２５ｇ（０．００３９ｍｏｌ）をクロロベンゼン９７ｍｌに溶解し、撹拌下３０℃にて４０％苛性ソーダ水４２．７ｇを滴下した。滴下終了後４０℃にて６時間撹拌後氷冷下１０℃以下にて水４０ｍｌを加えた。水層を分液後、有機層を水洗、乾燥（硫酸マグネシウム）、濃縮することによって淡褐色オイル７０．２ｇを得た。この淡褐色オイルを減圧下蒸留することにより目的とする５ーメチルー７、８ージヒドロー６ークロマンカルボン酸イソプロピル２７．３ｇを得た。Ｂ．ｐ．１３０ー１３５℃／ １、５ｍｍＨｇ。
【００２３】
実施例３ ５−メチル−７、８−ジヒドロ−６−クロマンカルボン酸メチルの製造
４−オキソ−２−メチル−２−シクロヘキセンカルボン酸メチル１０ｇ（純度８３％、０．０４９３ｍｏｌ）、ブロモクロロプロパン９．３ｇ（０．０５９１ｍｏｌ）及びテトラブチルアンモニウムブロマイド０．９ｇ（２．８ｍｍｏｌ）をジクロロメタン５０ｍｌに溶解し、撹拌下２０−２５℃にて４８％苛性ソーダ水１９ｇを滴下した。滴下終了後２５℃にて１時間、４０℃にて２時間撹拌後氷冷下水２０ｍｌを加えた。水層を分液後、有機層を水洗、乾燥（硫酸ナトリウム）、濃縮することによって淡褐色オイル１０．１ｇを得た。このオイルは室温で固化し、ＭｅＯＨから再結することによって白色結晶６ｇを得た。純収率５８％。
Ｍ．Ｐ．９０−９１℃
Ｈ−ＮＭＲ δ（ｐｐｍ） ４．００（２Ｈ，ｔ，Ｊ＝５Ｈｚ），３．７１（３Ｈ，ｓ）、２．４５（２Ｈ，ｍ），２．１７（３Ｈ，ｓ），２．３−１．８（６Ｈ，ｍ）
【００２４】
実施例４ ５ーメチルー７、８ージヒドロー６ークロマン酸エチルエステルの製造：
４ーオキソー２ーメチルー２ーシクロヘキセンカルボン酸エチル５０ｇ（純度９２．４％、０．２５４ｍｏｌ）、１ーブロモー３ークロロプロパン１２０ｇ，ＮＭＰ２３２ｇ及びヨウ化カリウム４．２ｇを仕込み、撹拌しながら窒素気流下で１４０℃まで加熱した。粉末の炭酸カリウム８４．３ｇを加え、１４０℃で２時間撹拌した。反応混合物は５℃以下に冷却した後、濾過した。残渣を酢酸エチルで洗浄し得られたろ液を飽和食塩水／ 水（１：１）で洗浄した。この酢酸エチル溶液を硫酸マグネシウムで乾燥した後濃縮して淡褐色オイル８７．６ｇを得た。
この淡褐色オイルを減圧下蒸留することにより目的の５ーメチルー７、８ージヒドロー６ークロマン酸エチル ３１．２ｇを得た。（Ｂ．ｐ．１２０−１４０／２ｍｍＨｇ 収率５５．３％）
【００２５】
実施例５ ５ーメチルー７、８ージヒドロー６ークロマン酸イソプロピルエステルの製造：
４ーオキソー２ーメチルー２ーシクロヘキセンカルボン酸イソプロピルエステル４０ｇ（純度９４．８％、０．１９３ｍｏｌ）、１ーブロモー３ークロロプロパン７５．６ｇ、ＮＭＰ１４４ｇ及びヨウ化カリウム２．６６ｇを仕込み、撹拌しながら窒素気流下で、１４０℃まで加熱した。粉末の炭酸カリウム５３．１ｇを加え、１４０℃で２時間撹拌した。反応混合物を５℃以下に冷却した後、濾過した。残渣を酢酸エチルで洗浄し得られたろ液を飽和食塩水／ 水（１：１）で洗浄した。この酢酸エチル溶液を硫酸マグネシウムで乾燥した後濃縮して淡褐色オイル６７．５ｇを得た。この淡褐色オイルを減圧下蒸留することにより目的の５ーメチルー７、８ージヒドロー６ークロマン酸イソプロピル２５．１ｇを得た。（Ｂ．ｐ．１３０−１３５／１．５ｍｍＨｇ 収率５５％ ）
【００２６】
実施例６ ５ーメチルー７、８ージヒドロー６ークロマン酸エチルエステルの製造：
ヨウ化カリウムを加えず、その他の条件、操作は実施例４と同じ方法を用いて５ーメチルー７、８ージヒドロー６ークロマン酸エチル２２．４ｇを得た（収率３９．６％ ）
【００２７】
実施例７ ４ーオキソー２ーメチルー２ーシクロヘキセンカルボン酸イソプロピルエステルの製造：
アセト酢酸イソプロピルエステル１４４．２ｇ（１ｍｏｌ）とピペリジン７ｍｌの混合溶液中に窒素雰囲気下、５０〜８５℃にてパラホルムアルデヒド１５ｇ（０．５ｍｏｌ）を小量宛添加した。９０〜９５℃にて３１時間撹拌後減圧下蒸留することにより４ーオキソー２ーメチルー２ーシクロヘキセンカルボン酸イソプロピル６２．９ｇ（純度９３％ ）を得た。油状物、Ｂ．ｐ．１２２−１３０ ℃／６ｍｍＨｇ。収率５９．６％ 。
【００２８】
参考例 ５ーメチルー７、８、ージヒドロー６ークロマンカルボン酸エチルの製造
４ーオキソー２ーメチルー２ーシクロヘキセンカルボン酸エチル１８．２ｇ（０．１０ｍｏｌ）をＫＯＢｕのｔ−ブタノール溶液（Ｋ：１２．０ｇとｔ−ブタノール２５０ｍｌで調整）に滴下後、１、３ージブロモプロパン２６．８ｇ（０．１３３ｍｏｌ）を滴下した。４時間加熱還流後、減圧下濃縮し、冷却下希塩酸（１．１ｅｑ）を加えエーテル２００ｍｌで抽出した。有機層を乾燥（硫酸マグネシウム）、濃縮後、減圧下蒸留した。Ｂ．ｐ．１２０ー１４０℃／ ２ｍｍＨｇ：１８ｇ
しかしこのものは、ガスクロマトグラフィー及び薄層クロマトグラフィーよりスピロ体と考えられる化合物やその他の副成物と目的物との混合物であり、純度良く目的物を得る事が出来なかった。
【００２９】
【発明の効果】
本発明によって、殺虫活性を有する事が知られている１ーアルキル１、２ージベンゾイルヒドラジン類を製造する工程に於ける有用な中間体である５ーメチルー７、８ージヒドロー６ークロマン酸エステルが、工業的に安価で収率良く製造する事が出来る。[0001]
[Industrial applications]
The present invention relates to a precursor of chromanic acid which is a useful intermediate in a process for producing 1-alkyl-1,2-dibenzoylhydrazines (JP-A-5-163266) which are known to have insecticidal activity. And a process for producing the same. The hydrazines are useful as agricultural pesticides.
[0002]
[Prior art]
A method is known in which cyclohexenone ester and 1,3-dibromopropane are reacted with potassium t-butoxide in t-butanol to obtain a dihydrochromancarboxylic acid ester. (J. Indian Chem. Soc., 45, 200 (1968)).
Also, 4-oxo-2-methyl-2-cyclohexenecarboxylic acid ethyl ester is
Known as Hagemanns esters. (J. Amer. Chem. Soc., 65, 631 (1943), JCS Prekin 1, 602, 1972).
[0003]
[Problems to be solved by the invention]
The prior art uses t-butoxide and water-soluble and difficult-to-recover solvent (t-butanol) which are intractable and expensive in terms of danger from an industrial point of view, and is difficult to purify spiro compounds. It is not an industrial production method such as by-producing. Therefore, there has been a demand for an industrially advantageous production method that uses a solvent that can be easily recovered, is inexpensive, and has a high yield.
[0004]
[Means for Solving the Problems]
The present invention provides the following formula (2)
[0005]
Embedded image
(In the formula, R represents a C 1 -C 6 lower alkyl group.)
4-oxo-2-methyl-2-cyclohexenecarboxylic acid ester represented by the following formula (3)
[0007]
Embedded image
(In the formula, X and Y represent a halogen atom.)
By reacting a halogen compound represented by the following formula (1)
[0009]
Embedded image
(In the formula, R represents a C 1 -C 6 lower alkyl group.)
The present invention relates to an industrially advantageous method for producing 5-methyl-7,8-dihydro-6 chromanate represented by the formula:
[0011]
Specifically, (A) a method in which a reaction is performed in a two-phase system of water and a water-insoluble solvent in the presence of a base, and (B) a reaction in a polar aprotic solvent in the presence of a base. It provides a method.
That is, according to the present production method, a dihydrochromate ester can be obtained with a high yield using an inexpensive base such as sodium hydroxide or potassium carbonate.
[0012]
Examples of the water-insoluble solvent used include halogenated hydrocarbons such as dichloromethane, chloroform, 1,1,1-trichloroethane, tetrachloroethylene, chlorobenzene, and dichlorobenzene, and methyl butyl ketone, t-butyl acetic acid, xylene, and toluene. Hydrogen can be given. Preferred are dichloromethane, chlorobenzene, dichlorobenzene, toluene and xylene.
Examples of the polar aprotic solvent used include N-methylpyrrolidinone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), N, N-dimethylimidazolinone (DMI), and dimethyl sulfo. Oxide (DMSO) and the like. Preferably, NMP and DMAC are used. The amount of the solvent to be used is 200-1500 ml / mol, preferably 400-1000 ml / mol, based on the compound of the formula (2).
[0013]
The base to be used includes hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide and calcium hydroxide, and carbonates of alkali and alkaline earth metals such as sodium carbonate, potassium carbonate and calcium carbonate. I can give it.
In the case of a method using water and a water-insoluble solvent (Method A), preferably, sodium hydroxide and potassium hydroxide are used.
In the case of a method using a polar aprotic solvent (method B), preferably, potassium carbonate and sodium carbonate are used.
The amount of the base to be used is 2-8 eq / mol, preferably 2-5 eq / mol, based on the compound of the formula (2).
The concentration of the base may be arbitrary, but is preferably as high as possible in view of productivity and reaction rate. For example, in the method (A), when sodium hydroxide is used, the higher the base concentration, the faster the reaction rate and the better the productivity per reactor. In the case of sodium hydroxide, it may be added as a solid (particulate to fine granular) without using water.
[0014]
In the method (A), the reaction rate can be increased by adding a phase transfer catalyst.
The phase transfer catalyst used is tetrabutylammonium bromide, tetramethylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltributylammonium chloride, methyltrioctylammonium chloride, methyltriphenylphosphonium bromide, amyltriphenylphosphonide. Ium bromide, preferably tetrabutylammonium bromide and methyltrioctylammonium chloride.
The amount of the phase transfer catalyst to be added is preferably 0.01 to 20% equivalent to the compound represented by the formula (2).
[0015]
In the method (B), it has been found that the addition of potassium iodide improves the yield. The amount of potassium iodide to be added is 0.05 to 1.0 equivalent, preferably 0.1 to 0.3 equivalent, relative to the compound of the formula (2).
[0016]
1,3 dihalogenopropane represented by the formula (3) used for alkylation and cyclization is 1,3 dichloro, 1,3 dibromo, 1,3 diiodo, 1-chloro-3-bromo, 1-chloro-3-iodo, 1 -Bromo-3-iodopropane.
Preferred are 1-chloro-3-bromo and 1-chloro-3-iodopropane, and more preferred is 1-chloro-3-bromopropane.
The amount of 1,3 dihalogenopropane used is 1 to 5 eq / mol, preferably 1 to 1.5 eq / mol in the method (A), and 1 to 3 eq / mol in the method (B). mol.
[0017]
The reaction temperature in the method (A) may be from 0 to 100 ° C, preferably from 0 to 60 ° C. In the method (B), the boiling point of the solvent is preferably from 50 to 170 ° C, more preferably from 90 to 170 ° C.
[0018]
As specific examples of the substituents of the compounds represented by the formulas (1) and (2), R is a straight-chain alkyl such as methyl, ethyl and propyl and a branched alkyl group such as isopropyl, t-butyl and sec-butyl. No. Here, R is a 4-oxo-2-methyl-2-cyclohexenecarboxylic acid ester represented by the formula (2) excluding a methyl group, an ethyl group and a t-butyl group, and R is a formula (1) excluding an ethyl group. The 5-methyl-7,8-dihydro-6-chromanoic acid ester is a compound not described in the literature.
[0019]
The compound of the formula (1) can be converted to 5-methyl-6-chromanoic acid by oxidizing it and then hydrolyzing the ester group to give 5-methyl-6-chromanoic acid. The compound can be used as a raw material for a dibenzoylhydrazine-based compound having excellent insecticidal activity against lepidoptera, hemipods and other pests described in JP-A-5-163266.
[0020]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto.
[0021]
Example 1 Preparation of ethyl 5-methyl-7,8-dihydro-6-chromancarboxylate 80 g of ethyl 4-oxo-2-methyl-2-cyclohexenecarboxylate (purity 95%, 0.418 mol), 1-bromo- 69 g (0.44 mol) of 3-chloropropane and 6.7 g (0.02 mol) of tetrabutylammonium bromide were dissolved in 300 ml of dichloromethane, and 134 g of 48% caustic soda water was added dropwise at 20-30 ° C with stirring. After completion of the dropwise addition, the mixture was stirred at 40 ° C. for 1 hour, and 80 ml of water was added at 10 ° C. or lower under ice cooling. After separating the aqueous layer, the organic layer was washed with water, dried (magnesium sulfate) and concentrated to obtain 111.3 g of a light brown oil. The purity was 55.1% (gas chromatography, internal standard method) and the net yield was 66%.
The light brown oil was distilled under reduced pressure to obtain 55.1 g of target ethyl 5-methyl-7,8-dihydro-6-chromancarboxylate. B. p. 130-135 ° C / 2 mmHg, melting point: 68-9 ° C.
H-NMR δ (ppm) 17 (2H, q, J = 7 Hz), 4.01 (2H, t, J = 4.6 Hz), 2.45 (2H, m), 2.17 (3H, s), 2.3-1. 8 (6H, M)
[0022]
Example 2 Preparation of isopropyl 5-methyl-7,8-dihydro-6-chromancarboxylate 40 g of isopropyl 4-oxo-2-methyl-2-cyclohexenecarboxylate (purity 94.8%, 0.193 mol), 31.9 g of 1-bromo-3-chloropropane (0.203 mol) and 1.25 g (0.0039 mol) of tetrabutylammonium bromide were dissolved in 97 ml of chlorobenzene, and 42.7 g of 40% sodium hydroxide solution was added dropwise at 30 ° C. with stirring. After completion of the dropwise addition, the mixture was stirred at 40 ° C. for 6 hours, and 40 ml of water was added at 10 ° C. or lower under ice cooling. After separating the aqueous layer, the organic layer was washed with water, dried (magnesium sulfate) and concentrated to obtain 70.2 g of a light brown oil. The light brown oil was distilled under reduced pressure to obtain 27.3 g of isopropyl 5-methyl-7,8-dihydro-6-chromancarboxylate. B. p. 130-135 ° C / 1,5 mmHg.
[0023]
Example 3 Preparation of methyl 5-methyl-7,8-dihydro-6-chromancarboxylate 10 g of methyl 4-oxo-2-methyl-2-cyclohexenecarboxylate (purity 83%, 0.0493 mol), bromochloropropane 3 g (0.0591 mol) and 0.9 g (2.8 mmol) of tetrabutylammonium bromide were dissolved in 50 ml of dichloromethane, and 19 g of 48% caustic soda water was added dropwise at 20-25 ° C with stirring. After completion of the dropwise addition, the mixture was stirred at 25 ° C for 1 hour and at 40 ° C for 2 hours, and then 20 ml of water was added under ice cooling. After separating the aqueous layer, the organic layer was washed with water, dried (sodium sulfate) and concentrated to obtain 10.1 g of a light brown oil. The oil solidified at room temperature and was recrystallized from MeOH to obtain 6 g of white crystals. Net yield 58%.
M. P. 90-91 ° C
H-NMR δ (ppm) 4.00 (2H, t, J = 5 Hz), 3.71 (3H, s), 2.45 (2H, m), 2.17 (3H, s), 2.3 -1.8 (6H, m)
[0024]
Example 4 Preparation of 5-methyl-7,8-dihydro-6-chromanoic acid ethyl ester:
50 g of ethyl 4-oxo-2-methyl-2-cyclohexenecarboxylate (purity 92.4%, 0.254 mol), 120 g of 1-bromo-3-chloropropane, 232 g of NMP and 4.2 g of potassium iodide were charged, and stirred at 140 ° C. under a nitrogen stream while stirring. Until heated. 84.3 g of powdered potassium carbonate was added, and the mixture was stirred at 140 ° C. for 2 hours. The reaction mixture was cooled to 5 ° C. or lower and then filtered. The residue was washed with ethyl acetate, and the obtained filtrate was washed with saturated saline / water (1: 1). The ethyl acetate solution was dried over magnesium sulfate and concentrated to obtain 87.6 g of a light brown oil.
The light brown oil was distilled under reduced pressure to obtain 31.2 g of the target ethyl 5-methyl-7,8-dihydro-6-chromanoate. (B.p. 120-140 / 2 mmHg yield 55.3%)
[0025]
Example 5 Preparation of 5-methyl-7,8-dihydro-6-chromanoic acid isopropyl ester:
40 g of isopropyl 4-oxo-2-methyl-2-cyclohexenecarboxylate (purity 94.8%, 0.193 mol), 75.6 g of 1-bromo-3-chloropropane, 144 g of NMP and 2.66 g of potassium iodide were charged, and stirred under a nitrogen stream. And heated to 140 ° C. 53.1 g of powdered potassium carbonate was added, and the mixture was stirred at 140 ° C. for 2 hours. The reaction mixture was cooled to 5 ° C. or lower and then filtered. The residue was washed with ethyl acetate, and the obtained filtrate was washed with saturated saline / water (1: 1). The ethyl acetate solution was dried over magnesium sulfate and concentrated to obtain 67.5 g of a light brown oil. The light brown oil was distilled under reduced pressure to obtain 25.1 g of the desired isopropyl 5-methyl-7,8-dihydro-6-chromate. (B.p. 130-135 / 1.5 mmHg, 55% yield)
[0026]
Example 6 Preparation of 5-methyl-7,8-dihydro-6-chromanoic acid ethyl ester:
Using the same method as in Example 4 except that potassium iodide was not added, 22.4 g of ethyl 5-methyl-7,8-dihydro-6-chromanoate was obtained (yield: 39.6%).
[0027]
Example 7 Preparation of isopropyl 4-oxo-2-methyl-2-cyclohexenecarboxylate:
A small amount of 15 g (0.5 mol) of paraformaldehyde was added to a mixed solution of 144.2 g (1 mol) of isopropyl acetoacetate and 7 ml of piperidine at 50 to 85 ° C under a nitrogen atmosphere. After stirring at 90 to 95 ° C. for 31 hours, the mixture was distilled under reduced pressure to obtain 62.9 g (purity: 93%) of isopropyl 4-oxo-2-methyl-2-cyclohexenecarboxylate. Oil, B.I. p. 122-130 ° C / 6mmHg. Yield 59.6%.
[0028]
Reference Example Preparation of ethyl 5-methyl-7,8, dihydro-6-chromancarboxylate 18.2 g (0.10 mol) of ethyl 4-oxo-2-methyl-2-cyclohexenecarboxylate was added to a solution of KOBu in t-butanol (K: 12.0 g and t -Adjusted with 250 ml of butanol), and 26.8 g (0.133 mol) of 1,3-dibromopropane was added dropwise. After heating under reflux for 4 hours, the mixture was concentrated under reduced pressure, diluted hydrochloric acid (1.1 eq) was added under cooling, and the mixture was extracted with 200 ml of ether. The organic layer was dried (magnesium sulfate), concentrated and distilled under reduced pressure. B. p. 120-140 ° C / 2mmHg: 18g
However, this is a mixture of a compound which is considered to be a spiro compound by gas chromatography and thin-layer chromatography and other by-products with the target product, and the target product could not be obtained with high purity.
[0029]
【The invention's effect】
According to the present invention, 5-methyl-7,8-dihydro-6-chromanoic acid ester, which is a useful intermediate in the process of producing 1-alkyl 1,2-dibenzoylhydrazines which are known to have insecticidal activity, is commercially available. It can be manufactured at low cost and high yield.
Claims (13)
で表される５−メチル−７，８−ジヒドロ−６−クロマン酸エステル。The following formula (1)
5-methyl-7,8-dihydro-6-chromanic acid ester represented by the formula:
で表わされる４−オキソ−２−メチル−２−シクロヘキセンカルボン酸エステルと下式（３）
で表わされるハロゲン化合物を塩基の存在下、水と非水溶性溶媒の２相系において反応させることを特徴とする下式（１）
で表わされる５−メチル−７，８−ジヒドロ−６クロマン酸エステルの製造方法。The following formula (2)
4-oxo-2-methyl-2-cyclohexenecarboxylic acid ester represented by the following formula (3):
Wherein a halogen compound represented by the following formula is reacted in a two-phase system of water and a water-insoluble solvent in the presence of a base:
A method for producing 5-methyl-7,8-dihydro-6 chromanate represented by the formula:
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24837894A JP3545466B2 (en) | 1993-09-24 | 1994-09-19 | Dihydrochromancarboxylic acids and method for producing the same |
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| Application Number | Priority Date | Filing Date | Title |
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| JP25888193 | 1993-09-24 | ||
| JP5-258881 | 1993-09-30 | ||
| JP5-265426 | 1993-09-30 | ||
| JP26542693 | 1993-09-30 | ||
| JP24837894A JP3545466B2 (en) | 1993-09-24 | 1994-09-19 | Dihydrochromancarboxylic acids and method for producing the same |
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| Publication Number | Publication Date |
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| JPH07179452A JPH07179452A (en) | 1995-07-18 |
| JP3545466B2 true JP3545466B2 (en) | 2004-07-21 |
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